core.ac.uk · iii acknowledgements i would like to take the opportunity to express my sincere...
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QUEENSLAND UNIVERSITY OF TECHNOLOGY
SCHOOL OF PHYSICAL AND CHEMICAL SCIENCES
THE MORPHOLOGY AND
STRUCTURE OF
INTERCALATED AND PILLARED
CLAYS
Submitted by Loc Van Duong to the school of Physical and Chemical Sciences, Queensland University of Technology, in partial fulfilment of the requirements of the degree of Doctor of Philosophy.
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This thesis is dedicated to my wife Bach-Yen Thi Nguyen
and children Tien-Nam Nguyen Duong, Thuy-Tien Nguyen Duong and
Dang-Khoa Nguyen Duong
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Acknowledgements
I would like to take the opportunity to express my sincere thanks to people who have
contributed greatly to my research:
My principal supervisor, Dr. Theo Kloprogge, for his support, advice and guidance
throughout my program of study. My co-supervisors Professor Ray Frost and Dr. Thor
Bostrom for their invaluable advice, encouragement and discussions.
Other people who involved in helping me with techniques and applications include:
• Dr Barry Wood, University of Queensland for his advice and assistance on the
XPS equipment and techniques.
• Dr Gregory Watson, Griffith University for assistance and comments on the
Scanning Probe microscope work.
• Dr Marek Zbik, Ian Wak Research Centre, South Australia for discussion on the
application of Atomic Force Microscope for clay minerals.
• Dr Wayde Martens for discussion and comments on vibrational spectroscopy
work on clay minerals.
• Professor H. Zhu and Professor HongPing He for the comments on organoclay
and pillared clay application.
Gratefully acknowledgements go to the X- Ray Analytical Facility, Mr Tony Raftery
and Mr Lambert Bekessy
The Queensland University of Technology (QUT) Faculty of Science is acknowledged
for providing time off and funding for me to complete my research.
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Finally I would like to thank my wife Bach-Yen and my children Tien-Nam, Thuy-
Tien and Dang- Khoa for their understanding, patience, assistance and supporting me
during the time of study.
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The work contained in this thesis has not been previously submitted for a
degree or diploma at any other tertiary educational institution. To the best of
my knowledge and belief, the thesis contains no material previously
published or written by another person except where due reference is made.
__________________________Signed
________________Date
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Abstract
This thesis is submitted in a format of published papers by the candidate. Advanced
methods of electron microscopy and X-ray spectroscopy have been used to study the
relationship between the pillars and the silicate structure ranging from Al13 and Ga13
complexes to the final products Al- and Ga-pillared clays. The Al13 and Ga13 pillared
montmorillonites have been prepared by conventional and ultrasonic methods. The
ultrasonic method has been proven to be effective and showed very good catalytically
activity. Transmission electron microscopy combined with elemental mapping by EDS
showed the distribution of the Ga and Al pillars in the clay structure. The use of gallium
allowed the independent observation of the Ga pillar distribution from the Al distribution
in the clay structure.
XPS spectra of the Ga13 pillared montmorillonites showed that the pillars has been
changed from the original Keggin structure with a 7+ charge to something more stable
with a lower charge upon intercalation. No direct evidence of the inverted silicon
tetrahedron structure bonding to the pillar structure, as suggested by Plee in his original
thesis, was observed. For comparative reasons the major aluminium hydroxide minerals
in bauxite (gibbsite, bayerite and (pseudo-) boehmite) were studied.
Detailed information about the Al13 structure was obtained by studying the basic
sulphate and nitrate salts with XPS. The XPS results of a set of starting clays in
comparison to the pillared clays indicated that small changes in the binding energy could
explain the changes in the pillar structure and the formation of chemical bonds to the
clay tetrahedral sheets during the calcination leading to the final products.
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LIST OF PUBLICATIONS DERIVED FROM THIS RESEARCH
1. Duong, L.V., Wood, B.J. and Kloprogge, J.T. (2005). XPS study of basic aluminium
sulphate and basic aluminium nitrate. Materials Letters, 59 (14/15), 1932-1936.
2. Duong, L., Bostrom, T., Kloprogge, T. and Frost, R., (2005). The distribution of Ga in Ga-
pillared montmorillonites: a transmission electron microscopy and microanalysis study.
Microporous and Mesoporous Materials, 82, 165-172.
3. Duong, L.V., Kloprogge, J.T., Frost, R.L. and van Veen, J.A.R. (2007) An improved route
for the synthesis of Al13-pillared montmorillonite catalysts. Journal of Porous Materials
14(1), 71-79
4. Kloprogge, J.T., Duong, L.V., Wood, B.J. and Frost, R.L. (2005) X-ray photoelectron
spectroscopic study of the major minerals in bauxite: gibbsite, bayerite and (pseudo-)
boehmite. Journal of Colloid and Interface Science, 296, 572-576.
5. He, H., Zhou, Q., Frost, R.L., Wood, B.J., Duong, L.V., and Kloprogge, J.T. (2007) A X-
ray photoelectron spectroscopy study of HDTMAB distribution in organoclays.
Spectrochimica Acta A, 66, 1180-1188.
6. Kloprogge, J.T., Duong, L.V. and Frost, R.L. (2005). A review of the synthesis and
characterization of pillared clays and related porous materials for cracking of vegetable oil
to produce biofuels. Environmental Geology, 47(7), 967-981
7. Kloprogge, J.T., Xi, Y., Duong, L.V. and Frost, R.L. (2005) High-resolution X-ray
photoelectron spectroscopy of alkyl ammonium intercalated montmorillonites. 13th
International Clay Conference, Tokyo, Japan, August 21-27, 113.
8. Kloprogge, J.T., Duong, L.V. and Frost, R.L. (2005). High-resolution XPS of boehmite:
What is the difference between boehmite and pseudoboehmite? 13th International Clay
Conference, Tokyo, Japan, August 21-27, 93.
9. Duong, L.V., Kloprogge, J.T., Frost, R.L. and Wood, B.J. (2005) The structure of Al13 and
Ga13 pillars in pillared montmorillonites. 13th International Clay Conference, Tokyo, Japan,
August 21-27, 77.
viii
LIST OF PUBLICATIONS RELATED TO THIS RESEARCH
1. Frost, R. L., W. N. Martens, Duong, L., Kloprogge, J. T. (2002). Evidence for molecular
assembly in hydrotalcites. Journal of Materials Science Letters 21(16): 1237-1239.
2. He, H., R. L. Frost, Bostrom, T.,Yuan P., Duong L.,Yang .D., Xi Y. Kloprogge T. (2006).
Changes in the morphology of organoclays with HDTMA+ surfactant loading. Applied
Clay Science 31(3-4): 262-271.
3. Kloprogge, J.T., Duong, L.V., Frost, R.L. and Wood, B.J. (2008) Baseline studies of the
Clay Minerals Society Source Clays: X-ray photoelectron spectroscopy. Clays and Clay
Minerals, submitted.
4. Kloprogge, J.T., Duong, L.V., Martens, W.N., van der Eerden, A.J.M. and Frost, R.L.
(2007) Mid- and Near-Infrared transmittance spectroscopy of hydrothermally synthesised
2:1 phyllosilicates in the system Na2O-Al2O3-SiO2-H2O. In Progress in Solid State
Chemistry Research (ed. Buckley R.W.), Chapter 7, 285-300.
5. Kloprogge, T., Duong L., Frost, R., Bostrom, T. (2005). Environmental SEM: Application
Of Low Voltage Sem, Heating Stage Sem And Variable Relative Humidity Sem To Study
Uncoated Minerals. Microscopy and Analysis(July):17-17. 17.
6. Kloprogge, J.T., Broekmans, M., Duong, L.V., Martens, W.N., Hickey, L. and Frost, R.L.
(2006) Low temperature synthesis and characterisation of lecontite, (NH4)Na(SO4).2H2O.
Journal of Materials Science, 41, 3535- 3529.
7. Ruan, H. D., R. L. Frost, Kloprogge, J. T., Duong, L., Schulze, D. G. (2001). Photo
acoustic spectroscopy of kaolinite and gibbsite surfaces. 12th ICC, 22-28July 2001, Bahia
Blanca. Argentina. 171.
8. Ruan, H. D., R. L. Frost, Kloprogge, J. T., Schulze, D. G., Duong, L. (2001). FT-Raman
spectroscopy and SEM of gibbsite, bayerite, boehmite and diaspore in relation to the
characterization of bauxite. The 12th International Clay Conference, 22-28 July 2001,
Bahia Blanca, Argentina. 184.
9. Ruan, H. D., R. L. Frost, Kloprogge, J. T., Duong, L. (2002). Infrared spectroscopy of
goethite dehydroxylation: III. FT-IR microscopy of in situ study of the thermal
transformation of goethite to hematite. Spectrochimica Acta, Part A:Molecular and
Biomolecular Spectroscopy 58(5): 967-981.
10. Ruan, H. D., R. L. Frost, Kloprogge, J. T., Duong L. (2002). Far Infared Spectroscopy of
Alumina phases. Spectrochim. Acta, Part A 58A (1): 265-272.
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11. Ruan, H. D., R. L. Frost, Kloprogge,T., Duong, L (2002). Infrared spectroscopy of goethite
dehydroxylation. II Effect of aluminium substitution on the behaviour of hydroxyl units.
Spectrochimica Acta 58: 479-491.
x
TABLE OF CONTENTS
Acknowledgments ………………………………………...……………………………..iv
Abstract ………………………..………………………………………...…….…………vi
List of publication derived from this research …………………….………….................vii
List of publication related to this research ……………………………………...………viii
Table of contents ……………………………………………….………………………....x
List of tables ………………………………………………………………..…………....xv
List of figures ……………………………………………………………...……......….xvii
CHAPTER 1 .................................................................................................................. 1
LITERATURE REVIEW ON CLAY MINERALOGY, PILLARED CLAY AND
TECHNIQUES USED FOR STUDYING PILLARED CLAYS
1.1 Introduction ...................................................................................................... 1
1.2 Clay Mineralogy .............................................................................................. .2
1.2.1 The basic structure of clay minerals ..................................................... 2
1.2.1.1 The tetrahedral sheet ……………………....……………. .3
1.2.1.2 The octahedral sheet ……………………....………….…..3
1.2.2 Classification of the clay minerals ....................................................... 8
1.2.2.1 The 1:1 structure ………………….…………………..…..8
1.2.2.2 The 2:1 structure ………………….…………………..…..9
1.3 Intercalated and pillared clays ...................................................................... 14
1.3.1 Introduction .................................................................................... …14
xi
1.3.2 Intercalated clays ................................................................................ 14
1.3.3 Pillared clays ...................................................................................... 16
1.4 Analytical techniques for studying clays and their modifications ............. 30
1.4.1 X-Ray Diffraction ............................................................................... 30
1.4.2 Electron Microscopy and Microanalysis ............................................ 34
1.4.3 Atomic Force Microscopy .................................................................. 41
1.4.4 Vibrational Spectroscopy and Solid State NMR ................................ 44
1.4.5 X-Ray Photoelectron Microscopy ...................................................... 45
1.5 General discussion .......................................................................................... 50
1.6 Aims and objectives ........................................................................................ 52
1.7 References ....................................................................................................... 54
CHAPTER 2 . ......................................................................................................... …...72
THE DISTRIBUTION OF Ga IN Ga-PILLARED MONTMORILLONITES: A
TRANSMISSION ELECTRON MICROSCOPY AND MICROANALYSIS STUDY
2.1 Abstract ........................................................................................................... 73
2.2 Introduction .................................................................................................... 73
2.3 Materials and methods ................................................................................... 76
2.3.1 Starting materials ................................................................................ 76
2.3.2 X-ray diffraction ................................................................................. 77
2.3.3 Sample preparation for Transmission Electron Microscopy .............. 77
2.3.4 Transmission Electron Microscopy .................................................... 80
2.3.5 Nitrogen adsorption-desorption .......................................................... 80
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2.4 Results and discussion .................................................................................... 82
2.5 Conclusions ..................................................................................................... 92
2.6 Acknowledgement ........................................................................................... 94
2.7 References ....................................................................................................... 95
CHAPTER 3. ................................................................................................................. 98
AN IMPROVED ROUTE FOR THE SYNTHESIS OF AL13 PILLARED
MONTMORILLONITE CATALYSTS
3.1 Abstract ........................................................................................................... 99
3.2 Introduction .................................................................................................. 100
3.3 Experimental . ................................................................................................ 102
3.3.1 Starting materials . ............................................................................. 102
3.3.2 Analytical techniques . ...................................................................... 102
3.3.2.1 ........ X-Ray diffraction (XRD) ………………….…………… ..102
3.3.2.2 Scanning Electron Microscopy (SEM) ...… ….… 103
3.3.2.3 Atomic Force Microscopy (AFM) ……………...… …. 103
3.3.3 N2 adsorption /desorption . ................................................................ 108
3.3.4 Catalytic testing . ............................................................................... 108
3.4 Results and discussion .................................................................................. 109
3.5 Conclusions ................................................................................................... 119
3.6 Acknowledgement . ........................................................................................ 119
3.7 References . .................................................................................................... 120
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CHAPTER 4 ............................................................................................................... 122
HIGH RESOLUTION XPS STUDY OF THE INTERNAL STRUCTURE OF AL-
AND Ga-PILLARS IN PILLARED CLAY CATALYSTS
4.1 Abstract ......................................................................................................... 123
4.2 Introduction .................................................................................................. 124
4.3 Experimental ................................................................................................. 126
4.3.1 Sample preparation ........................................................................... 126
4.3.2 X-ray diffraction (XRD) ................................................................... 126
4.3.3 N2 adsorption /desorption ................................................................. 127
4.3.4 X-ray Photo-electron Spectroscopy (XPS) ........................................ 127
4.4 Results and discussion .................................................................................. 128
4.5 Conclusions ................................................................................................... 140
4.6 Acknowledgement ........................................................................................ .140
4.7 References ..................................................................................................... 141
CHAPTER 5 . .............................................................................................................. 144
XPS STUDY OF BASIC ALUMINUM SULPHATE AND BASIC ALUMINIUM
NITRATE
5.1 Abstract ......................................................................................................... 145
5.2 Introduction .................................................................................................. 146
5.3 Experimental . ................................................................................................ 147
5.3.1 Basic aluminium sulphate and nitrate ............................................... 147
5.3.2 XPS analysis ..................................................................................... 148
xiv
5.4 Results and discussion . ................................................................................. 149
5.5 Acknowledgement . ........................................................................................ 157
5.6 References . .................................................................................................... 158
CHAPTER 6 . .............................................................................................................. 160
SUMMARY AND SUGGESTIONS FOR FUTURE WORK
6.1 SUMMARY . ...................................................................................................... 160
6.2 SUGGESTIONS FOR FUTURE WORK . ..................................................... 163
6.3 REFERENCES . ................................................................................................ 165
CHAPTER 7 . ................................................................................................................. 166
ADDITIONAL SUPPORT PAPERS
7.1 REVIEW OF THE SYNTHESIS AND CHARACTERIZATION OF
PILLARED CLAYS AND RELATED POROUS MATERIALS FOR
CRACKING OF VEGETABLE OIL TO PRODUCE BIOFUELS. ............ 167
7.2 X- RAY PHOTOELECTRON SPECTROSCOPIC STUDY OF THE
MAJOR MINERALS IN BAUXITE: GIBBSITE, BAYERITE AND
(PSEUDO-) BOEHMITE. ................................................................................. 204
7.3 A X-RAY PHOTOELECTRON SPECTROSCOPY STUDY OF HDTMAB
DISTRIBUTION WITHIN ORGANOCLAYS. ............................................. 212
xv
LIST OF TABLES:
Table 1.1 Classification of common phyllosilicates. ………………………………12
Table 1.2 Atomic and X-ray notations ……………………………………..………49
Table 2.1 Characteristic concentrations (single analysis) in weight % from X-ray
microanalyses in the TEM of the starting and the Ga13-, Al12Ga- and Al13-
pillared montmorillonites, and the formula calculation based on 22
oxygens ………………………………………………………….………83
Table 3.1 BET surface area and pore volume and average pore diameter of Al-
pillared montmorillonites …………………………...…………………103
Table 3.2 Temperatures for 40% n-heptane conversion on Pd-loaded pillared clays
(calcined 450°C, Pd loading 0.4 wt%) and two standard catalysts (ASA
and Pd/Al2O3:Si) …………………………...…………………………109
Table 4.1 XRD and N2 adsorption/desorption results for the starting montmorillonite
SWy-2, the Al13- and Ga13-intercalated montmorillonites and the calcined
Al13- and Ga13-pillared montmorillonites ……………………………...119
Table 4.2 Chemical analysis (at %) of the starting clay SWy-2 and the Al and Ga
pillared equivalents …………………………………………………….134
Table 5.1 Chemical composition (in atom%) from the XPS analyses of the basic
aluminium sulphate at room temperature and after calcination at 200 and
400°C and basic aluminium nitrate ………………………………….....137
Table 5 2 Binding energies (in eV) of the basic sulphate at room temperature and
after calcination at 200 and 400°C …………………………………….143
xvi
LIST OF FIGURES
Fig. 1.1 Diagram showing the single tetrahedron unit and the arrangement of the
tetrahedral sheet …………………………………………………........…….4
Fig. 1.2 Diagram showing the single octahedral unit and the arrangement of the
octahedral sheet ………………………………………………...…...………6
Fig. 1.3 Diagram showing the arrangement of the tetrahedral and octahedral sheet to
form an ideal structure of clay minerals with no substitution .………......….7
Fig. 1.4 The structure of typical montmorillonite minerals ……..….……….……..13
Fig. 1.5 Representation of the pillaring process showing d spacing changing from the
beginning and the end product after calcination ………………...………...19
Fig. 1.6 XRD patterns of untreated and treated montmorillonites from Miles,
Queensland, Australia ………………...……………………...………...….33
Fig. 1.7 Image formation in optical microscope, transmission microscope and
scanning electron microscope. In the optical microscope the source is light
bulb whereas in the SEM and TEM the source is an electron beam ………35
Fig. 1.8 SEM image of pillared montmorillonite (Top) and TEM image of particle of
Montmorillonite (bottom) ……………………...…….……………………39
Fig. 1.9 SEM images of Kaolinite in sandstone shows typical book structure ….....40
Fig. 1.10 Typical diagram of an atomic force microscope showing a tip mounted on a
cantilever (C). The tip scans over the surface of the sample. The laser light
from the back of the cantilever reflects to a two element photosensitive
xvii
diode (PSD) and the output signal can be used in a feedback loop to control
the vertical position of the sample ………………...………………………42
Fig. 1.11 Diagram showing Photoelectron and Auger electron processes …...…...…48
Fig. 2.1 Preparation of cross sections of a clay sample for TEM ………………….79
Fig. 2.2 XRD patterns of a) starting Wyoming SWy-2 montmorillonite, b)
montmorillonite exchanged with Ga13 showing an interlayer spacing of 19.9
Å, and c) Ga13 pillared montmorillonite with a spacing of 17.9Å ………...81
Fig. 2. 3 TEM image of a) a grain of Al12Ga pillared montmorillonite; and images
and electron diffraction patterns from sectioned material: b) Ga13 pillared
montmorillonite; c) Al12Ga pillared montmorillonite and d) Al13 pillared
montmorillonite …………………………………………………...………84
Fig. 2.4 Elemental X-ray maps for Ga, Si and Al from a cross section of a single
grain of Ga13 pillared montmorillonite ……… ……87
Fig. 2.5 EDX spectra from analyses in the TEM of small grains of (a) Ga13 pillared,
(b) Al12Ga pillared, and (c) Al13 pillared montmorillonites. The spectra are
shown overlaid with a spectrum from the starting material. The C and Cu
peaks derive from the resin or thin carbon coating and the TEM grid
material respectively ………………………………………………………88
Fig. 2. 6 Pore size distribution of Ga13 pillared montmorillonite ………………….91
Fig. 3.1a Non-calcined Al13- montmorillonite SAz-1 ……………………...………104
Fig. 3.1b Non-calcined Na-exchanged Miles montmorillonite intercalated with Al13
…………………….......................................................................………104
xviii
Fig. 3.1c Non-calcined Miles montmorillonite intercalated with Al13……....……105
Fig. 3. 2a Al-pillared montmorillonite SAz-1 calcined at 450°C ...…………...….107
Fig. 3. 2b Al-pillared Miles montmorillonite calcined at 450°C ……………….....107
Fig. 3. 2c Al-pillared Na-exchanged Miles montmorillonite calcined at 450°C .…108
Fig. 3.3a BET adsorption and desorption isotherms for Al-pillared montmorillonite
SAz-1 after ultrasonic treatment for 5 minutes and calcined at 450°C …..111
Fig. 3.3b BET adsorption and desorption isotherms for Al-pillared Miles
montmorillonite after ultrasonic treatment for 5 minutes and calcined at
450°C .……………………………………………………………………112
Fig. 3. 4a Al-pillared montmorillonite SAz-1 (ultrasonic treatment 5 minutes, calcined
at 450°C) ...…………...…………………………………………………..113
Fig. 3. 4b Al-pillared montmorillonite SAz-1 (ultrasonic treatment 10 minutes,
calcined at 450°C) ...…………...……………………………………..…..113
Fig. 3. 4c Al-pillared montmorillonite SAz-1 (ultrasonic treatment 20 minutes,
calcined at 450°C) ...…………...…………………………………..……..114
Fig. 3. 5a AFM raw image (left) and FTIR processed image (right) of Miles
montmorillonite ...…………...……………………………………..……..117
Fig. 3. 5b AFM raw image (left) and FTIR processed image (right) of Miles
montmorillonite after 10 minutes ultrasonic treatment ……..……..……..117
Fig. 3. 5c AFM raw image (left) and FTIR processed image (right) of Al-pillared
Miles montmorillonite after 20 minutes ultrasonic treatment ……..……..118
xix
Fig. 4.1 XPS survey scan of the Wyoming montmorillonite starting material …...131
Fig. 4.2 High resolution XPS spectra of Si 2p, Al 2p and O 1s of the starting
montmorillonite SWy-2 ………………………………………………....136
Fig. 4.3 High resolution XPS spectra of Si 2p, Al 2p, Ga 2p and O 1s of the Ga-
pillared montmorillonite SWy-2 ……………………………………..…..137
Fig. 4.4 High resolution XPS spectra of Al 2p of Al13 sulfate after calcination at
400°C (top ), gibbsite with only AlVI (middle), and corundum with AlVI
(bottom ) ……………………………………………………………....….138
Fig. 4.5 High resolution XPS spectra of Si 2p, Al 2p and O 1s of the Al-pillared
montmorillonite SWy-2 …………………………………………...….….139
Fig. 5.1 SEM images of a basic aluminium sulphate crystal at room temperature and
after calcination at 400°C …………………………………….………….141
Fig. 5.2 XPS survey scan of basic aluminum sulphate …………………….……..142
Fig. 5.3a Al 2p high resolution spectrum of basic aluminium sulphate ……………145
Fig. 5.3b O 1s high resolution spectrum of basic aluminium sulphate ……………146
Fig. 5.3c S 2p high resolution spectrum of basic aluminium sulphate …………….146
1
CHAPTER 1
1.0 LITERATURE REVIEW ON CLAY
MINERALOGY, PILLARED CLAY AND
TECHNIQUES USED FOR STUDYING
PILLARED CLAYS
1.1 Introduction
The term “clay” has been used to either indicate fine particles, with a grain size less
than 2 µm or minerals belonging to the clay minerals group (Velde, 1992). In this thesis
clay refers to a member of the clay minerals group, as part of the phyllosilicates. Clay is
present almost everywhere, flying up in the air as dust particles, covering the surface of
the earth as part of the soils, and below the surface as part of sedimentary rocks. Clay is
mainly formed through the process of weathering of primary silicate minerals such as
feldspars. The characteristics of clay deposits are depended on the source rocks, the
weathering processes, transportation and the environmental conditions (Velde, 1992).
The first documented use of clay under the term Kauling Earth was in the middle of
the Ming Dinasty, China, in AD 1604 (Liu and Bai, 1982). The two most popular clay
minerals are kaolinite and montmorillonite. Kaolinite is the main component of the kaolin
deposits, which has been used for making ceramics in China since the seventeenth
2
century (Chen et al., 1997). The name “kaolin” comes from the Chinese word kauling,
which is the name of a village near Jauchou Fu, central China (Chen et al., 1997).
In Europe Von Liebig used acid treated clay as catalyst (Liebig, 1865). Professor
Heinrich Ries of Cornell University was probably the first American geologist to study
clay minerals in 1920 (Grim, 1988). Montmorillonite, named after the town
Montmorillon, France, is the main component of bentonite deposits, and has the capacity
to absorb water molecules between the layers around the exchangeable cations. Bentonite
is used in many applications including drilling mud for oil drilling, as absorbents for
waste water or for stopping leakage in soils, rocks and dams (Grim, 1988)
The structure of clay minerals has only been understood since the discovery of X-rays
and the development of X-ray diffraction methods, with the first analyses of clay particles
published in 1923 (Hadding, 1923). The development of advanced analytical techniques
such as vibrational spectroscopy, electron microscopy and surface analysis have helped
clay mineralogists to study in detail the morphology, structure and chemistry of these
minerals down to the atomic scale.
1.2 Clay Mineralogy
1.2.1 The basic structure of clay minerals
The clay minerals belong to the phyllosilicates or layer silicates. Members of this
group have a platy habit and perfect (001) cleavage. They are generally soft, the hardness
ranges from 2 to 3 on the Mohs scale and the colour varies from yellow to pure white
depending mainly on the substitution of Fe into the structure. Most of the clay minerals
3
belong to the triclinic or monoclinic system. The four important clay mineral groups are:
kandites, illites, smectites and vermiculites. Kaolinite from the Kaolin group and
montmorillonite from the smectite group are the most common clay minerals found in
nature.
The basic structure of clay minerals can be obtained though the stacking of two sheets:
tetrahedral sheets and octahedral sheets sometime separated by an interlayer. Different
clay minerals are formed by (1) different combination of these two units and the
interlayer and (2) changes in the composition of the sheets.
1.2.1.1 The tetrahedral sheet
The basic unit of this layer is a tetrahedron, which contains normally one Si4+ in the
centre with four O2- at the corners. The tetrahedra are linked to neighbouring tetrahedra
by sharing three oxygen atoms each to form a hexagonal mesh pattern. All the unshared
corners with the apical oxygen atoms point in the same direction to form part of the
adjacent octahedral sheet (Figure 1.1).
1.2.1.2 The octahedral sheet
The basic unit of this layer is an octahedron, which contains mainly Al3+ or Mg2+
surrounded by six oxygen atoms or hydroxyl groups. When the cations are trivalent, the
sheet contains two cations per half unit cell and one vacancy. This is a structure similar to
gibbsite, Al(OH)3, and is known as a dioctahedral structure. When the cations are
divalent, the sheet contains three cations per half unit cell and no vacancy. This is a
structure similar to brucite, Mg(OH)2, and is known as a trioctahedral structure.
Octahedral sheets can contain other cations including Li+, Fe2+, and Fe3+ (Figure 1.2).
4
Fig. 1.1 Diagram showing the single tetrahedron unit and the arrangement of the
tetrahedral sheet
Silicon
Tetrahedral sheet formed by joining of tetrahedral unit (side view)
Single tetrahedron unit
Apical Oxygen
Corner linked tetrahedral sheet (top view)
5
The octahedral and tetrahedral sheets are covalently linked through sharing of the
apical oxygen atoms of the tetrahedral sheet with the octahedral sheet creating the metal
cation (octahedral) - O- Si (tetrahedral) link as seen in Figure 1.3. The octahedral sheet is
commonly slightly smaller than the tetrahedral sheet (Triolo et al., 1988). To compensate
for this difference, the tetrahedra in the tetrahedral sheet rotate resulting in a distortion
sheet.
The cations in the tetrahedral and/or octahedral sheet can be replaced by other cations
to cause a negative charge in the structure. The charge can be located in the tetrahedral
and/or octahedral sheet and is very useful to identify different species of clay minerals.
The structure of the clay minerals is quite complex. The combination of the basic clay
units and the interlayer with substitution of different cations in tetrahedral or octahedral
layers can result in different species. These different minerals have quite distinct
properties and can be grouped together by similar layer type, layer charges, or the type of
interlayer species. Not all clay minerals are suitable to make pillared clays; the groups
with layer charges ranging from 0.4 to 1.8 with hydrated exchangeable cations in the
interlayer are the most common starting material. In the structure of the clay mineral, the
charges can be unbalanced, resulting in minerals containing a permanent charge (negative
or positive) or no charge (on the surface) as in the case of kaolinite. A second source of
charge is found along the edges of clay minerals, which depended on the pH of the
solution. The classification of common phyllosilicates is listed in Table 1.1. The two
most popular minerals with the 1:1 and 1:2 structure, kaolinite and montmorillonite, are
discussed below.
6
Single octahedral unit
Octahedral sheet formed by joining of octahedral unit (side view) Al, Mg
O, OH
Edge linked octahedral sheet (top view)
Fig. 1.2 Diagram showing the single octahedral unit and the arrangement of
the octahedral sheet
7
Fig. 1.3 Diagram showing the arrangement of the tetrahedral and octahedral sheet to form an ideal structure of clay minerals with no substitution: (a) and (b) showed the 1:1 and 2:1clay mineral structure (side view), (c) The link between the tetrahedral and octahedral layers is the result of sharing apical oxygen from the tetrahedral layers and the unshared ions normal to the octahedral sheet
T
O
(a)
(b)
O
T
T
(c)
Octahedral
Tetrahedra
8
1.2.2 Classification of the clay minerals
1.2.2.1 The 1:1 structure
The so called 1:1 clay structure contains one tetrahedral and one octahedral sheet as
the repeat unit with no layer charge. The interlayer is occupied by hydroxyl groups and
oxygen atoms from the octahedral and tetrahedral sheets connected by weak hydrogen
bonds. Members of this group can be dioctahedral such as kaolinite, containing Al and Si
with no substitutions, or trioctahedral such as chrysotite containing Mg and Si ( see Table
1.1)
Kaolinite belongs to a group of 1:1 clay minerals known as the Kaolin group. In this
group dickite and nacrite are the polymorphs of kaolinite and distinguished by the
stacking of layers along the c axis. Halloysite has similar structure as kaolinite but has
more water in the interlayer resulting in the d (001) spacing increasing from 7.15 Å to
10Å. The structure of kaolinite consists of a repetition of layers existing of one Al
(O,OH) octahedral sheet coupled to a single SiO4 tetrahedral sheet.
Within this structure a differentiation can be made between four hydroxyl groups.
These hydroxyl groups are generally known as the inner and outer hydroxyl groups.
Three of these groups stick out of the layers and form the hydrogen bonds to the next
layer. The outer hydroxyl groups (OuOH) are located in the outer, upper and unshared
plane whereas the inner hydroxyl groups are located in the lower shared plane of the
octahedral sheet. The location of the hydrogen atoms is very difficult to study by XRD
due to X-ray scattering by hydrogen atoms but they do have a large neutron incoherent
scattering (Bailey, 1988). Vibrational spectroscopic techniques have been found very
9
useful for studying the location of hydroxyl groups in kaolinite (Ledoux and White,
1966), hence a large amount of literature may be found on this subject. The IR OH-
stretching modes of the hydroxyl groups from of the kaolinite can be observed in the
region between 3600 and 3700cm-1, (Bailey, 1988; Frost, 1997). The source of interlayer
bonding in kaolinite structure comes from the hydrogen bonds between the octahedral
layer and the oxygen of the tetrahedral layer.
The two sheets of the kaolinite are bonded together by Van der Waals forces and
hydrogen bonding. No interlayer cations or layer charge are present in the kaolinite
structure. The layers are connected by Si-O-Al bonds. Kaolinite has quite often been
qualified as clay that is not capable of expansion. However specific organic molecules
can be inserted into the kaolinite structure resulting in the expansion of kaolinite along
the c axis (Kristof et al., 1998; Sidheswaran et al., 1987; Frost et al., 2000b; Frost et al.,
1999c).
1.2.2.2 The 2:1 structure
The 2:1 clay layer type is characterized by an octahedral sheet sandwiched between
two tetrahedral sheets. Depending on the layer charge the 2:1 layers groups can be
divided into two subgroups:
• Subgroup 2:1 with no layer charge and no exchangeable cations
The dioctahedral mineral of this group is pyrophyllite, Al4Si8O20(OH)4, and the
trioctahedral equivalent is talc, Mg6Si8O20(OH)4. The layer thickness of the octahedral
and two tetrahedral sheets together is about 9.5 Ǻ.
10
• Subgroup 2:1 with layer charge and exchangeable cations
The layer charge of the smectite group range from 0.4- 1.2 and the species of this
group correspond to the most commercial clays known as bentonite. Members of this
group have the ability to exchange interlayer cations and water with the surrounding
environment.
Smectite is a name for a group of 2:1 layer minerals, either dioctahedral or
trioctahedral in nature, which can expand when water or organic molecules are
introduced into the interlayer space. Montmorillonite and beidellite are dioctahedral
smectites with mainly Al in the octahedral sheet, which have been formed by alteration of
volcanic ash or tuffs (Hewitt, 1917). The trioctahedral smectites, such as saponite,
hectorite and stevensite, contain mainly Mg+ (with or without Li+ or vacancies) in the
octahedral sheet. The charge can be located in the tetrahedral sheet (saponite) or in
octahedral sheet (hectorite).
The substitution of cations, which have different valencies, can lead to charge
unbalances within a sheet and can be totally or partially balanced by the adjacent sheet.
The remaining net charge or layer charge is negative for the 2:1 layer. This charge is
balanced by large hydrated cations, such as Na+, K+, Ca2+ and Mg2+, which coordinate to
the basal surfaces of the tetrahedral sheets from the adjacent layers. These charged
cations are referred to as “interlayer cations” (see Figure 1.4). The layer charge arises
primarily in the octahedral sheet for montmorillonite, hectorite and in the tetrahedral
sheet for beidellite, saponite and nontronite. Smectites are often referred to as “swelling
clays” due to the ability of expanding when contact with water. The distance between two
11
clay layers can vary from 12Ǻ to 16Ǻ depending on the size of the exchangeable ions and
the amount of water. The charge imbalance is much higher compared to illites and these
electrical property results in the high cation adsorption capacity of the smectite structure.
The smectites may be Fe3+-rich (nontronites) or Al-rich (montmorillonite-beidellites)
although complete compositional substitutions are possible. Volkhonskoite is a Cr rich
(>15% Cr2O3) dioctahedral smectite with Cr contains mainly in octahedral sheet.
Sauconite is a trioctahedral smectite contaning Zn in the octahedral sheet. Other smectites
containing vanadium, nickel and copper have also been reported (Guven and Hover,
1979, Brindley and Maksimovic, 1974). The ability to absorb water can result in an
increased distance along the c axis of the clay layers. The free and rapid exchange of
cations, complexes and water in the smectite interlayer depends largely on the physico-
chemistry of the environment (Weaver and Pollard, 1973; Velde, 1985; Newman, 1987)
and can be used to produce a large variety of intercalated and pillared clays.
Layer type
Interlayer species
Layer charge
Octahedral sheet type
Formula Mineral name
12
1:1 none or H2O
only
~0 di
tri
Al4Si4O10(OH)8
Mg6Si4O10(OH)8
kaolinite
chrysotile
2:1 None ~0 dil
tri
Al4Si8O20(OH)4
Mg6Si8O20(OH)4
pyrophyllite
talc
hydrated
exchangeable
cations
0.4-1.2 di
di
di
tri
tri
tri
Mgx/nn+[Al4-xMgx][Si8]O20(OH)4
.nH2O
Mgx/nn+[Al4] [Si8-xAlx]O20(OH)4
.nH2O
Mgx/nn+[Fe4][Si8-xAlx]O20(OH)4
.nH2O
Mgx/nn+[Mg6][Si8-xAlx]O20(OH)4
.nH2O
Mgx/nn+[Mg6-xLix][Si8]O20(OH.F)4
.nH2O
Mgx/nn+[Mg6-xVacancyx][Si8]O20(OH)4
.nH2O
montmorillonite
beidelite
nontronite
saponite
(F-)hectorite
stevensite
1.2-1.8 intermediat
e
tri
[Mg,Ca]x/22+[Al4-xMgx][Si8]O20(OH)4
.8H2O
[Mg,Ca]x/22+ [Mg6][Si8-xAlx]O20(OH)4
.nH2O
vermiculite
vermiculite
non-hydrated
cations
1.8-2.0 di
tri
Na2[Al4][Si6Al2]O20(OH)4
K2[Mg.Fe]6[Si6Al2]O20(OH,F)4
paragonite
phlogopite
2:2 hydroxyl sheet 0.4-2.0 tri
tri
[(AlxMg6-x)(OH)6][Mg6][Si8-xAlx]O20(OH)4.
[Fe3+xFe2+
6-x)(OH)6x][Fe2+6-yMgy][Si8-xAlx]O20(OH)4
clinochlore
thuringite
13
12-16Ǻ
Fig. 1.4 The structure of typical smectite minerals
14
1.3 Intercalated and pillared clays
1.3.1 Introduction
Clay minerals with an ability to exchange interlayer cations have attracted a lot of
interest for use in industrial applications. To modify the clay structure, different
compounds have been used to intercalate between the layers with the hope of increasing
the pore size. Barrer and McLeod were the first to introduce the process of intercalation
of organic compounds into the structure of clay minerals (Barrer and MacLeod, 1955).
These products are quite suitable for applications such as absorbent, fillers and thickeners
(Schoonheydt et al., 1993), but were found to decompose at relatively low temperatures
making them unsuitable for most catalytic applications (Barrer and MacLeod, 1955).
The next development stage of pillared clay coincided with a crisis in the oil industry.
The search for new type of materials with relatively large pore-sizes to deal with larger
molecules in the crude oil, and good thermal and hydrothermal stability has resulted in
the development of inorganic polyoxocations as pillaring agents that could be intercalated
between the clay layers and, when calcined, produced fixed metal oxide pillars, providing
new types of acidic, highly porous, thermally stable materials with a high specific surface
area (200 to 500 m2g-1).
1.3.2 Intercalated clays
Intercalation is the process of inserting organic or inorganic molecules into the
interlayer of the clay structure The principle of the intercalation process in kaolinite was
pointed out by Lagaly in 1984 (Lagaly, 1984). The new organic molecules, which were
introduced into the kaolinite layers were found to have broken the hydrogen bond
15
between the hydroxyl group of the octahedral sheet and the oxygen atoms of the
tetrahedral sheet to form new bonds with the more hydrophobic siloxane layer or with the
more hydrophilic hydroxyl groups.(Weiss et al., 1966; Lagaly, 1984; Costanzo and Giese,
1990).
The intercalation of organic molecules such as hydrazine, urea, formamide, acetamide,
DMSO and acetate has been discussed in a review by Frost et al. (2000a). The ideas of
intercalation kaolinite with organic molecules to make it expanded has given rise to a
new field of research and since then more molecules have been tested for dimensions and
bonding properties with the kaolinite structure. The most common molecules, which
have been used for kaolinite intercalation are hydrazine (NH2-NH2), urea (NH2-C=O-
NH2) and formamide (HC=O-NH2).
In general, the organic molecules that intercalated into kaolinites can be divided into
three groups. Group I contains molecules that can form strong hydrogen bonds with the
siloxane layer. These molecules include hydrazine (NH2-NH2), urea (NH2-C=O-NH2) and
formamide (HC=O-NH2). Kaolinite intercalated with molecules from this group gives
expansion of the basal spacing from 7.2Å to 10.4Å. (Ledoux and White, 1966); (Johnston
and Stone, 1990); (Frost et al., 1999b), (Cruz and Franco, 2000).
Group II contains molecules with strong dipole interactions. These molecules can
interact with the siloxane layer of the kaolinite. Members of this group include
dimethylsulfoxide ([CH3]2SO), and dimethylselenoxide. ([CH3]2SeO). Kaolinite
intercalated with molecules from this group results in a large expansion of the basal
spacing, from 7.2Å to approximately 11.2Å (Frost et al., 1998b). The intercalation of
16
kaolinite with these molecules can be used as a precursor for other inorganic alkaline
salts.(Lahav, 1990; Lapides et al., 1997).
Group III contains alkali salts of short chain fatty acids such as acetic and propionic
acid. (Wada, 1961;Ledoux and White, 1966; Weiss et al., 1966). The surface hydroxyl
groups on the kaolinite can form hydrogen bonds with fatty acid salt. Kaolinite
intercalated with molecules from this group gives a basal expansion from 7.2Å to
approximately 14.2Å.
Organoclays have been used for treating soil to remove contaminants, e.g.,
polychlorinated biphenyls and polyaromatic hydrocarbons. Organoclays have been
modified with a range of pillaring agents such as Al(OH)3, SiO2, and TiO2 and been
found to have organophilic properties (McLeod, 1997). In a study of HDTMA+ /
montmorillonite , the morphology of organoclay has been shown strongly depending on
the surfactant packing density within the montmorillonite interlayer space. Thermal
treatment has an important effect on the stability of organoclays, reflected by significant
changes in the basal spacing (He et al., 2006).
1.3.3 Pillared clays
The use of inorganic compounds as pillaring agents has provided an alternation to
organic compounds as pillaring agents which suffer the low thermostability. Most of the
recent research on pillared clays has been concentrated on Al13 pillared clays which use
the Al13 polyoxocation [Al13O4(OH)24(H2O)12]7+, as the pillaring agent of which was first
studied by Johansson in the ‘60s (Johansson, 1960).
17
The Al13 complex consists of a central tetrahedral aluminium cation, which is
surrounded by twelve edge-linked octahedrally coordinated aluminium cations
(Johansson, 1962).
In general the pillaring process can be described according to the diagram in Figure
1.5. The smectite used as a starting material is ion exchanged with Na or Li in order to
obtain maximum swelling prior to the exchange with the large inorganic pillaring
complex. To obtain for example Al pillared clays, a solution containing the Al13
polyoxocation is mixed with the Na or Li exchanged clay (smectite group) suspension.
After the cation exchange reaction between the clay and the polyoxocation has taken
place, the suspension is washed; the expanded clay is separated, dried and calcined at
around 400 to 500°C to convert the complex to intercalated fixed metal oxide pillars in
the clay interlayers. The calcination process of Al pillared smectites can liberate protons
from the pillar, which can then diffuse into the clay sheet, lowering the thermal stability.
In pillared beidellite, the formation of Si-OH groups was observed during dehydration
in the IR emission spectra. This indicated that at the same time protons are liberated,
which can interact with the tetrahedral Si-O-Al bonds upon calcination and forming new
Si-OH-Al bonds. A reaction between the Al13 pillar and the protonated Si-OH-Al linkage
will yield Altetrahedral-O-Alpillar linkages (Chevallier et al., 1994; Kloprogge and Frost,
1999; Kloprogge et al., 1999b; Kurschner et al., 1998). No clear reaction has been
observed so far between pillars and montmorillonite upon calcination although a stable
bond is formed, whereas in pillared beidellite a structural transformation links the pillar
to some sort of inverted tetrahedra of the tetrahedral sheet (Kloprogge, 1998).
18
The first reports on Al13 pillared montmorillonite were published around 1977-1981 by
several authors.(Brindley and Sempels, 1977; Lahav et al., 1978; Vaughan and Lussier,
1980; Vaughan et al., 1981). The Al13 complex has been used to prepare pillared clays
with the d(001) around 17-18 Å and thermal stability up to 500ºC (Brindley and Sempels,
1977; Miehe et al., 1997)
The stability of Al13 pillared montmorillonite has been suggested to result from the
formation of Al metal oxides through dehydration and dehydroxylation of the Al13 cations
at high temperature as shown by the equation below. (Pinnavaia, 1983; Schoonheydt et
al., 1994)
HOAlOHOAl nn OH
n
+−
+−+⎯⎯ →⎯
−+
+
)3(5.6)3(3228413
2)(
The number and strength of the acid sites occurring in the clay minerals are important
factors for catalytic applications. Two types of acid sites have been discussed in the
literature: the Brönsted and Lewis acid sites. Both types of acid sites have been reported
in pillared clays (Occelli and Tindwa, 1983; Pinnavaia, 1983). In general, a Brönsted acid
is defined as a substance which can supply a proton and a Brönsted base is a substance
which can accept a proton. A Lewis acid is defined as a substance that can receive a pair
of electrons and the Lewis base can donate a pair of electrons.
19
Fig. 1.5 Representation of the pillaring process showing d spacing changing from the
beginning and the end product after calcinations
Modified after Gil et al. (Gil et al., 2000b)
20
The acidity of the pillared clays can be studied by calorimetric adsorption of pyridine
and monitoring of pyridine desorption by IR spectroscopy (Occelli, 1985; Figueras et al.,
1990; Gonzalez Luz et al., 1990). Lewis acid sites have been found to be correlated with
the number and nature of the pillars, whereas the Brönsted acid sites are located within
the clay sheets (Bagshaw and Cooney, 1993). For example, Cr pillared clays show
stronger Lewis acid sites than other pillared clays (Jiang et al., 1991; Auer and Hofmann,
1993). Acid sites can also be studied by IR combined with temperature programmed
desorption of ammonium (Bodorado et al., 1994; Vogels et al., 2004; Zhao et al., 1994).
Bagshaw and Cooney (Bagshaw and Cooney, 1993) found that the characteristics of
surface Lewis acid sites were associated with the pillar species while those of the
Brönsted acid sites are determined by both the pillar and the starting clays. The pillared
clays have been found to have more Lewis acid sites than Brönsted acid sites (Kurian and
Sugunan, 2005). The surface acidity varies with the pillaring agents and stems from their
pillars. During calcination the pillars are transformed to oxides. In this process protons
are released and can produce the Lewis and Brönsted sites (Barrer and MacLeod, 1955;
Plee et al., 1985b; Xie et al., 1994).
When Na- exchanged saponite was used as a starting material, the Brönsted acid sites
were not present but were later formed in the Al-pillared product, based on the
observation of a pyridinium band at 1549 cm-1 in the infrared spectrum after the
absorption of pyridine (Bergaoui et al., 1995). The Brönsted acid sites are thought to be
related to OH groups formed by the acidic attack of Si-O-Al linkages, which occurs on
the clay sheets during the pillaring process (Chevallier et al., 1994; Kurschner et al.,
21
1998). These hydroxyl groups were observed in the infrared spectrum at 3740-3720 cm-1
and 3597-3594 cm-1.
Changes in the local environment, such as short range order and coordination, in the
interlayer, the octahedral or tetrahedral sheets in smectites or their pillared equivalents
can be studied by Magic-Angle Spinning Nuclear Magnetic Resonance spectroscopy
(MAS-NMR).
The movement of water and interlayer cations in synthetic beidellite (Na0.7Al4.7Si7.
3O20(OH)4.nH2O) has been studied by Kloprogge et al. (Kloprogge, 1992) using solid-
state 23Na and 27Al magic-angle spinning (MAS) NMR. The 23Na NMR chemical shift of
0.2 ppm indicated that the hydrated sodium cations in the interlayer resemble Na+ in
solution. From 25°C to 85°C four water molecules per Na+ were found to be removed,
which caused the basal spacing to decrease from 12.54 Å to 9.98 Å and the remaining
water molecules with the Na+ was relocated much closer to the tetrahedral sheet, as
indicated by the chemical shift of 1.5 ppm after the first dehydration step. The second
dehydration occurs at a temperature around 400ºC but the removal of the remaining 2
water molecules did not cause any further decrease of the basal spacing (Kloprogge et al.,
1992).
Plee et al (1985a) used 27Al and 29Si to study pillared beidellite and suggested that the
linking of Al13 and tetrahedral layer as a result of inversion of tetrahedral unit and the
formation of Si-OH-Al group. In Plee’s original PhD thesis there is also evidence of a
separate Al(IV) peak for the pillar next to the tetrahedral Al peak of the clay which shows
22
changes with calcinations. However, no one has been able to reproduce these results. In
all cases a severe overlap of the two signals has been observed.
The study of saponite from Ballarat pillared with Al polycations by 29Si and 27 Al solid
state NMR suggests that the pillaring mechanism involved H+ attack of the clay
tetrahedral sheet followed by AlO4 tetrahedra inversion. 27Al NMR revealed that the
pillars are not modified upon calcination at 500°C although they undergo reversible
dehydration reactions; at 750°C and above, a strong pillar reorganisation occurs prior to
collapse of the global structure (Bergaoui et al., 1993).
The work of Kloprogge et al in 1999 showed that the structure of the pillared clays
changed during the pillaring process. During calcination up to 500°C the pillars were not
completely converted to the oxide and remained as hydroxyl groups (Kloprogge and
Frost, 1999; Kloprogge et al., 1999a; Kloprogge et al., 1999b). This fits in nicely with the
work by Balek et al (Balek et al., 1998) using emanation thermal analysis, which showed
that after heating to 500 C° followed by cooling to room temperature and a second
heating cycle that there were still some volatiles present that were driven off during this
second heating cycle.
In a study of montmorillonite pillared with single and mixed Keggin polycations and
calcination to 900°C using 27Al and 29Si MAS-NMR, the result showed that the
tetrahedral layers (SiO4) were not significantly affected by the pillaring process whereas
the OH regions changed during the pillaring and calcination (Espinosa et al., 1994). The
OH vibration in the corresponding infrared spectra, which occurred at 3543cm-1,
disappeared around 400°C owing to the formation of pillar-layer bonds. The new pillar
23
OH vibration occurring at 3695cm-1 and the Si-OH at 3750cm-1 disappeared after the
samples were heated to 700°C (Espinosa et al., 1994).
Due to its similar electronic configuration, gallium (Ga) has chemical properties
comparable to aluminum (Al) and can be used to improve the catalytic activity of the
pillared clays (Bellaloui et al., 1990; Bradley and Kydd, 1993a). Bradley and coworkers
have done an extensive research of the hydrolysis of gallium (Bradley, 1991; Bradley and
Kydd, 1993 a, b, c, d, e; Bradley et al., 1990). They found that Ga could form a similar
Keggin-type polyoxocation and may be used as pillaring agents in a similar method to
Al13. In Bradley’s study, the Al at the tetrahedral site in the Al13 structure was replaced by
Ga resulting in a better fit in the Keggin structure (Bradley, 1991). The small size of the
Al cation causes a slight distortion in the tetrahedral site in the Al13 structure. This
distortion is minimized by replacing the Al cation by the larger Ga cation, which results
in an increase of the stability of the GaAl12 Keggin structure (Bradley, 1991).
The structure of Ga pillared clays and the relationship between the physico-chemical
properties and the local pillar structure was studied by Montarges et al., 1997; Montarges
et al., 1999 and Bradley and coworkers (Bradley and Kydd, 1993a; b; d; e). They showed
that the pillared products are structurally analogous to materials synthesized using Al13
polycations and possess similar physicochemical properties. Furthermore, the properties
of Ga13- polyethyleneoxide (PEO) modified montmorillonites exhibit similar properties to
Al13-PEO-modified samples. (Montarges et al., 1999).
The use of Ga13 as a pillaring agent can be advantageous as it allows independent
observation of the structural changes in both the pillar and the clay during calcination.
24
The basal spacing of Ga-pillared montmorillonite was found in some cases to collapse to
9.5 Å at 350°C due to the Ga polymer decomposing to Ga3+ cations (Kloprogge, 1994).
The reason for this collapse is still unclear.
Mixed Ga/Al pillared clays prepared by Coelho and Poncelet (1990) with partly
hydrolyzed Ga/Al salt solutions with various Ga/Al ratios showed basal spacings between
18.7- 20.1 Å after intercalation, which decreased to 17.5Å after calcination .
Bradley and coworkers have contributed largely to the understanding of the hydrolysis
of aqueous Ga and mixed Ga/Al solutions (Bradley, 1991; Bradley and Kydd, 1993c).
The hydrolysis of a mixed Ga/Al solution resulted in the presence of a sharp Ga NMR
signal at 137.8 ppm that belongs to tetrahedral Ga indicating that the GaAl12 Keggin
structure was formed. The GaO4 formed the central tetrahedron and was surrounded by
12 Al octahedra (Bradley and Kydd, 1993c). The basal spacings and surface areas of the
Ga/Al pillared clays were found to be very similar to those found by Coelho and Poncelet
(1991) and Gonzalez et al. (1991; 1992). The decrease in tetrahedral distortion by
substituting GaIV for AlIV in the Keggin structure was found to be reflected in the increase
of thermal stability in the following order: GaAl12- PILC > Al 13-PILC> Ga13-PILC
(Bradley and Kydd, 1993c). The Lewis acid strength decreases in the order Ga13 >Al13 >
GaAl12 whereas the Brönsted acid strength decreases in the opposite order (Bradley,
1991).
Bentonites pillared with Ga13, GaAl12 and Al13 were found to be thermally stable up to
700°C with catalytic data indicating the following order for activity for Ga13 >GaAl12>
25
Al13. The acidity studies showed more acid sites were present in all pillared clays, with
both Lewis and Brönsted sites being detected (Berkeliev et al., 1992).
The methods of preparation and characterization of Ga12Al pillared clays have been
reported by (Bellaloui et al., 1990; Holmgren, 1996, Kloprogge, 1994, Bagshaw and
Cooney, 1995, Caballero et al., 1995, Gil et al., 2000b). The current methods of making
pillared clays may be divided into six types which are (1) Traditional method using Al13,
(2) Surface analysis /polymerization used for making chromia pillared clay (3) Via the sol
gel.method (4) Direct intercalation of nano particles. (5) Using amines and surfactant. (6)
Using platelets themselves as pillars (De Stefanis and Tomlinson, 2006).
To improve the hydrothermal stability and catalytic properties of the pillared clays,
mixed Al/metals pillared clays have been studied. Apart from mixed Ga/Al pillared clays,
the most important combinations with Al are Fe, Si, and Zr. (Torii et al., 1992; Bergaya
and Barrault, 1990; Bergaya et al., 1990; Doff et al., 1988).
The FeAl pillared clays can be prepared by using solutions of AlCl3, FeCl3 and NaOH.
Fe cations have been found to replace a few octahedral Al in the Al13 pillars (Bergaya and
Barrault, 1990; Carrado et al., 1988). There are two different methods of preparing mixed
Fe/Al complexes in solution. In the first method, Fe salts (nitrate or chloride) were added
to a commercially available Al13 solution known as Chlorhydrol (ACH, commercially
available from Reheis Chemical Company). A basal spacing of 18.8Å was observed after
calcination at 480oC (Carrado et al., 1986a; Skoularikis et al., 1988). The second method
comprises the co-hydrolysis of FeCl3 and AlCl3 by NaOH (Doff et al., 1988, Bergaya et
al., 1990) or Na2CO3 before cation exchange with the clays; (Bergaya and Barrault,
26
1990). Further preparation and characterization of mixed Fe/Al pillared clays have been
reported by several authors, e.g. (Kiricsi et al., 1997; Zhao et al., 1993; Huang et al.,
1991; Carrado et al., 1986a) and reviewed by Kloprogge (1998a).
Mixed Si/Al pillared clays were prepared by Gaaf et al. (1983) by using a solution of
aluminum chlorhydrol and sodium silicate. The final products showed a weak XRD
signal of an expanded structure together with the original non-expanded clay basal
reflection indicating only partial intercalation. Another successful route was explored by
Occelli (1986) using sub-micron positively charged colloidal particles of alumina coated
silica from. The basal spacing of the final products after treatment at 400°C was 18.8Å
and they were stable up to 600°C in air. Other authors who have done extensive studies
on hydroxy-silicoaluminum (HAS) include Tichit et al. (1988); Sterte and Shabtai
(1987b); Zhao et al. (1992). The basal spacings of the products were found to range from
17 Å to 26.5Å (Sterte and Shabtai, 1987a; Huang et al., 1991).
Occelli and his group has prepared mixed Zr/Al pillared clays using the REZAL67 and
RETZEL 36G (commercially available from Reheis Chemical Company) (Occelli, 1987).
The formula of the complex is [Al8(OH)20ZrO]6+ and the Al/Zr ratio is about 6.7. The
cracking activity was intermediate between the cracking activities of Si/Al and Al
pillared clays (Occelli, 1987).
Other mixed metal/Al pillared clays used for cracking that have been prepared include
UO2/Al, B/Zr/Al, and B/Si/Al ; (Wenyang et al., 1991a; Wenyang et al., 1991b, Carrado
et al., 1986a, Carrado et al., 1986b). To produce the mixed UO2/Al pillared clay, a
mixture of UO2(NO3)2 H2O and Al13 was used to react with Ca bentonite. The
27
incorporation of the uranyl has been found not to affect the cracking properties of the
pillared clay (Carrado et al., 1986a). Wenzang et al. (1991) found that adding boron (B)
to Si/Al or Zr/Al mixed metal pillared clays could improve the cracking ability of the
pillared clays (Wenyang et al., 1991a; Wenyang et al., 1991b).
Although Al – pillared clay is the most popular material for industrial applications,
other stable pillared clays have been prepared. The preparation, characterization and
application of pillared clays and their catalytic properties have been discussed in a
number of reviews including a special issue of Catalysis today in 1988 (Burch, 1988);
and more recently by Kloprogge and coworkers (Ding et al., 2001; Kloprogge, 1998;
Kloprogge et al., 2005) and others (Baiker, 1996; Ballantine, 1986; De Stefanis and
Tomlinson, 2006; Gil et al., 2000a; Vaccari, 1998).
The most stable pillared clays that have been produced are Ti and Zr- pillared clays.
Ti pillared clays have been prepared and studied by a number of researchers: (Kurek,
1992; Bergaya et al., 1995; Chae et al., 1999, Liu et al., 2006, Binitha and Sugunan,
2006). Titanium has been found to form polymeric species in solution (Nabivanets and
Kudritskaya, 1967; Einaga, 1979). Various methods of preparing Ti complexes for
pillaring processs have been investigated. The first method in which Ti complexes were
formed comprised adding TiCl4 to 5 or 6 M HCl solution followed by dilution with
distilled water and ageing from 3 hours up to as long as 20 days (Baksh et al., 1992;
Sterte, 1989; Bernier et al., 1991). This method produced highly acidic conditions which
could cause leaching of a small amount of Al and Si from the clay structure (Bernier et
al., 1991; Baksh et al., 1992).
28
The second method is based on the hydrolysis of various Ti alkoxides under milder
acidic conditions (mostly 1 M HCl) (Farfan-Torres et al., 1992; Malla et al., 1989;
Yoneyama et al., 1989; Sychev et al., 1992; Del Castillo and Grange, 1993; Choudary et
al., 1990). The d-spacing has been increased to around 24 – 25 Å for both methods. The
experimental conditions of the Ti complexes-clay suspension were found to be critical to
the morphology and texture of the pillared clays (Bernier et al., 1991; Sterte, 1989). The
formation of an anatase phase outside the clay structure upon calcination has been
reported based on XRD and IR spectral evidence (Bernier et al., 1991; Bagshaw and
Cooney, 1993).
The acidity of Ti pillared clays has been found to be increased during the synthesis
process. Using temperature programmed desorption (TPD) of ammonia and pyridine
adsorpsition/desorption experiments Bagshaw and Cooney (1993) and Bernier et al.,
suggested that the Lewis acid site must be located at the interface between pillar and the
siloxane surface. (Bagshaw and Cooney, 1993; Bernier et al., 1991). The dealumination
of the Ti-pillared clays during the synthesis process is the main reason for the increased
acidity (Sychev et al., 1992). The formation of Brönsted acid sites has been reported from
the pillaring of rectorite (Bagshaw and Cooney, 1993). Organic titanium pillared clays
have been prepared by mixing a TiCl4 ethanol solution with a solution of glycerin and
water. The final products showed basal spacings from 17.4 Å, to 21.3 Å (Jong et al.,
1994). In 1999, Ooka studied Ti pillared clays prepared by hydrothermal treatment. The
study indicated that the relationship between the size of the crystallized TiO2 pillars and
the average pore diameter was in good agreement, and could be controlled by changing
the treatment conditions. The catalytic activity of the TiO2 pillars was found to be
29
enhanced by quantum-size effects: as the TiO2 pillar size decreased, the pillared
montmorillonites exhibited higher catalytic activity and showed larger blue-shifts in their
UV absorption spectra. (Ooka et al., 1999). The photochemical and photocatalytic
properties of the microcrystalline TiO2, which formed in the interlayer space after
calcination of the pillared clays is very important for catalytic applications ; (Sychev et
al., 1992; Yoneyama et al., 1989).
Other pillared clays using Zr, Cr, Fe, Si, V as pillars has been reviewed by Kloprogge
(Kloprogge, 1998), and Kloprogge and coworkers (Ding et al., 2001; Kloprogge et al.,
2005). In a more recent review in 2006, the method of making pillared clays for catalytic
applications was discussed by De Stefanis and Tomlinson. In this review, small angle
neutron scattering was mentioned as a new tool for studying interpillar distances (De
Stefanis and Tomlinson, 2006).
Boehmite AlOOH pillared montmorillonite has been studied by Sivakumar and
coworkers (Sivakumar et al., 1997a; 1997b; 1994).
Imogolite and boehmite pillared clays have been prepared for some applications.
Imogolite Si2Al4O6(OH)8 is a semi-ordered structure which has been used successfully to
intercalate montmorillonite and beidelite (Pinnavaia, 1992). The imogolite intercalated
montmorillonite showed regular microporosity of adsorbates molecules with kinetic
diameters from 8.6-10Ǻ (Johnson et al., 1988).
Recently, it has become possible to look at the morphology and the internal structure
of clay minerals and pillared structures on an atomic scale with the development of
Atomic Force Microscopy (AFM) and high resolution Transmission Electron Microscopy
30
(HRTEM), vibrational spectroscopy and X ray photoelectron spectroscopy (XPS). There
are still many questions about the relationship between the morphology and structure of
clay minerals. The understanding of this structure will produce tailored clays for
industrial applications.
1.4 Analytical techniques for studying clays and their modifications
1.4.1 X- Ray Diffraction
The discovery of X-rays by Röntgen in 1895 has given clay scientist a new method to
study the fine structure of clay minerals. In 1923, Harding in Sweden published the fist
XRD pattern of the finest clay particles and found that the smallest clay particles were
crystalline and had the same composition as other bigger particles in other samples
(Harding, 1923). The principles and application of the XRD method can be found in most
textbooks covering geology, chemistry or material science (Moore and Reynolds, 1997;
Birks, 1969).
Since the first XRD pattern of clay was published, the technique has developed into an
important tool for clay scientists for the characterization of crystalline materials. XRD
can not only be used to study the structure of pure clays, mixed layer clays, but also to
study changes in structure when expanding and pillaring clays with organic and/or
inorganic molecules. Figure 1.6 shows the changes in XRD patterns of montmorillonite,
intercalated montmorillonite and pillared montmorillonite with Ga pillars.
Mixed-layered clay structures, such as illite/smectite, can be determined by XRD, (Pons
et al., 1995).
31
With the development of computing technology, there are a number of programs for
the interpretation of XRD patterns. For example Krumm in 1999 discussed how to apply
WinStruct software to simulate XRD patterns of oriented clay minerals (Krumm, 1999).
Another program called “an expert system” has been used by Plancon in 2000 to interpret
the mixed layer illite/ smectite patterns (Plancon and Drits, 2000). Other programs that
have been used for clay structure are NEWMOD and mudmaster. (Denis Eberl et al 2000;
Plancon et al 1990).
The ratio of illite/ smectite has been found to be very stable in sedimentary bedding
and could be used as an indicator to study basin history and correlation. Changes in
structure of the clay particles, in particular the stacking, can be seen from the variety of d
spacings which allows scientists to identify the different species with ordered or
disordered structures.
Heating stage XRD is another way of studying clay minerals. The temperature can be
controlled and XRD patterns can be collected at certain temperatures allowing the direct
observation in situ of any structural changes taking place.
Aceman et al. (1997) studied Al-pillared clays preparing from five different smectites
using heating stage X-ray diffraction. These clays, dioctahedral beidellite and
montmorillonite and trioctahedral saponite, hectorite and Laponite, differ in the origin of
isomorphic substitution and represent a series of decreasing basicity along the siloxane
plane. They concluded that the Keggin ion lost its structural water around 200°C and
dehydroxylated above 350°C. After heating to 500°C to 600°C, this polymeric cation,
32
which is thought to form the Al2O3 oxide, did not rehydrate. (Aceman et al., 1997)
(Aceman et al., 2000).
Recent developments in diffraction techniques include techniques such as small angle
neutron scattering which can provide information about the inter pillar distances and
permits the modelling of the pore structure (De Stefanis and Tomlinson, 2006).
33
3 8 13 18 23
degrees 2θ Cukα
Cou
nts
14 Å
19.9 Å
17.9 Å
Ga13 exchanged
Ga13 calcined
Starting montmorillonite
Fig. 1.6 XRD patterns of clay and pillared clays showing structural changes from starting
montmorillonite to Ga exchanged montmorillonite and after calcination process
34
1.4.2 Electron Microscopy and X- Ray Microanalysis
In electron microscopy, a focused electron beam is used to illuminate a specimen.
Electrons are produced from a tungsten, LaB6 or field emission cathode, accelerated
along the column and are focused by electromagnetic lenses. At the same time X-ray are
generated from the interaction between the electrons and the specimen which can be used
for elemental microanalysis of the specimen. Scanning electron microscopy can provide
higher resolution information of clay materials than optical microscopy, down to a few
nanometers in practice, but only of surfaces of the particles. It does provide a very good
depth of field for three-dimensional imaging of clay particles. However, transmission
electron microscopy with electron diffraction and microanalysis provides very high
resolution images of clay particles and their structures. The first TEM was introduced in
1931 by the work of Knoll and Ruska (Marton, 1968) and since then has rapidly
expanded for studying clay structures. The formation of an image in an optical
microscope, transmission electron microscope and scanning electron microscope can be
seen in Figure 1.7.
35
Fig. 1.7 Image formations in optical microscope, transmission microscope and scanning
electron microscope In the optical microscope the source is light bulb whereas in the
SEM and TEM the source is an electron beam (Buseck, P.R., 1992)
36
In an early study of clay minerals using electron microscopy techniques, TEM was
mentioned in the Symposium held at the 7th International Clay Conference, Bologna,
Italy as one of the important advanced techniques for clay mineral analysis (Fripiat,
1982). The principle of transmission electron microscopy and application to clay
structures including electron diffraction of a small particle, have been discussed by
Goldstein et al (1981), Buseck (1992). Occelli et al. (1986) used TEM to analyse the
macro structure of pillared and delaminated hectorite catalysts. Two types of structure
were reported: the “house of card” and the “face to face” structures. (Lipsicas et al.,
1984; Occelli, 1987). In kaolinite, high resolution transmission microscopy (HRTEM)
revealed three types of surface layers crystals and defects present in the structure. Type 1
has a 7Å kaolinite surface layer, type 2 has a 10Å pyrophyllite like layers and type 3 has
one or several 10Å collapsed smectite like layers (Ma and Eggleton, 1999).
The electron diffraction pattern of the kaolinite structure was used to determine the
hydrogen atom position in the crystal structure (Raupach et al., 1987), and to study mix-
layer illite/smectite (Veblen et al., 1990). Results from high-resolution transmission
electron microscopy and lattice-energy calculations of mixed layering of illite-smectite
showed the unit layers are O0.5TITO0.5 with O, T and I are octahedral , tetrahedral and
interlayer sheets (Olives et al., 2000; Klimentidis and Mackinnon, 1986; Kohyama and
Fukami, 1982).
Crozier et al.,(1999) used the combination of TEM techniques such as bright field,
dark field imaging and energy dispersive X- ray spectroscopy (EDX) to determine the
location of the pillars in the [001] direction (or the basal plane projection) of the Zr-
pillared montmorillonite. The results showed that zirconia pillars have an irregular shape
37
and the sizes were <50 Å, which indicated that zirconia dispersion was not ideally
distributed throughout the whole sample.(Crozier et al., 1999).
In geological applications, TEM and high resolution TEM have been used to study the
mixed layer of illite-smectite, to understand the diagenetic changes in clay minerals and
to reconstruct the temperature history of the basin. Few SEM studies of clay minerals
have been undertaken, except for some studies mainly focusing on kaolinites (Zbik and
Smart, 1998) and have not compared the morphology of the pillared clays with starting
materials.
The exposure of the clays to the electron beam can lead to some structural damage.
The loss of some alkali elements (K, Na, Mg), low atomic number elements (Al), and
high atomic number elements ( Fe, Ti ) during the process of microanalysis of silicates
(kaolinite, smectite, biotite, muscovite and pyrophyllite) at about 300 kV, were also
reported (Ma et al., 1999).
The ability of smectites to expand when in contact with water causes complication
with sample preparation for SEM and particularly TEM. Several attempts have been
made to overcome this problem. Resin embedding techniques seem to be a popular for
clay samples preparation (Bateman, 1995). Two popular types of resins, which are used
by clay mineralogists, are LR White and Spurr (Spurr, 1969; Bateman, 1995). Araldite
has previously been used to embed mixed layer illite-smectite and this was cut with
diamond knife to obtain thin sample for TEM (Olives et al., 2000). The method of
preparing oriented clay particles for TEM has been discussed by Duong et al. (2005). Ga
38
and Al pillared montmorillonite were embedded in Spurr resin, and sectioned in an
ultramicrotome using a diamond knife (Duong et al., 2005).
Scanning electron microscopy and X-ray microanalysis permit an evaluation of surface
morphology, chemical composition and the overall structure of clay particles (Figure 1.8,
Figure 1.9). This allows a comparison to be made between the final products and the
starting materials which enables the results to be related to other observations made by
AFM and other techniques. The introduction of a heating stage, which could be fitted
with an SEM, TEM, or field emission SEM and TEM and environmental SEM, would
help clay mineralogists to study in much more detail the changing structure of pillared
clays with increasing pressure and temperature. Kloprogge and coworkers used ESEM
and low voltage SEM to study mineralogy of a bauxite sample (Kloprogge et al., 2006)
and characteristics of uncoated minerals have also been studied (Lin et al., 2005). This
work may open up the new areas in future, which can overcome the problem of sample
preparation due to the expansion of montmorillonites when in contact with water.
Lee and Peacor (1986) noted that laurylamine hydrochloride destroys the original
texture of the samples and should be used very carefully when characterize mixed layer
illite/smectite clays.
39
Fig. 1.8 SEM image of pillared montmorillonite (Top) and TEM image of particle of
Montmorillonite (bottom)
40
Fig. 1.9 SEM images of Kaolinite in sandstone shows typical book structure
41
1.4.3 Atomic Force microscopy
The atomic force microscope (AFM) was invented in the 80s by Binnig et al., 1986. It
gives topographic images by using highly local interactions between a very fine tip and
the surface of a sample. The tip and cantilever are made as one unit (Figure 1.10), and are
made of silicon nitride (Si3N4) or silicon (Si). The shape of the tip can be pyramidal or
conical depending on applications and ultra sharp tips are also available. The tip is
scanned across the surface and its movement is used to form a high-resolution image.
Because the interaction between the tip and a sample interaction is a very small force, the
AFM does not require conductive samples and is therefore of interest for the study of
mineral surfaces. The clay minerals with layered structure usually have a good cleavage
so they are potentially very good samples for AFM study. On the other hand, the
scanning tunneling microscope (STM) relies on a tunneling current between the tip and
surface hence samples of this method need to be at least semi conductive.
AFM has been used to study the surface of clay minerals on a nanoscale (Zbik and
Smart, 1998; Hartman et al., 1990) but very few studies have been found on AFM
directly of pillared clays
42
Fig. 1.10 Typical diagram of an atomic force microscope showing a tip mounted
on a cantilever (C). The tip scans over the surface of the sample. The
laser light from the back of the cantilever reflects to a two element
photosensitive diode (PSD) and the output signal can be used in a
feedback loop to control the vertical position of the sample (Binnig et
al., 1986)
43
The AFM images of illite and montmorillonite collected in air and under humidities
near 80% showed an ideal hexagonal array of oxygen ions in the siloxane surface of a 2:1
clay mineral. The distance from the center of the ring to another across the hexagonal is
about 11Å (Hartman et al., 1990). The hexagonal pattern of bright spots has also been
seen on the surface of Al- pillared rectorite as the collection of basal oxygens in the
tetrahedral sheet of the pillared clay (Occelli, 1994). The AFM has been used for
characterization of small kaolinite particles and compared with TEM results. AFM
images of kaolinite from Weipa deposit, northern of Queensland, Australia showed steps
on the basal plane of the kaolinite crystals in agreement with TEM images (Zbik and
Smart, 1998). The ratios of edge surface area (ESA) to total surface area (TSA) of
kaolinite particles has been studied and compared with the BET method. The edge
surface area is 18.2- 30.0% of the total surface area depending on the kaolinite standard.
(Bickmore et al., 2002; Zbik and Smart, 1998). Wu et a. (2001) imaged untreated
montmorillonite and pillared montmorillonite with the Digital Nanoscope III AFM in
contact mode and pointed out that the surface of untreated montmorillonite appeared
more intergrated whereas pillared montmorillonite showed more layer steps, which could
be the pillaring effect of the Keggin ions.
The effect of the pillaring process can be seen from the AFM images of Al13 pillared
montmorillonite. A powder of pillared clays was formed by pressing the sample at 34
000kPa, gluing it on to a steel disk with epoxy resin and then imaging with a Nanoscope
III Digital Instrument AFM. The images showed that the surface of the Al13 pillared clays
is free of Al species. The dimensions of the white spots on the surface are in good
44
agreement with the unit cell of other pillared montmorillonite but larger than the parent
montmorillonite (Campos et al., 1998).
The AFM non-contact mode, which uses the weak attractive force between the tip and
the sample to get the true atomic resolution has been reported recently (Lantz et al., 2001)
In the experiments performed by a low temperature AFM, operating with an ultrahigh
vacuum environment with a commercial silicon cantilever, the short range chemical
bonding forces between the apex of the silicon tip and the specific atomic sites on a
silicon sample have been measured (Lantz et al., 2001).
Sayed Hassan et al. (2006) studied the distribution of edge and basal surface of
phyllosilicate particles using low pressure argon adsorption and AFM analysis. The
results show very good agreement between the two methods .
1.4.4 Vibrational Spectroscopy and solid state NMR
Vibrational spectroscopic techniques involve the interaction of electromagnetic waves
(light) and the vibration modes of molecules. Infrared and Raman spectroscopic
techniques are the most common techniques, which have been used for studying
minerals, organic and inorganic materials. Further reading about those techniques can be
found from the publications of Banwell (1983), Farmer (1974), Gadsden (1975). Griffith
(1987), McMillan and Hofmeister (1988), Ross (1972). Raman spectroscopy is a non-
destructive technique, which is based on the experiment by Sir C.V. Raman in 1928
(Raman, C.V and Krishnan, K.S., 1928). The difference between Raman and infrared is
that Raman spectroscopy looks at the change in polarization of molecules where infrared
looks at the changes in dipole moment of molecules. Raman microscopy and Fourier
45
transform Raman have been used to determine the location of the OH of the kaolinite
structure (Frost and van der Gaast, 1997; Frost et al., 1998a; Frost et al., 1999a) and for
the identification of minerals.
Nuclear Magnetic Resonance (NMR) is a domain of absorption spectroscopy. This
method is based on the principle that certain nuclei possess a magnetic moment which
interacts with an applied magnetic field. The NMR studies of a number of clay minerals
and pillared clays have indicated that chemical shift in Al13 pillars and the relation
between OH/Al molar ratio and the Al 13 concentration (Kloprogge, 1992).
NMR has been used to recognise the tetrahedral Al and octahedral Al in pillared
smectite structure. Pillared beidellite showed a deep structural transition that can be
described as the growth of a pillar network grafted on the structure of the clay. There is
no reaction in pillared smectites with no substitution in the tetrahedral (hectorite and
Laponite) during the calcination process (Plee et al., 1985a; 1987).
The combination of vibrational and NMR techniques can give more detail
understanding of the arrangement of atoms and their environment. However as is
indicated in the literature, the position of the hydroxyls and the oxidation state of the clay
minerals are very difficult to determine by these two techniques.
1.4.5 X-Ray Photoelectron spectroscopy
X-ray photoelectron spectroscopy (XPS) was first introduced in 1981 through the
work of Siegbahn and coworkers in 1967 (Siegbahn et al., 1967) and since has been
applied as a surface analysis technique for studying surface materials and thin films
46
including minerals. Clay minerals, however, due to the small particle size and special
layer structure, are very good candidates for this technique. XPS has been regarded by
clay mineralogists as one of the advanced techniques for studying of clay minerals
(Fripiat, 1982).
X-ray photoelectron spectroscopy uses photons from an X-ray source of known energy
to eject core electrons from atoms at the surface of solids and the instrument is used to
measure the kinetic energy of that electron. Table 1.2 shows the atomic and
corresponding X-ray notations used in XPS. The binding energy of the free electron is
determined by the relationship:
hυ = Ekinetic + Ebinding
where hυ represents the energy of the photon, Ekinetic the kinetic energy of the free
electron and Ebinding the original (negative) binding energy. Hence this technique
measures, at a given hυ, the kinetic energy of the emitted electrons and can therefore be
used to determine the binding energy of each element present in the solid near the
surface. Changes in the binding energy reflect changes in the local environment (nearest
neighbours and next nearest neighbours) around a particular atom. At the same time as
the core electrons are removed, it is also possible to remove Auger electrons. Figure 1.11
shows the photoelectric effect, which produces both a photoelectron and an Auger
electron as a result.
It will be clear that only those electrons can be detected with a binding energy lower
than the energy of the photons used. Most common photon sources are monochromatic
Al-Kα and Mg-Kα X-rays resulting in photons with energies of 1486.6 and 1253.6 eV,
47
respectively, while older instruments often use non-monochromatic Mg X-rays. In these
cases the technique is known as X-ray Photo-electron Spectroscopy (XPS) or Electron
Spectroscopy for Chemical Analysis (ESCA). The second name points to the fact that by
analysing the energy of the photoelectrons, their energy levels and thus the chemical
identity can be determined. Especially for surfaces of solid materials XPS is a good
qualitative and quantitative analytical technique.
48
Fig. 1.11 Diagram showing Photoelectron and Auger electron processes
(Wagner, 1979 a)
49
Table 1.2 Atomic and X-ray notations (Wagner, 1979a)
50
Photoelectron spectroscopy as an analytical tool has only received limited interest in
the field of clay mineral science. Photoelectron spectroscopy, together with Auger
electron spectroscopy, gives information about the positions of the energy levels in atoms
or molecules. XPS has been widely used to study for thin films and for other surface
analysis. The application of this technique to study clay minerals will result in
information about the band structure of these materials and the local atomic environment
(Duong et al., 2005; Duong et al., 2006).
1.5 General discussion
Clay minerals are naturally produced by weathering processes and have structures that
belong to the group of phyllosilicates. Due to their special structures and properties, they
can be mined in large quantities at low cost, have a wide variety of industrial
applications, e.g. in the brick and tile industry. In addition a large amount of research has
been focused on modifying clay to obtain a suitable structure for special industrial
purposes. A good example of this is the delamination of kaolinite used in the production
of paper. Intercalated and pillared clays have been studied and produced for catalytic
purposes in the oil industry.
Due to the extremely small particle size and the complex sheet structure, many
techniques have been used to study clay minerals. The morphology can be directly
studied by techniques such as AFM and SEM and TEM. X-ray interactions with the
crystal structure such as these used in techniques such as XPS or XRD can be used to
obtain information not only on the crystal structure but also on its chemical composition.
Vibrational spectroscopy, including techniques such as Mid-infrared and Raman
51
spectroscopy, allow the investigation of the molecular structure of clay minerals based on
measurement of the vibrations between atoms.
Many types of pillared clays have been produced to suit industrial applications.
Techniques used for producing pillared clays vary from simple hydrolysis followed by
calcination in either an oven or a hydrothermal vessel to microwave treatment and with
the pillars ranging from small relatively simple complexes to large metal complexes. The
starting clays are mainly from the smectite group with montmorillonite and beidelite as
the most popular species. Kaolinite has been used for intercalating of organic molecules
with only limited industrial applications, while smectite clays intercalated with specific
organic molecules to produce organoclays have a wide range of uses in environmental
applications such as treatment of wastewater to remove unwanted organic species.
From the literature, a large variety of pillared clays have been produced based on
different metal complexes and with different methods depending on the purposes of
application. Although many papers have been published on the general structure of
pillared clays, the detailed structure of the pillars and the type of bonding of the pillars to
the silicate layers is still not fully understood. The literature review given in this chapter
shows a large number of good research papers focusing on the general structure and the
applications of pillared clays but hardly any research concentrating on high-resolution
techniques such as AFM or TEM to study the pillar structure and its bonding to different
types of clay layers. Current literature does not show any publication on the use of XPS
as a technique to learn more about pillared clays.
52
This type of research based on the use of advanced techniques for studying clay
products will provide a better understanding of the structure of pillared clays, further the
relationship between the pillar structure and bonding mechanism to the silicate structure
and the final catalytic properties of the pillared clays will be investigated.
1.6 Aims and objectives
The aims of this study are: 1) to develop a more efficient, less waste producing and
less time consuming method for the preparation of pillared clays, 2) to gain a better
understanding of the structure of pillared clays, and 3) to obtain a better understanding of
the bonding mechanisms between the pillars and the silicate structure. As the pillared
clay structure only varies along the c axis and in the interlayer region, this study will be
focused mainly on the cross sections of the clays. For this reason, the similarity of the
structures of Ga and Al pillars will be taken into account when preparing pillared clays
for studies with TEM and XPS. A new method of preparing TEM samples in cross
section will be developed for use with X-ray mapping and microanalysis.
Characterisation of the morphology of pillared montmorillonite with electron microscopy
including scanning electron microscopy, microanalysis, X-ray mapping and transmission
electron microscopy will be compared with the results from X-ray photoelectron
spectroscopy.
The objectives of the study are to obtain a better understanding of the pillar structure
and the bonding of the pillars to the silicate structure. This will be achieved by direct
methods, such as TEM, and indirect methods such as XPS and XRD. The study will also
look at the binding energies of various atoms in different types of clays, in particular Si,
53
Al and O and how these binding energies change upon the introduction of the Ga and Al
pillars. This will help to better understand the results from electron microscopy to which
will be useful to determine the effects of pillars and clay type on the final structure with
emphasis on Al13 and Ga13 pillared montmorillonites.
54
1.7 References
Aceman, S., Lahav, N. and Yariv, S., 1997. XRD study of the dehydration and
rehydration behavior of Al-pillared smectites differing in source of charge. J.
Therm. Anal., 50(1-2): 241-256.
Aceman, S., Lahav, N. and Yariv, S., 2000. A thermo-XRD study of Al-pillared smectites
differing in source of charge, obtained in dialyzed, non-dialyzed and washed
systems. Appl. Clay Sci., 17(3-4): 99-126.
Auer, H. and Hofmann, H., 1993. Pillared clays: characterization of acidity and catalytic
properties and comparison with some zeolites. Appl. Catal., A, 97(1): 23-38.
Bagshaw, S.A. and Cooney, R.P., 1993. FTIR spectroscopic studies of surface-site probe
species on metal oxide pillared clay surfaces. Proc. SPIE-Int. Soc. Opt. Eng., 2089
(9th International conference on fourier transform spectroscopy, 1993): 162-3.
Bagshaw, S.A. and Cooney, R.P., 1995. Preparation and Characterization of a Highly
Stable Pillared Clay: GaAl12-Pillared Rectorite. Chem. Mater., 7(7): 1384-9.
Baiker, A., 1996. Heterogeneous catalysis. From fundamentals to reaction engineering.
Chimia, 50(3): 65-73.
Bailey, S.W., 1988. Chlorites: structures and crystal chemistry. In: Hydrous
phyllosilicates (exclusive of micas). Rev. Miner., 19, 1 pp.
Baksh, M.S., Kikkinides, E.S. and Yang, R.T., 1992. Characterization by physisorption of
a new class of microporous adsorbents: pillared clays. Ind. Eng. Chem. Res.,
31(9): 2181-9.
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In the case of this chapter:
THE DISTRIBUTION OF Ga IN Ga-PILLARED MONTMORILLONITES: A TRANSMISSION ELECTRON MICROSCOPY AND MICROANALYSIS STUDY
Loc Duong, Thor Bostrom, Theo Kloprogge, and Ray Frost
Published in Microporous and Mesoporous Materials 2005, 82, 165-172
Contributor Statement of contribution*
Loc Duong wrote the manuscript, designed experiments, conducted experiments, data analysis, data interpretation
Date
Thor Bostrom
aided with data analysis and interpretation
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72
CHAPTER 2
2.0 THE DISTRIBUTION OF Ga IN Ga-PILLARED
MONTMORILLONITES: A TRANSMISSION
ELECTRON MICROSCOPY AND
MICROANALYSIS STUDY
Loc Duong1,2*, Thor Bostrom1,2, Theo Kloprogge1, and Ray Frost1
Published in. Microporous and Mesoporous Materials 2005, 82, 165-172
Loc Duong, Inorganic Materials Research Program, School of Physical and Chemical
Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Qld 4001,
Australia
Thor Bostrom, Analytical Electron Microscopy Facility, Queensland University of
Technology, GPO Box 2434, Brisbane, Qld 4001, Australia
Theo Kloprogge, Inorganic Materials Research Program, School of Physical and
Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane,
Qld 4001, Australia
Ray Frost, Inorganic Materials Research Program, School of Physical and Chemical
Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Qld 4001,
Australia
73
2.1 Abstract
The distribution of Ga in the interlayer of montmorillonite pillared with a Ga13
polyoxocation complex has been studied by transmission electron microscopy, energy-
dispersive X-ray microanalysis (EDX), X-ray mapping and powder X-ray diffraction in
combination with N2 adsorption-desorption. To view the clay layers by TEM, the pillared
clay was embedded in Spurrs resin in a preferred orientation, and sectioned with an
ultramicrotome perpendicular to the layers. Montmorillonites pillared with Al13 and
Al12Ga complexes were also prepared for microanalysis in the TEM. The Ga X-ray peaks
could be easily distinguished in the EDX spectra, allowing concentrations relative to
other elements to be determined. Elemental X-ray maps for Ga, Si and Al in the Ga13
pillared clay cross-sections demonstrated that the Ga was homogeneously distributed
throughout the crystal thickness. Comparison of the analytical data with that from the
Al13 and Al12Ga pillared clays and the starting material suggested that an approximately
constant amount of the intercalated species per amount of Si in the clay became
incorporated into the structure in each case. Calculation of the formula for the Ga-
pillared montmorillonite showed that 0.89 Ga is present per formula unit containing 8
(Si+Al), which is equivalent to 20 silicate rings, each consisting of 6 tetrahedra, for every
Ga13 pillar. The actual dimension of the pillar, based results from the elemental analyses
and XRD is 8.7Å and the mean distance between the pillars is 44.3Å, which is in good
agreement with the average pore size of 39Å obtained by N2 adsorption-desorption
measurements. This study shows a new approach for obtaining more detailed information
on the pillars in pillared clay by combining analytical data from X-ray microanalysis
with measurements by XRD and N2 adsorption-desorption.
74
Keywords: Ga13, Montmorillonite, Pillared clay, Textural properties, Transmission Electron Microscopy
2.2 Introduction
Pillared montmorillonites are microporous materials, obtained by ion exchange of
montmorillonites with highly charged metallic species followed by a calcination process,
that in the last 25 years have been developed as a new class of catalysts [1-5]. Producing
suitable pillared montmorillonites for catalytic applications requires detailed
understanding of the structure of the starting clay, the pillaring agent, and the size, shape
and location of the oxidic pillars in the final products. Although extensive research has
been undertaken in the field of pillared clay structures [1, 6-8], the complete structure of
pillared clays especially the location, structure and bonding to the clay layers of the oxide
pillars is still unknown.
Montmorillonites pillared with different polyoxocations have been prepared and
studied for many years [1]. Al13 montmorillonites are the most common pillared clays [9],
mainly because the Al polyoxocation gives a large basal d-spacing and, together with the
very similar Al12Ga pillared montmorillonites, are quite stable at high temperatures, up to
about 750oC. The structures of Al13 and Ga13 are very similar with both having a Keggin
structure in which a central AlIVO4 or GaIVO4 is surrounded by twelve AlVI octahedra with
water and hydroxyl groups [10-15] resulting in similar basal d-spacings in the final
pillared clays.
75
Transmission electron microscopy (TEM) has provided the necessary spatial
resolution for studying the microstructure of clays down to the lattice level, but has
required specific sample preparation procedures to achieve this. A preparation method for
studying smectite layers by TEM has been discussed by Kim et al. [16]. TEM together
with energy-dispersive X-ray spectrometry (EDX) has allowed chemical analysis of small
areas down to about 20 nm and X-ray mapping of regions of a few hundred nanometers.
This combination of structural and chemical analysis in the TEM is a powerful tool for
studying complex, fine-grained clay minerals, and in particular pillared clays. However
the achievable analytical spatial resolution may be limited by the electron beam
sensitivity of some specimens. Ma et al. [17] used EDX in a TEM to study the loss of
certain elements from a clay structure. The diffusion of alkali elements and higher atomic
number elements (Fe, Ti) from clay minerals was found to be associated with crystal
habit and instrumentation conditions. More specimen damage due to the electron beam
was seen when the crystals were viewed in the plane perpendicular to the (001) direction
than in the plane parallel to (001). The loss of elements may be reduced by using a lower
beam current and a larger analysis area [17]. Crozier et al. [18] used analytical electron
microscopy to confirm the location of Zr pillars in Zr-pillared montmorillonite. The Zr
pillars were found to have an irregular shape and distribution in the silicate layers [18].
Montmorillonite pillared with Ga13 has some advantages over that pillared with Al13
for analytical TEM studies. As Ga has a higher atomic number (31) than Al, the
intercalated Ga may potentially improve contrast in TEM images. Further, the element
can be clearly detected by X-ray microanalysis without confusion with the Al in the clay
structure. For comparative studies Al13 and Al12Ga pillared clays were also prepared. The
76
pillared montmorillonites were examined and analysed in the TEM mainly in cross-
section, in other words with the c-axis oriented perpendicular to the electron beam. In this
paper the results from transmission electron microscopy, EDX microanalysis, powder X-
ray diffraction and N2 adsorption-desorption measurements have been used to deduce the
distribution of Ga in the structure of Ga13 pillared montmorillonite. It is shown that an
approximately constant proportion of the intercalated species is incorporated into the clay
structure in pillaring, and it is possible to calculate an average size and distribution of the
pillars.
2.3 Materials and methods
2.3.1 Starting materials
The starting materials used for this study were ≤ 2 μm fractions of Wyoming
montmorillonite SWy-2, and Miles montmorillonite from Queensland, Australia. The
Miles montmorillonite has a significantly higher CEC than Swy-2. All samples were
saturated with sodium through exchange with 1 M NaCl for 8 hours. The clays were
washed five times with deionised water in order to remove residues of NaCl. A detailed
description of the Miles material and the Al13-pillaring procedure have been provided by
Kloprogge et al. [19]. Miles montmorillonite was used to prepare the Al13 and Al12Ga
pillared clays and SWy-2 montmorillonite was used to prepare the Ga13 pillared clay. The
preparation of the Al12Ga and Ga13-pillared clays was analogues to that of the Al13-
pillared clay. A 0.1M solution of NaOH was added to Ga(NO3)3 at a rate of 0.01 ml/min
using a peristaltic pump under vigorous stirring at room temperature. The OH/Ga ratio
was 2:1. The Al13, Al12Ga and Ga13 solutions were added to the aqueous clay suspensions
77
under continuous stirring for a period of four hours. The suspensions were then allowed
to stand for several days. The pillared clays were washed 5 times with deionised water
using a centrifuge. The samples were allowed to dry in air at ambient temperature.
Finally, the samples were heated at 2°C/min and calcined at 450°C for 8 hours.
2.3.2 X-ray diffraction
X-ray diffraction (XRD) was used to check for the intercalation process of Ga into the
clay structure before and after calcination by observing the changes in the (001) spacings.
For powder XRD, the sample was ground and mixed with ethanol, deposited on a low
background plate and dried at room temperature. Preferential orientation of the clay
platelets is very common under these conditions, thus enhancing the (00l) reflections
relative to other reflections. XRD patterns were collected using a PANalytical X’Pert Pro
diffractometer with a rotating anode source and a diffracted beam curved graphite
monochromator and CuKα radiation. Scans were made using a 0.05o step size at
0.5sec/step.
2.3.3 Sample preparation for Transmission Electron Microscopy
Smectites, due to their ability to absorb and desorb water and exchange cations, are
very sensitive to the method used to prepare them for examination in the TEM and
therefore care must be taken not to introduce preparation artefacts. For viewing the clay
particles mainly parallel to the c-axis, a dilute suspension of montmorillonite in 70%
alcohol was briefly ultrasonicated and a small drop of the suspension was placed on a thin
carbon film on a TEM copper grid, allowed to dry and coated with a thin carbon layer to
improve stability under the beam.
78
In order to observe the clay in a direction perpendicular to the c-axis so that the layers
could be viewed in cross-section, the clay was embedded in Spurrs resin [20] for
ultramicrotoming. The morphology, swelling properties, water absorption, and reaction
with the resin have to be taken into account when preparing smectite samples for TEM.
Because of its low viscosity, Spurrs has long been used as an embedding agent for
biological and material samples for electron microscopy, and was used here to obtain
good penetration into the clay material. However the resin is intolerant of moisture in the
sample, and therefore the samples had to be adequately dried before embedding. Figure
2.1 shows the steps used in the preparation of cross-sections of the pillared clays. Pillared
montmorillonite was diluted with water and allowed to settle for about one week. The
water was removed leaving the clay particles preferentially aligned with the bottom of the
container. The sample was dried at 60-100oC for two weeks before addition of the resin.
After polymerisation overnight at 60oC, the small resin plug was removed from the base
of the container, rotated 90° and sectioned with a diamond knife using a Reichert
ultramicrotome to produce cross-sections of the embedded particles. The sections were
60-80 nm in thickness. The starting montmorillonites were also prepared for
microanalysis, but as these materials had not been calcined they was first dehydrated with
alcohol and acetone to remove any residual water before impregnation with Spurrs resin.
79
STAGE 1
STAGE 2
STAGE 3
Clay in suspension, clay particles deposit slowly at the bottom of the container with flat grains mainly parallel to the bottom
Oriented clay embedded in Spurrs resin
Cross sections cut using an ultramicrotome
Fig. 2.1 Preparation of cross sections of a clay sample
for TEM
80
2.3.4 Transmission Electron Microscopy
Specimens were examined in a Philips CM200 transmission electron microscope fitted
with a LaB6 cathode and operated at 200kV. For measurements of lattice spacings and
electron diffraction patterns, TEM negatives were scanned at 600 or 1200dpi and
measurements carried out on the digital images using image analysis software. Energy-
dispersive X-ray microanalysis and X-ray mapping was carried out mainly in scanning
transmission (STEM) mode using a Link thin-window X-ray detector and Link ISIS 300
microanalysis system (Oxford Instruments, UK). Quantitative calculations of element
concentrations and atomic ratios were carried out using a thin-film matrix correction
procedure, in which the total concentrations are normalised to 100%. For these
calculations, the density of the material was taken as 3.0 g.cm-3 and the specimen
thickness for each analysis was estimated from STEM images and the Si X-ray intensity.
2.3.5 Nitrogen adsorption-desorption
The surface areas of the starting montmorillonite and Ga13 pillared montmorillonite
were calculated by the BET method using N2 adsorption-desorption on a Micromeritics
ASAP 2010 at a partial pressure range of 0.06 to 0.30. The pore size distribution and pore
volume were calculated using the Tristar software.
81
3 8 13 18 23
degrees 2θ Cukα
Cou
nts
14 Å
19.9 Å
17.9 Å
Ga13 exchanged
Ga13 calcined
Starting montmorillonite
Fig. 2.2 XRD patterns of:
(a) starting Wyoming Swy-2 montmorillonite
(b) montmorillonite exchanged with Ga13 showing an interlayer spacing of 19.9 Å
(c) Ga13 pillared montmorillonite with a spacing oft 17.9 Å
(a)
(b)
(c)
82
2.4 Results and discussion
X-ray powder diffraction (XRD) patterns of the starting montmorillonite and Ga13
pillared montmorillonite demonstrated that the Ga had been pillared successfully. As the
Ga is intercalated into the structure the layers of the montmorillonite are propped apart,
and the basal spacing (the d-spacing along the c-axis, or 001 reflection) increases from
about 14Å to 19.9Å (Figure 2.2). After calcination at 450oC the d001 spacing reduced to
17.9Å. The clean pattern of the intercalated clay indicated that the intercalation process
had completed and that no non-pillared montmorillonite remained in the sample.
Figure 2.3a shows the laminar structure of a single grain of Al12Ga pillared
montmorillonite, prepared by simple deposition from suspension onto a TEM grid.
Figures 2.3b-d are high magnification TEM images of resin embedded sections of the
Ga13, Al12Ga and Al13 pillared montmorillonites, together with electron diffraction
patterns showing the (001) diffraction spots. The images also show detailed views of
lattice fringes and corresponding spacings in specific areas. The observed lattice fringe
spacings from TEM of the pillared clays ranged from 12.9 to 18.2 Å, with a mean value
of about 15.2 Å. However, it is clear from the micrographs that the fringe spacings can
vary quite considerably, particularly where there is pronounced curvature of the crystals
(Figure 2.3c, arrow). Two different fringe spacings can be observed in the detailed view
in Figure 3d. This variability should be reflected in some broadening of the (001) peak in
the XRD pattern and this is what is observed (Figure 2.1). There is some suggestion that
the layers are more clearly defined in the Al12Ga pillared montmorillonite, and this may
be due to the fact that the central GaIV atom fits much better in the Keggin-type complex,
thereby not only increasing the thermal stability [9], but also the stability of the pillared
83
clay under the electron beam in the TEM. We did observe a noticeable loss of structure in
these materials due to beam damage after a short period of TEM viewing, especially at
high magnifications.
Measurements of the (001) spacing from electron diffraction patterns of cross-sections
of the pillared clays gave a mean value of 15.6 Å (range 14.4 – 17.4 Å), which is
consistent with the spacings observed in the micrographs. The patterns also showed fine
arcs at 4.45 Å, corresponding to (100) reflections, and in one case spots at 2.29 Å,
probably (113) reflections from an adjacent crystal. Overall, the electron diffraction
patterns were most consistent with the Montmorillonite-15A structure for a Wyoming
montmorillonite (ICDD powder diffraction database #29-1498), for which d001, d100 and
d113 are 15.542, 4.473 and 2.311 Å respectively. However both the observed lattice
spacings in the micrographs and the measured (001) spacings from the electron
diffraction patterns are on average lower than the basal spacing of 17.9 Å measured by
XRD for the Ga13 pillared clay. This difference may arise from the different preparation
methods used. The XRD measurements were made on powdered material in ambient air,
while the TEM measurements were made from thin sections of resin-embedded clay in a
high vacuum. The TEM preparation required extensive drying of the clay samples prior
to resin embedding and polymerisation and this may explain the differences observed.
84
Fig. 2.3 TEM image of:
(a) a grain of Al12Ga pillared montmorillonite; and images and electron diffraction
patterns from sectioned material
(b) Ga13 pillared montmorillonite
(c) Al12Ga pillared montmorillonite and
(d) Al13 pillared montmorillonite
85
Figure 2.4 shows an X-ray intensity map for Al, Si and Ga in a thin cross-section of a
single grain of the Ga13 pillared clay. The map demonstrates that the distribution of Ga is
closely related to that of Al and Si, and that Ga is present throughout the grain thickness.
The estimated electron probe diameter in STEM mode under the conditions used was
about 4 nm, consequently there is insufficient spatial resolution to distinguish the layers
directly. To measure the amount of Ga in the Ga13 pillared clay, eight EDX analyses were
taken from individual small grains or very small clusters of grains. Ga was present in all
these spectra in roughly equivalent amounts. The other pillared clays were analysed in a
similar manner. EDX spectra from the three pillared clays, compared in each case with a
spectrum from the starting montmorillonite, are shown in Figure 2.5. The Ga K and L X-
ray lines are clearly discernible even in the Al12Ga pillared material, and excess Al is
evident in the clays pillared with Al13 and Al12Ga. Both atomic ratios to silicon and
concentrations of the elements were calculated from the spectra. The ratio to Si was used
since Si is a relatively constant element within the structure and is not affected by the
pillaring process. The mean concentrations from EDX analyses of the three pillared clays
as well as from the starting materials are listed in Table 2.1, and do show some variation
between the different pillared and starting clays analysed.
From the spectra, the mean atomic ratio of Ga to Si was 0.024 ± 0.001 (SD, n = 10) for
the Al12Ga pillared clay, and 0.235 ± 0.015 (SD, n = 8) for the Ga13 pillared clay. The
ratio of total Al/Si was 0.646 in the Al13 pillared material, as compared to a mean of
0.373 in the Miles starting clay, therefore the overall Al13/Si ratio was 0.273. For the
Al12Ga pillared material, the total (Al+Ga)/Si ratio was 0.608, which gives an overall
86
Al12Ga/Si ratio of 0.235 after allowing for the Al in the starting material. Thus the ratios
of pillared element to Si were 0.273, 0.235 and 0.235 respectively in the three pillared
clays, suggesting that a roughly constant proportion of the pillared element is
incorporated into the structure.
A more reliable correction for the Al content in the tetrahedral and octahedral layers is
obtained by calculating the stoichiometric formula of the clay. This has been done in
Table 2.1 for the analysed clays using the mean element concentration data from the X-
ray microanalyses. The analyses were calculated into a chemical formula based on a net
negative charge of 44 (20 oxygen atoms + 4 hydroxyls). The calculated formula reflects
the chemical analysis of SWy-2 montmorillonite well and is very close to the
composition described for this CMS source clay [21]. For the Ga13 pillared clay, the
formula indicates an average of 0.89 Ga atoms per structural unit.
87
Fig. 2.4 Elemental X-ray maps for Ga, Si and Al from a cross section of a single grain of Ga13
pillared montmorillonite
88
Fig. 2.5 EDX spectra from analyses in the TEM of small grains of:
(a) Ga13 pillared
(b) Al12Ga pillared
(c) Al13 pillared montmorillonites
The spectra are shown overlaid with a spectrum from the starting material.
The C and Cu peaks derive from the resin or thin carbon coating and the TEM grid material
respectively
89
Element
Starting Mont.
(Swy-2)
Starting Miles Mont.
Ga13 Pilc Swy-2
Al13-Pilc Miles
Al12Ga- Pilc Miles
Na 1.23 2.15 0 0 0.20 Mg 1.49 1.71 0.3 1.21 1.07 Al 10.68 9.86 10.00 13.87 13.82 Si 27.12 26.66 25.15 25.85 29.41 K 0.06 0.22 0.02 0 0.03 Ca 0.09 0.64 0.15 0 0.09 Ti 0.10 0.05 0 0.25 0.18 Fe 2.78 2.39 2.55 2.26 2.88 Ga 0 0 2.85 0 0.72
Calculated formula based on 22 oxygens
Starting montmorillonite Swy-2
(Na0.14K0.08Ca0.04)(Mg0.49Fe3+0.40Ti0.04Al3.09)(Si7.87Al0.13)O20(OH)4.nH2O
Ga13 pillared montmorillonite Ga0.89(Mg0.60Fe3+
0.21Ti0.02Al3.09)(Si7.87Al0.13)O20(OH)4.nH2O
Starting Miles montmorillonite (Na0.95K0.02Ca0.084)(Mg0.60Fe3+
0.12Ti0.005Al3.11)(Si7.95Al0.05)O20(OH)4.nH2O
Al13 pillared montmorillonite Al1.46(Mg0.65Fe3+
0.18Ti0.010Al3.11)(Si7.95Al0.05)O20(OH)4.nH2O
Al12Ga pillared montmorillonite Al2.28Ga0.19(Mg0.40Fe3+
0.78Ti0.017Al0.91)(Si7.95Al0.05)O20(OH)4.nH2O
Table 2. 1: Characteristic concentrations (single analysis) in weight % from X-ray
microanalyses in the TEM of the starting and the Ga13-, Al12Ga- and
Al13-pillared montmorillonites (top), and the formula calculation based
on 22 oxygens (bottom)
90
From the information above obtained by EDX analysis and the structure of the
montmorillonite, it is possible to calculate the size of the Ga pillars in the Ga13 pillared
clay. From the literature the thickness of a single clay layer (consisting of one octahedral
sheet sandwiched between two tetrahedral sheets) is about 9.8 Å. A basal spacing for the
Ga pillared clay of 18.5 Å then results in a height of the Ga pillars of around 8.7 Å, which
is close to the value of 9.8 Å for the hydrated complex in solution taking into account the
decrease in size during the calcination in which the complex looses all its water and
hydroxyl groups [22, 23]. The formula calculated from the EDX analyses shows 0.89 Ga
per unit formula, which contains about 8 (Si+Al). There are 6 tetrahedra needed to form a
silicate ring, so a total of 19.45 rings are needed to accommodate one Ga13 pillar. If we
consider a total number of 20 silicate rings per pillar this will result in 10 rings of the top
layer and another 10 rings of the bottom layer. From the literature the dimension of the
silicate ring is about 5.3 Å [24] so 10 rings correspond to 53 Å. The Ga13 shape being a
Keggin structure can be considered to be equi dimensional so it is possible to use the
height of Ga13 as indicated from XRD measurements of the basal spacing for the size of
the pillar. Then the actual dimension of the pillars is 8.7 Å and the distance between the
pillars is 53Å – 8.7Å = 44.3Å. The N2 adsorption-desorption measurements show a quite
homogeneous pore size distribution with an average pore size of 39 Å (Figure 6), and the
value of 44.3 Å calculated above is in very good agreement with this mean pore size
91
00.0010.0020.0030.0040.0050.0060.0070.0080.009
20 40 60 80 100
Pore diameter (Å)
Pore
vol
ume
(cm
3 /g)
Fig. 2.6 Pore size distribution of Ga13 pillared montmorillonite
92
This calculation is based on average dimensions and it is clear from the TEM images
and electron diffraction measurements that the basal spacing does vary within the
structure, so it would be expected that the actual distribution of the pillars within the
interlayer space may not be homogeneous, but may be analogous to that found for Zr
pillars by Crozier et al. [18].
2.5 Conclusions
Wyoming SWy-2 montmorillonite has been used to produce Ga13 pillared clay with a
mean basal spacing of about 17.9Å, as determined by XRD. This material was prepared
for analysis by TEM by orienting the clay particles, embedding them in Spurrs resin, and
then ultramicrotoming to produce cross-sections of the clay grains. For comparison Al13
and Al12Ga pillared montmorillonites were prepared in a similar manner. Ga13 pillared
montmorillonite appears to have a similar structure to the Al13 and Al12Ga pillared
materials, but has the advantage that the Ga incorporated in the clay can be easily
analysed by energy-dispersive X-ray microanalysis without confusion with the Al in the
structure. Detailed X-ray maps of Ga, Si and Al in cross-sections of the clay grains
showed a good correlation between the three elements and also indicated that the Ga was
present throughout the structure. Direct measurements of basal layer spacings from TEM
micrographs, as well as determinations of spacings from electron diffraction patterns,
gave layer spacings that were about 10% lower than the values expected from XRD
measurements. However this difference may have been mainly due to the drying, resin
embedding and polymerisation used for processing the specimens for TEM.
93
By allowing for the average amount of Al in the structure of the starting clay material,
it is estimated from the EDX microanalyses of the three clays that an approximately
constant amount of the intercalated elements is incorporated into the montmorillonite
structure. The estimated atomic fractions of the total intercalated species to silicon were
0.273, 0.235 and 0.235 for the Al13, Al12Ga and Ga13 pillared clays respectively. By
detailed calculation of the clay stoichiometries from the EDX data, it was shown that 0.89
Ga atoms are present per formula unit, which indicates that there are 20 silicate rings
consisting of 6 tetrahedral each per Ga13 pillar. Thus the average distance between the
pillars has been calculated to be 44 Å. This value is close to the average pore size of 39 Å
that was determined from N2 adsorption-desorption measurements of the pillared clay. As
the ratio of Al12Ga to Si was similar to that for Ga13/Si, we expect that the distribution of
Al12Ga pillars is similar to that of Ga13. The ratio Al13/Si was somewhat higher than for
Al12Ga and Ga13, hence the average distance between the Al13 pillars should be somewhat
less than the 44 Å estimated for the Ga13.
The information from microanalyses in the TEM, in combination with data from XRD
and N2 adsorption-desorption measurements, has allowed us to determine some
fundamental information about the distribution of the pillars in the pillared clay. The
finding that nearly one pillared atom is incorporated per structural unit in the clay
suggests that a specific bonding site may be involved in the pillaring process within the
interlayer. Further details of the pillaring mechanism are currently being investigated
using other techniques.
94
2.6 Acknowledgements
We wish to thank Mr Tony Raftery for his expert assistance with the XRD
measurements, and members of the clay group in the Inorganic Materials Research
Program for helpful advice and discussion. We acknowledge financial support from the
Inorganic Materials Research Program, Faculty of Science, Queensland University of
Technology.
95
2.7 References
1. J. T. Kloprogge, J. Porous Mater. 5 (1998) 5.
2. S. M. Bradley, R. A. Kydd and K. K. Brandt, Stud. Surf. Sci. Catal. 73 (1992)
287.
3. S. M. Bradley and R. A. Kydd, J. Catal. 142 (1993) 448.
4. R. T. Yang, J. P. Chen, E. S. Kikkinides, L. S. Cheng and J. E. Cichanowicz, Ind.
Eng. Chem. Res. 31 (1992) 1440.
5. A. Vaccari, Catal. Today 41 (1998) 53.
6. T. J. Pinnavaia, NATO ASI Ser., Ser. C 165 (1986) 151.
7. F. Figueras, Catal. Rev. - Sci. Eng. 30 (1988) 457.
8. W. Jones, Catal. Today 2 (1988) 357.
9. S. M. Bradley, R. A. Kydd, R. Yamdagni and C. A. Fyfe, Synth. Microporous
Mater. (1992) 13.
10. S. M. Bradley, R. A. Kydd and R. Yamdagni, Magn. Reson. Chem. 28 (1990)
746.
11. S. M. Bradley, R. A. Kydd and R. Yamdagni, J. Chem. Soc., Dalton Trans. (1990)
2653.
12. A. Bellaloui, D. Plee and P. Meriaudeau, Appl. Catal. 63 (1990) L7.
13. A. V. Coelho and P. G., Appl. Catalysis 77 (1991) 303.
14. F. Gonzalez, P. C., B. I. and M. S., J. Chem. Soc. (1991) Chem. Commun.
15. E. Montarges, L. J. Michot and P. Ildefonse, Microporous and Mesoporous Mater.
28 (1999) 83.
16. J.-W. Kim, D. R. Peacor, D. Tessier and F. Elsass, Clays Clay Miner. 43 (1995)
51.
17. C. Ma, D. Fitzgerald, R. A. Eggleton and D. J. Llewellyn, Clays Clay Miner. 46
(1998) 301.
18. P. A. Crozier, M. Pan, C. Bateman, J. J. Alcaraz and J. S. Holmgren, Clays Clay
Miner. 47 (1999) 683.
19. J. T. Kloprogge, R. Evans, L. Hickey and R. L. Frost, Appl. Clay Sci. 20 (2002)
157.
96
20. A. R. Spurr, Journal of Ultrastructural Research 26 (1969) 31–43.
21. A. R. Mermut and A. F. Cano, Clays Clay Miner. 49 (2001) 381.
22. M. L. Occelli, A. Auroux and G. J. Ray, Microporous Mesoporous Mater. 39
(2000) 43.
23. M. L. Occelli, J. A. Bertrand, S. A. C. Gould and J. M. Dominguez, Microporous
Mesoporous Mater. 34 (2000) 195.
24. W. A. Deer, R. A. Howie and J. Zussman, An introduction to the Rock-Forming
Minerals, 2nd ed., Addison Wesley Longman Ltd., Harlow, 1996.
Statement of Contribution
The authors listed below have certified* that: 1. they meet the criteria for authorship in that they have participated in the conception,
execution, or interpretation, of at least that part of the publication in their field of expertise; 2. they take public responsibility for their part of the publication, except for the responsible
author who accepts overall responsibility for the publication; 3. there are no other authors of the publication according to these criteria; 4. potential conflicts of interest have been disclosed to (a) granting bodies, (b) the editor or
publisher of journals or other publications, and (c) the head of the responsible academic unit, and
5. they agree to the use of the publication in the student’s thesis and its publication on the
Australasian Digital Thesis database consistent with any limitations set by publisher requirements.
In the case of this chapter:
AN IMPROVED ROUTE FOR THE SYNTHESIS OF AL13PILLARED MONTMORILLONITE CATALYSTS
Loc V. Duong, Jacob T. Kloprogge, Ray L. Frost, and Job A. Veen
Published in Journal of microporous and mesoporous materials 2007, 14, 71-79
Contributor Statement of contribution*
Loc Duong wrote the manuscript, designed experiments, conducted experiments, data analysis, data interpretation
Date
Jacob Kloprogge aided with data analysis and interpretation
Ray Frost editing
Job Veen Aid with catalytic testing
Principal Supervisor Confirmation I have sighted email or other correspondence from all Co-authors confirming their certifying authorship and. _______________________ ____________________ ______________________ Name Signature Date
98
CHAPTER 3
3.0 AN IMPROVED ROUTE FOR THE
SYNTHESIS OF AL13PILLARED
MONTMORILLONITE CATALYSTS
Loc V. Duong*1, Jacob T. Kloprogge1, Ray L. Frost1, and Job A. Veen2
Published in Journal of microporous and mesoporous materials 2007, 14, 71-79
Loc Duong, Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Qld 4001, Australia
Theo Kloprogge, Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Qld 4001, Australia
Ray Frost, Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Qld 4001, Australia
Rob van Veen, Shell International Chemicals, B.V., Shell Research and Technology Centre Amsterdam, Badhuisweg 3, 1031 CM Amsterdam, The Netherlands
99
3.1 Abstract
The distribution of Al13 pillars and the process of intercalation in montmorillonite
can be enhanced through the application of an ultrasonic treatment. This paper
describes the results of ultrasonic treatment in the preparation of Al-pillared
montmorillonite with and without prior exchange with Na+. The resulting materials
have been charactersed by X-ray diffraction, N2 adsorption/desorption, Scanning
Electron Microscopy and Atomic Force Microscopy. The catalytic activity was tested
with the n-heptane hydroconversion test. Optimum results were obtained after
ultrasonic treatment up to 20 minutes without prior Na-exchange before the Al13
intercalation. Longer ultrasonic treatment resulted in partial destruction of the
pillared structure. The pore size diameter also increased with increasing ultrasonic
treatment up to 20 minutes with values in the range of 4 nm. This behaviour can be
explained by the loss of the typical house of cards structure after prolonged ultrasonic
treatment. AFM showed that the pillars in the interlayer of the montmorillonite
resulted in a distortion of the tetrahedral sheets of the clay. At atomic scale resolution
it was clear that the pillar distribution is not homogenous, confirming earlier results
using high resolution TEM. The effects of ultrasonic treatment on the catalytic activity
is rather limited, although the pillared clays prepared with short ultrasonic
treatments of 5 and 10 minutes performed slightly better.
Key words: AFM, Al13, pillared clay, montmorillonite, n-heptane conversion, N2
adsorption/desorption, SEM, ultrasonic treatment.
100
3.2 Introduction
Acid treated montmorillonite clays were the catalysts commonly initially used for
cracking reactions of hydrocarbons in the 1930’s [1]. These acid-treated smectites
catalysts were replaced after World War II with a more stable synthetic silica-alumina
type which also gave better product distribution [1]. The emergence of zeolites in the
1960's revolutionised the process mainly because of their high activity, selectivity and
resistance to collapse when treated at high temperatures [2, p30]. Nowadayds, ZSM-5
and Y-zeolite are among the most popular heterogeneous catalysts in the
petrochemical industry. The interest now is in producing a catalyst with a larger pore
size compared to zeolite (∼8 Å) so as to handle the cracking of heavier crude oil. The
use of pillared clays has received considerable attention [3]because of their ability to
achieve large pore sizes, but factors such as the large volumes of water and chemicals
involved in the preparation, the thermal stability and coking properties still need to be
overcome.
Altering the preparation of a PILC can have dramatic effects on properties such as
thermal stability and acidity [3-5]. This area also has received considerable attention
with many authors who are looking at ways to economise the process for commercial
viability. Current problems in preparation are time and energy costs, water usage and
preparation of the expanded clay suspensions.
The preparation of a pillared clay normally starts with an cation exchange step
where the hydrated interlayer cation of the smectite clay is exchanged for sodium.
This way an increase in swellability is achieved, making it easier to incorporate those
large metal polyoxocomplexes. This cation exchange involves the use of large
101
amounts of water and sodium salts. It would be a significant improvement if this step
could be altered into a less waste producing step.
The use of ultrasonics for the cation exchange step has been reported [6, 7]. A Ca-
montmorillonite was intercalated with the Al13 complex using ultrasonic treatment
over a number of time periods. The most intense and sharpest peaks in the XRD
patterns were observed for the calcined sample that had been left in the ultrasonic bath
for 20 minutes. The same authors, in a later study [7], described how the
exchangeable cations present in the smectite affected the ultrasonic treatment. They
converted the Ca-montmorillonite to Na+ and La3+ forms by ion exchange. This gave
exchangeable cations with valencies of +1, +2 and +3. The optimum times for
ultrasonic treatment were found to be 5 minutes for the Na-exchanged form, 20
minutes for the Ca-exchanged form and 80 minutes for the La-exchanged form. The
increase in time was ascribed to the higher charge ions being more tightly bound to
the clay layers. This method of intercalation has a number of advantages that help to
make large-scale production of pillared clays more viable. Firstly, it reduces the time
needed from several hours to less than 30 minutes. It also requires no heat for the
process, thus saving in costs and reducing the safety risks, although some safety issues
arise with ultrasonics that would need to be addressed. Finally, the clay suspension
required don’t have to be cation exchanged and can be more concentrated compared
to conventional methods, thus using less water, sodium salts and space.
This paper describes a detailed study on the use of ultrasonic treatment of a number
of smectite clays for the intercalation with Al13 Keggin complexes.
102
3.3 Experimental
3.3.1 Starting materials
The starting materials used for this study were ≤ 2 μm fractions of Cheto
montmorillonite SAz-1, and Miles montmorillonite from Queensland, Australia. The
Miles montmorillonite has a significantly higher CEC than SAz-1 (see special issue
nr. 5 of Clays and Clay Minerals, volume 49, 2001 for a detailed characterization of
SAz-1). A detailed description of the Miles material and the conventional Al13-
pillaring procedure have been provided by Kloprogge et al. [8]. Pillaring with Al13 of
non-exchanged and Na-exchanged montmorillonites was executed in an ultrasonic
bath with increasing time intervals from 0 to 30 minutes at room temperature. For all
experiments a clay suspension of 30 % (w/w) in distilled water was prepared under
stirring for 30 minutes prior to the intercalation with Al13. After washing and drying at
room temperature for 24 hours the expanded clays were calcined at 450°C for 2 hours
(heating rate 5°C/min.).
3.3.2 Analytical techniques
3.3.2.1 X-ray diffraction (XRD)
The nature of the resulting material was checked by X-ray powder diffraction
(XRD). The XRD analyses were carried out on a Philips wide angle PW 1050/25
vertical goniometer equipped with a graphite diffracted beam monochromator (Fig.
3.1). The d-values and intensity measurements were improved by application of an in-
house developed computer aided divergence slit system enabling constant sampling
area irradiation (20 mm long) at any angle of incidence. The goniometer radius was
enlarged to 204 mm. The radiation applied was CoKα from a long fine focus Co tube
103
operating at 35 kV and 40 mA. The samples were measured at 50 % relative humidity
in stepscan mode with steps of 0.02° 2θ and a counting time of 2s.
3.3.2.2 Scanning Electron Microscopy (SEM)
Scanning electron microscope (SEM) images were obtained on a FEI Quanta 200
Environmental Scanning Electron Microscope (FEI Company, USA) operated at an
accelerating voltage of 15 kV.
3.3.2.3 Atomic Force Microscopy (AFM)
Sample preparation involved a SiO2 surface for attachment of the clay sheets. An
industry-standard n-type Si wafer with RMS roughness of 0.2 nm covered by a native
oxide layer constituted the surface. The Si surface was exposed to ultrasonic cleaning
with iso-propyl-alcohol, followed by rinses in doubly distilled and deionized water
(DDDW). Specimens of 1 cm2 area were sectioned and attached to standard AFM
mounts. The clay was diluted with DDDW (filtered) and allowed to dry on the Si
surface at room temperature (~23 °C).
104
2.5 7.5 12.5 17.5 22.5Degrees 2 θ
Cou
nts
5 minutes
10 minutes
20 minutes
2.5 7.5 12.5 17.5 22.5
Degrees 2θ
Cou
nts
Non-exchanged - 5min Usound
Non-exchanged - 10min Usound
Non-exchanged - 20min Usound
Na-exchanged - 10min Usound
Na-exchanged - 5min Usound
Na-exchanged - 20min Usound
Fig. 3.1a Non-calcined Al13- montmorillonite SAz-1
Fig. 3.1b Non-calcined Na-exchanged Miles montmorillonite intercalated with Al13
105
2.5 7.5 12.5 17.5 22.5Degrees 2 q
Cou
nts
5 minutes
10 minutes
20 minutes
Fig. 3.1c Non-calcined Miles montmorillonite intercalated with Al13
106
The work was carried out on a JEOL JSPM-4200 system with a 25 μm tube
scanner, with a z-range of ca. 3 μm. The system is based on the detection of the tip-to-
surface forces through monitoring optical deflection of a laser beam incident on a
force-sensing/imposing lever. The analyses were carried out under air-ambient
conditions (temperature of 23°C and 65% relative humidity). The probes were of the
beam-shape variety in order to ensure that only the simple lowest-order bending
modes contributed to the response. Probes were obtained from Ultrasharp NT-MDT.
The characteristics of probes employed in the present study are listed below.
Designation RTip Ar Surface Chem. kN (Nm-1)
A <10 <20° Si-oxide 0.03 RTip = Manufacturers radius of curvature at tip apex; Ar = quoted full tip cone angle;
kN= the force constant of the lever along the z-axis (i.e., normal to the surface plane).
3.3.2.3.1 Operational modes
Contact mode: Frictional images were carried out in constant height mode with a
lever-imposed loading in the range 5-20 nN. The scanning rate in the fast-scan
direction was ca. 3 Hz, and a typical image was composed of 256x256 pixels.
3.3.2.3.2 Data processing
Frictional images were processed by subtraction of background and adjustment of
brightness and contrast. Some images were enhanced through Fast Fourier Transform
processing.
107
2.5 7.5 12.5 17.5 22.5
Degrees 2-Theta
Cou
nts
Sonicated 5 minutes
30 minutes
20 minutes
10 minutes
2.5 4.5 6.5 8.5 10.5 12.5 14.5 16.5 18.5
Degrees 2-Theta
Cou
nts
Sonicated 5 minutes
30 minutes
20 minutes
10 minutes
Fig. 3.2a Al-pillared montmorillonite SAz-1 calcined at 450°C
Fig. 3.2b Al-pillared Miles montmorillonite calcined at 450°C
108
3.3.3 N2 adsorption/desorption
The surface areas of the starting montmorillonite and Al13 pillared
montmorillonites were calculated by the BET method using N2 adsorption-desorption
on a Micromeritics ASAP 2010 at a partial pressure range of 0.06 to 0.30. The pore
size distribution and pore volume were calculated using the Tristar software.
3.3.4 Catalytic testing
The pillared clays were prepared for hydroconversion of n-heptane by loading the
pillared clays with 0.4 wt% Pd by impregnation with tetramine. Catalysts were dried
at 120°C for 16 hours and subsequently reduced in a hydrogen flow (H2 flow rate 2.24
Nml/min, total pressure 30 bar) at 400°C for 2 hours. The conversions were carried
out in a conventional fixed bed reactor under various reaction temperatures to obtain a
constant conversion of 40%. Reaction conditions were: n-heptane/H2 molar ratio of
2.5 4.5 6.5 8.5 10.5 12.5 14.5 16.5 18.5
Degrees 2-Theta
Cou
nts
Sonicated 5 minutes
30 minutes
20 minutes
10 minutes
Fig. 3.2c Al-pillared Na-exchanged Miles montmorillonite calcined at 450°C
109
0.25, total pressure 30 bar, and GHSV = 1020 Nml/(g.h). Effluents were analysed by
on-line gas chromatography. For comparative reasons two commercial catalysts were
treated in a similar fashion as the pillared clays.
3.4 Results and discussion
Conventionally, the starting clay is pre-exchanged with sodium to assist the ion
exchange process that occurs during the intercalation step. Then the Na-exchanged
clay suspension is mixed with the pillaring solution over a time period with heat. This
process can take up to 6 hours to complete as the pillaring solution is added drop-wise
and the mixture is stirred for at least 2 hours at around 80oC. Although this method
has had success in laboratory synthesis of pillared clays, it is not an ideal preparation
technique for large-scale production as large amounts of water and heat are necessary.
Intercalation of Miles montmorillonite, its Na-exchanged form and SAz-1 with
Al13 in an ultrasonic bath resulted in PILCs with interlayer spaces of around 8.5 Å,
taking into account a thickness of 9.8 Å for the 2:1 silicate layers, which compares
well to that of a conventionally prepared PILC (Fig. 3.1). However, experiments at 0
minutes ultrasonic treatment did not give an expanded montmorillonite, the XRD
pattern of a normal montmorillonite was obtained instead. The results showed that the
Na-exchanged PILC retained its XRD peak up to 20 minutes ultrasound treatment. It
also showed no difference between the Na-exchanged form and the non-exchanged
form thus doing away with the need for this preliminary step. The XRD patterns of
the intercalated clay however, did show the formation of another peak at 30 minutes
ultrasound duration, suggesting some loss of regularity in the layer structure. In
general the best results were obtained with the shortest ultrasonic treatments,.i.e. 5 or
10 minutes (Fig. 3.2).
110
The N2 adsorption/desorption isotherms of the pillared clays display a typical
hysteresis loop (Fig. 3.3), consistent with slit-like pores in the pillared clays. The BET
surface areas are the highest for the pillared clays prepared with 5 or 10 minutes
ultrasonic treatment (Table 3.1). Longer treatment does not result in a further increase
and in most cases a significant decrease in surface area, supporting the XRD results.
The change in BET surface area however is not accompanied by any significant
changes in the total pore volume (<144 nm pores), which is on average 0.13 cm3/g for
all pillared clays.
The SEM images show that with increasing the ultrasonic treatment time the house
of cards type structure, where most of the clay particles are in an edge-to-edge or
edge-to-face type orientation is lost and is being replaced with an increasing amount
of face-to-face orientations (Fig. 3.4). This difference in particle orientation can
explain the loss in BET surface area, as a significant part of the external surface is lost
upon face-to-face orientation of the clay particles. This also means that the changes
observed in the XRD are mainly due to the changes in the interlayers of the clay
where the regularity in the pillar distances is the main contributor to the width of the
basal reflections.
111
Fig. 3.3a BET adsorption and desorption isotherms for Al-pillared
montmorillonite SAz-1 after ultrasonic treatment for 5 minutes and calcined at 450°C
112
Fig. 3.3b BET adsorption and desorption isotherms for Al-pillared Miles
montmorillonite after ultrasonic treatment for 5 minutes and calcined at 450°C
Clay SAz-1 Na-
exchanged Miles
Na-exchanged Miles
Na-exchanged Miles
Miles Miles Miles
Treatment 5 min. Ultrasonic, calcined 450°C
5 min ultrasonic, calcined 450°C
10 min ultrasonic, calcined 450°C
20 min ultrasonic, calcined 450°C
5 min. Ultrasonic, calcined 450°C
20 min ultrasonic, calcined 450°C
30 min ultrasonic, calcined 450°C
BET surface area (m2/g)
174 121 129 119 172 154 156
Total pore volume of pores < 144 nm (cm3/g)
0.13 0.13 0.12 0.12 0.14 0.14 0.14
Average pore diameter (nm)*
2.98 4.25 3.83 4.01 3.34 3.52 3.62
Table 3.1 BET surface area and pore volume and average pore diameter of Al-
pillared montmorillonites
113
Fig 3.4b Al-pillared montmorillonite SAz-1 (ultrasonic treatment 10 minutes, calcined at 450°C)
Fig 3.4a Al-pillared montmorillonite SAz-1 (ultrasonic treatment 5 minutes, calcined at 450°C)
114
Fig 3.4c Al-pillared montmorillonite SAz-1 (ultrasonic treatment 20 minutes, calcined at 450°C)
115
In order to obtain a better understanding of the pillar distribution and how this is
related to the changes in the pore size high resolution AFM has been used. Fig. 3.5a
gives an example of the starting montmorillonite with its layers oriented parallel to the
mica surface. It clearly shows the hexagonal pattern associated with the six-membered
rings of SiO4 tetrahedra in the tetrahedral sheet of the montmorillonite. The
introduction of the Al-pillars results in a rather broad distortion of this pattern. Figures
3.5 show examples of the effects of Na-exchange prior to the pillaring and the
prolonged ultrasonic treatment. The introduction of the Al-pillars with increasing
ultrasonic treatment resulted in an increase in the distortion of the tetrahedral sheet.
The images also show that these distortions are not present at a regular interval, which
may indicate that the pillars are not present in the interlayers at a regular distance.
There is no evidence for the presence of any pillars on the outside surface of the clay
particles. This supports earlier work where high resolution TEM showed similar
irregularities in the pillar distances between layers but also within layers [9].
The catalytical activity of the pillared clays was tested for the n-heptane conversion
after loading the pillared clays with 0.4 wt% Pd. For comparison two commercially
used catalysts have been tested (Table 3.2). In general the starting clay and Al-pillared
clay prepared via the standard method without ultrasonic treatment did not perform
well with the temperature required for 40% conversion around 425°C, which is
comparable to Pd loaded on Al2O3 modified with TEOS (resulting in a very weak
solid acid). In contrast the commercially used catalyst ASA (amorphous
silica/alumina from American Cyanamid loaded in a similar fashion, and previously
described in [10]) gives a temperature of 348°C. All the pillared clays gave
temperatures in the range between 355 and 368°C. Minor differences are observed
with respect to the preparation methods used. The use of Na-exchange prior to the
116
pillaring resulted in the worst performing catalysts. This reaffirms the previous XRD
observation that the best material was obtained without the Na-exchange. The effect
of the time used for the ultrasonic treatment shows no significant differences although
the pillared clays ultrasonically treated for 5 or 10 minutes performed slightly better
than those treated for 20 minutes. Overall the selectivity for the isomers is high and
there is almost no cracking up to about 60% conversion. Exceptions are the starting
montmorillonite and the pillared clay prepared via the standard method without
ultrasonic treatment, as thermal cracking is easily achieved at temperatures above
400°C.
117
Fig 3.5a AFM raw image (left) and FTIR processed image (right) of Miles montmorillonite
Fig 3.5b AFM raw image (left) and FTIR processed image (right) of Miles montmorillonite after 10 minutes ultrasonic treatment
118
Sample T(°C) required for 40% conversion
Pd/Al2O3:Si 425 ASA 348
Cheto montmorillonite 424 Al-pillared Miles conventional method 426
Na-exchanged Al-pillard Miles 5 min US 368 Na-exchanged Al-pillard Miles 10 min US 362 Na-exchanged Al-pillard Miles 20 min US 368
Al-pillared Miles 5 min US 360 Al-pillared Miles 10 min US 363 Al-pillared Miles 20 min US 359 Al-pillared Cheto 5 min US 366 Al-pillared Cheto 5 min US 355 Al-pillared Cheto 5 min US 363
Fig 3.5c AFM raw image (left) and FTIR processed image (right) of Al-pillared Miles montmorillonite after 20 minutes ultrasonic treatment
Table 3.2 Temperatures for 40% n-heptane conversion on Pd-loaded pillared clays (calcined 450°C, Pd loading 0.4 wt%) and two standard catalysts (ASA and Pd/Al2O3:Si)
119
3.5 Conclusions
This work shows that the use of ultrasonic treatment results in pillared clays
without the need for Na-exchange prior to the pillaring process. The pillar distribution
is clearly affected by the ultrasonic treatment. Overall best results are obtained with
short ultrasonic treatment times, while prolonged ultrasonic treatment results in a
decrease in surface area and pore diameter associated with a loss of regularity in the
interpillar distances. The decrease in pore size and pillar distribution has a minor but
observable effect on the catalytic activity in the n-heptane conversion test, where the
pillared clays with the longest ultrasonic treatment performed worst. This means that
the preparation of pillared clays on a commercial scale can be easier achieved since
the extensive washing and sodium-exchange step can be left out and the intercalation
of the pillaring complexes can be achieved in a much smaller timeframe without
loosing catalytic activity.
3.6 Acknowledgements
The Inorganic Materials Research Program is thanked for the financial Support.
The authors wish to thank Chris Hildebrandt for his help in the experimental work.
We would also like to thank Shell Research and Technology Centre Amsterdam for
their help with the catalytic testing and Greg Watson of the Scanning Probe
Microscopy Laboratory of Griffith University, Brisbane, for his help with the AFM
work.
120
3.7 References
1. J. M. Thomas and W. J. Thomas, Principles and practice of heterogeneous
catalysis, VCH Publishers Inc., New York, 1997.
2. P. B. Venuto and J. E. Thomas Habib, Fluid catalytic cracking with zeolite
catalysts, Vol. 1, Marcel Dekker, Inc New York, 1979.
3. J. T. Kloprogge, Journal of Porous Materials 5, 5 (1998).
4. A. Vaccari, Applied Clay Science 14, 161 (1999).
5. R. Burch, Catalysis Today 2, 185 (1988).
6. S. P. Katdare, V. Ramaswamy and A. V. Ramaswamy, Catalysis Today 49,
313 (1999).
7. S. P. Katdare, V. Ramaswamy and A. V. Ramaswamy, Microporous and
Mesoporous materials 37, 329 (2000).
8. J. T. Kloprogge, R. Evans, L. Hickey and R. L. Frost, Applied Clay Science
20, 157 (2002).
9. L. V. Duong, T. E. Bostrom, J. T. Kloprogge and R. Frost, L., Microporous
and Mesoporous Materials 82, 165 (2005).
10 E. Booij, J.T. Kloprogge and van Veen, J.A.R., Clays and Clay Minerals 44,
774 (1996)
Statement of Contribution
The authors listed below have certified* that: 1. they meet the criteria for authorship in that they have participated in the conception,
execution, or interpretation, of at least that part of the publication in their field of expertise; 2. they take public responsibility for their part of the publication, except for the responsible
author who accepts overall responsibility for the publication; 3. there are no other authors of the publication according to these criteria; 4. potential conflicts of interest have been disclosed to (a) granting bodies, (b) the editor or
publisher of journals or other publications, and (c) the head of the responsible academic unit, and
5. they agree to the use of the publication in the student’s thesis and its publication on the
Australasian Digital Thesis database consistent with any limitations set by publisher requirements.
In the case of this chapter:
HIGH RESOLUTION XPS STUDY OF THE INTERNAL STRUCTURE OF Al- AND Ga-PILLARS IN PILLARED CLAY CATALYSTS
Loc V. Duong, .Theo Kloprogge, R. Frost and Barry J. Wood
Submited December 2007
Contributor Statement of contribution*
Loc Duong wrote the manuscript, designed experiments, conducted experiments, data analysis, data interpretation
Date
Theo Kloprogge Supervision, aided with data analysis and interpretation
Ray Frost editing
Barry Wood Aid with XPS techniques
Principal Supervisor Confirmation I have sighted email or other correspondence from all Co-authors confirming their certifying authorship and. _______________________ ____________________ _____________________ Name Signature Date
122
CHAPTER 4
4.0 HIGH RESOLUTION XPS STUDY OF THE
INTERNAL STRUCTURE OF AL- AND GA-
PILLARS IN PILLARED MONMORILLONITE
Loc V. Duong, J.Theo Kloprogge, R. Frost and Barry J. Wood
Submitted
Loc Duong, Inorganic Materials Research Program, School of Physical and Chemical
Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Qld
4001, Australia
Theo Kloprogge, Inorganic Materials Research Program, School of Physical and
Chemical Sciences, Queensland University of Technology, GPO Box 2434,
Brisbane, Qld 4001, Australia
Ray Frost, Inorganic Materials Research Program, School of Physical and Chemical
Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Qld
4001, Australia
Barry J. Wood, Brisbane Surface Analysis Facility, University of Queensland,
Brisbane, Qld 4072, Australia
123
4.1 Abstract
Ga and Al-pillared clays were prepared using montmorillonite (SWy-2) as the starting
material. The complexing agents Al13 and Ga13 were prepared through hydrolysis of
Al and Ga nitrate solutions with NaOH up to a Al/OH and Ga/OH molar ratio of 2/1.
After ion exchange the resulting intercalated montmorillonites were calcined at 450°
for 8 hours. XRD shows an increase in the basal spacing from 14Ǻ to about 19Ǻ. XPS
high resolution scans of Si 2p confirms the presence of only 1 type of Si in both the
starting montmorillonite and the pillared samples. The Al 2p scan of the starting
montmorillonite shows two bands at 75.90 eV associated with octahedral Al and at
76.23 eV associated with tetrahedral Al in the clay layers. The corresponding O 1s is
dominated by a single strong band at 532.62 with a minor water band at 535.44 eV.
The Ga-pillared montmorillonite shows two bands in the Ga 2p high resolution scan at
1118.99 eV and 1120.77 eV associated with GaVI and GaIV , respectively. In the O 1s
spectrum an extra band at 531.93 eV is visible, associated with the oxygen in the
pillar structure in addition to the earlier observed bands associated with the clay
layers. A similar result is obtained for the O 1s spectrum in the case of the Al-pillared
clay. Chemical analysis of the montmorillonite and its corresponding pillared samples
shows that 2.01 Ga and 2.76 Al are present in the clay interlayer per formula unit of
Al4(Si7.38Al0.62)O20(OH)4. Based on the montmorillonite layer charge and the amount
of pillars present in the interlayer it is calculated that progressive hydrolysis has
reduced the effective charge of 7+ present on the Al13 or Ga13 complex in solution to
around 3 to 4+ in the pillars present in the clay interlayers.
Key words: Al13 Keggin structure, pillared clay, montmorillonite, XPS
124
4.2 Introduction
Smectite, the 2:1 dioctahedral phyllosilicates with the surface charge per unit cell
from 0.4-1.2, has been commonly used as starting material for pillaring with different
inorganic species for mainly catalytic purposes. Pillaring is a process in which the
clay layers are propped apart by large inorganic species or props followed by a
calcination step during which the prop is converted to a covalently bonded structure
known as the pillar (Kloprogge, 1998, Kloprogge, 2005,(Bergaya, 2006 *). The most
common inorganic complex which has been used is Al13. The Al13 was first reported
by Johansson in 1960 (Johansson, 1960)and has a Keggin type cage structure. The
final Al pillared montmorillonite would provide the microporous structure with the d
spacing of about 18Å. Most of research has been done on the structure of the Al13
pilllared montmorillonite using XRD, SSA, NMR and TEM. Vibrational spectroscopy
is a technique which helps to uncover the changes in the structure of the pillars after
calcination
A major problem in this type of characterization is that it is not easy to distinguish
between the Al from the pillars and the Al from the silicate structure. Ga13 provides a
similar Keggin structure as Al13 but is in general more stable and fit in much better
than Al in the Keggin structure. The similarity in the structure between Ga and Al
pillared montmorillonite has been discussed by (Duong et al., 2005a) using TEM and
microanalysis study. The use of gallium cation however allows one to now clearly
distinguish between what is happening in the pillar structure and in the clay layers
during the calcination step.
X ray photoelectron spectroscopy, introduced in 1967, is a surface technique
which using the concept of binding energy different from one element to other and
varies from local environment which reflects the bonding details of the element
125
involved in the structure (Siegbahn et al., 1967). The penetration depth (escape depth
of the photoelectron) is about 0.5 - 10nm (50-100 Ǻ) which equals to about 5 atomic
clay layers and is depended on the matrix and the X-ray source. Due to the very small
size of smectite particles of less than 5 micron in diameter and up to about 20 nm in
thickness, XPS can be used for the study of clay minerals as a bulk analytical
technique instead of a surface technique. Earlier work in our laboratory has used XPS
to study a series of Source Clays from The Clay Minerals Society Repository
(Kloprogge et al., 2008)
This paper reports the first experiments done on Al13- and Ga13-pillared
montmorilonites using XPS with the objective to study in detail the changing in the
pillar structure of the pillared clays. The structure of Al13 pillars has been compared to
the Keggin structure in a basic aluminium sulphate and Ga13 pillars in the Ga13
pillared montmorillonite in order to gain a better understanding of the changes in the
pillar structure upon calcination and the bonding structure of the pillared clay before
and after calcination
126
4.3 Experimental
4.3.1 Sample preparation
The starting materials used for this study were ≤ 2 μm fractions of Wyoming
montmorillonite SWy-2. All samples were saturated with sodium through exchange
with 1 M NaCl for 8 hours. The clays were washed five times with deionised water in
order to remove residues of NaCl. A detailed description of the Al13-pillaring
procedure have been provided by Kloprogge et al. (2002). SWy-2 montmorillonite
was also used to prepare the Ga13 pillared clay. The preparation of the Ga13-pillared
clays was similar to that of the Al13-pillared clay. A 0.1M solution of NaOH was
added to Ga(NO3)3 at a rate of 0.01 ml/min using a peristaltic pump under vigorous
stirring at room temperature. The OH/Ga ratio was 2:1. The Al13 and Ga13 solutions
were added to the aqueous clay suspensions under continuous stirring during four
hours. The suspensions were then allowed to stand for several days. The pillared clays
were washed 5 times with deionised water using a centrifuge. The samples were
allowed to dry in air at ambient temperature. Finally, the samples were heated at
2°C/min and calcined at 450°C for 8 hours.
4.3.2 X-ray diffraction (XRD)
The nature of the resulting material was checked by X-ray powder diffraction.
The XRD analyses were carried out on a Philips wide angle PW 1050/25 vertical
goniometer equipped with a graphite diffracted beam monochromator. The d-values
and intensity measurements were improved by application of an in-house developed
computer aided divergence slit system enabling constant sampling area irradiation (20
mm long) at any angle of incidence. The goniometer radius was enlarged to 204 mm.
The radiation applied was CoKα from a long fine focus Co tube operating at 35 kV
127
and 40 mV. The samples were measured at 50 % relative humidity in stepscan mode
with steps of 0.02° 2θ and a counting time of 2s.
4.3.3 N2 adsorption/desorption
The surface areas of the starting montmorillonite and Al13 pillared
montmorillonites were calculated by the BET method using N2 adsorption-desorption
on a Micromeritics ASAP 2010 at a partial pressure range of 0.06 to 0.30.
4.3.4 X-ray Photo-electron Spectroscopy
The samples were analyzed in freshly powdered form in order to prevent
surface oxidation changes. Prior to the analysis the samples were outgassed under
vacuum for 72 hours. The XPS analyses were performed on a Kratos AXIS Ultra with
a monochromatic Al X-ray source at 150 W. Each analysis started with a survey scan
from 0 to 1200 eV with a dwell time of 100 milliseconds, pass energy of 160 eV at
steps of 1 eV with 1 sweep. For the high resolution analysis the number of sweeps
was increased, the pass energy was lowered to 20 eV at steps of 100 meV and the
dwell time was changed to 250 milliseconds.
Band component analysis was undertaken using the Jandel ‘Peakfit’ software
package, which enabled the type of fitting function to be selected and allows specific
parameters to be fixed or varied accordingly. Band fitting was done using a Lorentz-
Gauss cross-product function with the minimum number of component bands used for
the fitting process. The Gaussian-Lorentzian ratio was maintained at values greater
than 0.7 and fitting was undertaken until reproducible results were obtained with
correlations of r2 greater than 0.995.
128
4.4 Results and discussion
X-ray powder diffraction patterns of the starting montmorillonites and Ga13
and Al13 pillared montmorillonites demonstrated that the Ga and Al had been pillared
successfully. The exchange of montmorillonite Swy-2 with large Keggin type
molecules such as Al13 and Ga13 results in an expansion of the basal spacing from 14
Ǻ to about 19-20Ǻ (Table 4.1). Upon calcination these rather bulky complexes
convert to a stable oxide bonded to the tetrahedral sheets. During this conversion there
is a slight decrease in basal spacing. In addition pillaring with both the Ga and Al
complexes strongly increased the BET surface area (Table 4.1).
Earlier work of Duong et al. (2005a) has shown that the pillars are relatively
evenly distributed between the clay layers at crystal size resolution but that at high
resolution there are distinct differences in the distribution. The use of high resolution
TEM did not provide any detailed information about the exact structure of the pillar
after calcination. Kloprogge et al. (1999) used infrared emission spectroscopy to
determine the changes that take place upon calcination of Al13 exchanged clays.
Exchange of montmorillonite with Al13 gave Al–OH and Al–H2O OH-stretching
modes of Al13 at 3682 and 3538 cm−1. Calcination resulted in removal of the Al–OH
mode >400°C. The Al–H2O band was replaced by bands at 3574 and 3505 cm−1, due
to structural rearrangement within Al13. The intensities diminished, but are still
observed at 800°C, suggesting that the pillar structure incompletely converted to
"Al2O3." A similar observation was made by Balek et al. (1998) using Emanation
Thermal Analysis. Below 1750 cm−1the Al13–montmorillonite displays bands at 642,
1008, 1321, 1402, and 1512 cm−1. The 1512 cm−1 band disappeared at 500°C,
followed by the other bands above 600°C. The 642 cm−1 band intensity diminished but
129
is still observed at 800°C. At 700°C a new band is observed at 722 cm−1due to Al–O
bond formation. However no details about the exact pillar structure were obtained.
Table 4.1 XRD and N2 adsorption/desorption results for the starting montmorillonite SWy-2, the Al13- and Ga13-intercalated montmorillonites and the calcined Al13- and Ga13-pillared montmorillonites
Plee et al.(1985) have used 27Al and 29Si solid state nuclear magnetic
resonance (MAS-NMR) techniques to study the thermal transformation of Al pillars
and their linkage with the clay sheets. Their 27Al MAS NMR spectra of beidellite
revealed two separate AlIV resonances due to the tetrahedral Al present in the clay
structure and in the centre of the Al13 pillar. In all other publications an overlap of
both signals is reported instead of separate signals making it impossible to draw any
definitive conclusions on the changes in the pillar structure upon calcination
(Kloprogge et al., 1994; Malla and Komarneni, 1993).
X-ray photoelectron spectroscopy is not only sensitive to the chemical
composition but is also sensitive to the local environment of atoms in a crystal
structure, which is reflected in changes in the binding energy and the occurrence of
Basal spacing (001) (Ǻ)
BET surface area (m2/g)
Total Pore volume (<144nm) (cm3/g)
SWy-2 14.0 22.3 SWy-2
Al13 exchanged 18.3 na Al13 exchanged
Ga13 exchanged 19.9 na Ga13 exchanged
GaAl12 pillared 19.1 122 GaAl12 pillared
Al13 pillared 17.3 120 Al13 pillared
Ga13 pillared 17.9 118 Ga13 pillared
130
multiple bands associated with different chemical environments. A good example of
this was recently published on bauxite minerals, where boehmite (AlOOH) showed
two distinct oxygen bands associated with an oxygen atom linked to the aluminium
atom and the hydroxyl group. Similar observations for pillared clays might shed more
light on the pillar structure after calcination.
XPS is in general considered to be a surface analysis technique. However, for
powders with very small particle sizes, such as commonly observed for clay minerals,
the analysis can be assumed to be close to a bulk analytical technique since the
penetration depth of the X-rays is in the order of up to 100 Å. Figure 4.1 shows the
XPS survey scan of the starting montmorillonite. The major advantages of XPS as an
analytical tool are the absence of sample preparation, rapid analysis and multi-
elemental analysis including elements such as F, Cl or Li. Fig. 4.2 exhibits the high
resolution scans for the O 1s, Si 2p and Al 2p of the starting clay. Since all clay
minerals belong to the phyllosilicate group where silicon is only present as SiO4
tetrahedra linked together through their three basal oxygen atoms, a single band will
be observed. This is indeed the case; a single Si 2p band is observed with a binding
energy of 103.42 eV. Aluminium in montmorillonite can however be present in two
different positions. First of all aluminium in six-coordination can be present in the
octahedral sheet, which is sandwiched between two silicon tetrahedral sheets and
secondly aluminium can be present in four-coordination as substitution of silicon in
the tetrahedral sheet. A similar split has been observed in a series of clay minerals
provided by the Clay Minerals Society Source Clay Repository (Kloprogge et al.,
2008). The O 1s is dominated by a single strong band at 532.62 eV with a minor band
at 535.44 eV.
131
Fig. 4.1 XPS survey scan of the Wyoming montmorillonite starting material
The main band is due to the oxygen in the clay layers while the minor band is
associated with a small amount of strongly absorbed water. Interestingly no
distinction can be made between oxygen atoms and hydroxyl groups in the clay layers
in contrast to some of the oxohydroxides. Exchange with Ga13 followed by calcination
is thought to result in the transformation of the Ga13 into an oxidic material covalently
bonded to the tetrahedral sheets of the montmorillonite. Ga13 is a Keggin complex
similar to Al13 and thus exists of a central four-coordinated Ga surrounded by 12 six-
coordinated Ga. Upon calcination of the Ga13-exchanged clay the resulting high
resolution Ga 2p spectrum show two bands that, similar to Al13 in basic aluminium
sulfate (Duong et al., 2005b), reflect the presence of both tetrahedral and octahedral
0
5000
10000
15000
20000
0100200300400500600700800900100011001200
Binding Energy (eV)
Inte
nsity
(CPS
)
Na 1s
O 1s
Fe 2p
O Auger
Na Auger
C 1s
Si 2p
Al 2pMg Auger
Mg 2p
Starting montmorillonite Swy-2
Si 2s
Al 2s
132
Ga in the pillar even after calcination (Fig. 4.3). The major band observed at 1118.99
eV is associated with the six-coordinated Ga while the small band at 1120.77 eV is
associated with the four-coordinated Ga. The observed ratio of 1:11 is close to the
theoretical ratio of 1:12. The Si 2p (103.53 eV) and Al 2p (75.42 and 76.31 eV)
spectra do not change upon pillaring with Gallium. The O 1s spectrum is also rather
similar to that of the original starting clay with a major band at 532.81 eV and a minor
band associated with strongly bonded water at 534.37 eV. However a new band can
be observed at 531.93 eV. Based on the above observations there is direct evidence
for the formation of a different type of oxygen in the pillar structure. It appears that
the local environment of the Si and Al in the tetrahedral sheets as reflected in the high
resolution Si 2p and Al 2p spectra is not significantly influenced through the
formation of covalent bonds with the Ga-pillar.
The observation of changes in the pillar structure and the bonding to the clay
layers of aluminium pillars has always been hampered by the fact that a significant
amount of aluminium is present in the clay structure. This makes independent
observation of what happens in the pillar structure upon calcination very difficult.
Earlier work has shown that basic aluminium sulfate with the Al13 Keggin structure
still intact exhibits two bands in the high resolution Al 2p spectrum (Duong et al.,
2005b). These two bands at 74.6 and 73.8 eV have been identified as the octahedral
and tetrahedral Al respectively (Fig. 4.4). The interpretation of the 74.6 eV band as
the octahedral Al is supported by similar binding energies observed for gibbsite and
corundum. Upon exchange of Al13 and subsequent calcination of the intercalated
montmorillonite a similar high resolution Al 2p spectrum is obtained with a major
band at 74.37 eV and a minor band at 73.89 eV in both the exchanged and calcined
samples (Fig. 4.5). Similar to the Gallium pillars the presence of tetrahedral
133
coordinated Aluminium is preserved in the pillared clay. Due to the excess amount of
aluminium present in the pillared clay it is impossible to observe the bands associated
with the aluminium in the clay layers. However, the high resolution Si 2p spectrum
shows that there is no change in the binding energy of the silicon in the tetrahedral
sheets, in agreement with the observations for the Ga-pillared montmorillonite.
Similarly the high resolution O 1s spectrum is almost identical to that observed for the
Ga-pillared montmorillonite with the O 1s of the clay layer at 532.75 eV, strongly
bonded water at 534.38 eV and that of the pillar at 532.02 eV.
The chemical analyses based on the XPS spectra of the starting clay and its
Al- and Ga-pillared equivalents are represented in Table 4.2. The analysis of the
montmorillonite SWy-2 and the Ga-pillared clay are in close agreement with earlier
published chemical analyses based on single crystal energy dispersive X-ray analysis
within the Transmission Electron Microscope (Duong et al., 2005a), taking into
account that no analysis was included of the Fe and Mg content in the starting
material. Comparison between the starting montmorillonite and the Ga- and Al-
pillared clay shows the presence of 2.01 Ga and 2.76 Al per formula unit of
Al4(Si7.38Al0.62)O20(OH)4. The amount of Al bound in the interlayer per unit cell has
been shown to vary only within a small range (2.78–3.07), equivalent to
approximately one Al13 per 4.2 to 4.6 unit cells, and shows no correlation with the
charge of the layer. The absence of a correlation suggests a more or less uniform
monolayer of hydrated Al or Ga polyoxocations to be present in the interlayer
(Kloprogge, 1998),. Bergaoui et al., (1995) indicated that the amount of Al never
exceeds one Al13 per 6 unit cells, due to steric constraints at the solid-liquid interface.
134
Swy2 Al13
exchanged Al-pilc GaAl13-
pilc Ga-pilc
Si 19.21 13.44 16.21 15.73 15.90
Al 11.81 13.68 16.21 14.43 9.78
Na 0.77 - - - -
Ca 0.73 - - - -
O 67.47 72.88 67.57 69.45 72.37
Ga - - - 0.39 1.97
Si/Al 1.6263 0.9825 1.0000 1.0901 1.6263
Si/O 0.2847 0.1844 0.2397 0.2265 0.2197
Si/Ga - - - 40.33 8.0711
Si 7.38 7.38 7.38 7.38 7.38
Al clay 4.62 4.62 4.62 4.62 4.62
Al pillar - 2.89 2.76 2.15 -
Ga - - - 0.18 2.01
Na 0.21 - - - -
Ca 0.42 - - - -
O clay layer 24.00 24.00 24.00 24.00 24.00
O pillar - 8.90 5.25 6.26 6.85
H2O 1.92 7.11 1.53 2.74
O 1s clay 92% 78% 72%
O 1s pillar - 17% 20%
O 1s H2O 8% 5% 8%
Table 4.2 Chemical analysis (at%) of the starting clay SWy-2 and the Al and Ga pillared equivalents
The montmorillonite layer charge of 0.62 and the amount of Ga and Al present
in the pillars indicates that the charge on the Ga13 pillar upon intercalation and
135
washing has changed due to progressive hydrolysis from 7+ to about 4+ and for Al13
from 7+ to about 3+ in agreement with earlier work on Al13-pillared clays. Jones and
Purnell (1993) have shown that the Al-pillars exhibit an ionic charge slightly above
3+ instead of 7+ as assumed for Al13, which explains why more Al is introduced in
the clay interlayer than a 7+ charged Al13 would allow (Purnell, 1990).
The Ga/O ratio in the pillar is about 0.29 indicating that the overall chemical
composition of the pillar is rather different from that of the standard oxide Ga2O3 with
a ratio of 0.67 as would be expected. Similarly the Al/O ratio in the Al pillars is about
0.53 instead of 0.67 as expected for Al2O3. A possible explanation for the difference
may be the presence of residual hydroxyl groups on the outside of the pillars as a
result of incomplete conversion of the Al13 complex upon calcination. Infrared
emission spectroscopy and Emanation Thermal Analysis have shown that surface
hydroxyls are present on Al13 pillared clays after calcination at 450°C (Kloprogge et
al., 1999; Balek et al., 1998).
136
Fig. 4.2 High resolution XPS spectra of Si 2p, Al 2p and O 1s of the
starting montmorillonite Swy-2
0
100
200
300
400
500
600
700
800
900
1000
100101102103104105106107
Binding energy (eV)
Inte
nsity
(CPS
)
Si 2p montmorilonite
103.42 eV
0
100
200
300
400
500
600
71727374757677787980Binding energy (eV)
Inte
nsity
(CPS
)
AlVI 75.90 eV
AlIV 76.23 eV
Al 2p montmorillonite
0
500
1000
1500
2000
2500
3000
528529530531532533534535536537538
Binding energy (eV)
Inte
nsity
(CPS
)
O 1s H2O 535.44 eV
O 1s 532.62 eVO1s montmorillonite
137
Fig. 4.3 High resolution XPS spectra of Si 2p, Al 2p, Ga 2p and O 1s of the Ga-pillared montmorillonite Swy-2
0
100
200
300
400
500
600
700
800
900
1000
100101102103104105106107
Binding energy (eV)
Inte
nsity
(CPS
)
Si 2p montmorilonite
103.42 eV
0
100
200
300
400
500
600
71727374757677787980Binding energy (eV)
Inte
nsity
(CPS
)
AlVI 75.90 eV
AlIV 76.23 eV
Al 2p montmorillonite
0
100
200
300
400
500
600
700
1115111611171118111911201121112211231124
Binding energy (eV)
Inte
nsity
(CPS
)
Ga 2p Ga-pillared montmorillonite
GaIV 1120.77 eV
GaVI 1118.99 eV
0
200
400
600
800
1000
1200
1400
1600
528529530531532533534535536537538
Binding energy (eV)
Inte
nsity
(CPS
)
O 1s Ga-pillared montmorillonite
O 1s H2O 534.37 eV
O 1s clay 532.81 e V
O 1s pillar 531.93 eV
138
Fig. 4. 4 High resolution XPS spectra of Al 2p of Al13 sulfate after calcination at 400°C (top ), gibbsite with only AlVI (middle), and corundum with AlVI (bottom )
0
50
100
150
200
250
300
350
400
7071727374757677787980
Binding energy (eV)
Inte
nsity
(CPS
)
Al 2p Al13 sulfate calcined 400οC
AlVI 74.6 eV
AlIV 73.9 eV
0
50
100
150
200
250
300
71727374757677787980
Binding energty (eV)
Inte
nsity
(CPS
) AlVI 74.37 eV
AlIV 73.89 eV
Al 2p Al-pillared montmorillonite
0
500
1000
1500
2000
2500
3000
7071727374757677787980
Binding energy (eV)
Inte
nsity
(CPS
)
Al 2p corundum
AlVI 74.2 eV
139
Fig. 4. 5 High resolution XPS spectra of Si 2p, Al 2p and O 1s of the Al-pillared montmorillonite Swy-2
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
528529530531532533534535536537538
Binding energy (eV)
Inte
nsity
(CPS
)
O 1s Al-pillared montmorillonite
O 1s pillar 532.02 eV
O 1s clay 532.75 eV
O 1s H2O 534.38 eV
0
50
100
150
200
250
300
71727374757677787980
Binding energty (eV)
Inte
nsity
(CPS
) AlVI 74.37 eV
AlIV 73.89 eV
Al 2p Al-pillared montmorillonite
0
50
100
150
200
250
100101102103104105106107
Binding energy (eV)
Inte
nsity
(CPS
)
102.66 eV
Si 2p Al-pillared montmorillonite
140
4.5 Conclusions
This paper successfully describes the use of high resolution XPS for the study of pillared
clays. Detailed XPS analysis has shown to provide detailed information not only about
the chemical composition of the clay and its pillared equivalents, but also provided
insight in the chemical composition of the pillars itself. The change in ionic charge due to
progressive hydrolysis during the intercalation and washing steps can be calculated to be
from 7+ to values around 3 to 4+. The results of the Ga and Al-pillared clay are in close
agreement with earlier published work applying different analytical techniques.
4.6 Acknowledgements
We wish to thank Wayde Martens for his expert assistance with preparation of the
pillared clays, and members of the clay group in the Inorganic Materials Research
Program for helpful advice and discussion. We acknowledge financial support from the
Inorganic Materials Research Program, Faculty of Science, and Queensland University of
Technology.
141
4.7 References
Balek, V., Malek, Z. and Klosova, E., 1998. Emanation thermal analysis of intercalated
montmorillonitic clay. J. Therm. Anal. Calorim., 53(2): 625-631.
Bergaoui, L., Lambert, J.-F., Franck, R., Suquet, H. and Robert, J.-L., 1995. Al-pillared
saponites. Part 3. Effect of parent clay layer charge on the intercalation-pillaring
mechanism and structural properties. J. Chem. Soc., Faraday Trans., 91(14):
2229-39.
Bergaya, F., 2006 *. Handbook of Clay Science.
Duong, L., Bostrom, T., Kloprogge, T. and Frost, R., 2005a. The distribution of Ga in
Ga-pillared montmorillonites: A transmission electron microscopy and
microanalysis study. Microporous and Mesoporous Materials, 82(1-2): 165-172.
Duong, L., Wood, B. and Kloprogge, T., 2005b. XPS study of basic aluminium sulphate
and basic aluminium nitrate. Materials Letters . 59(14/15): 1932-1936.
Johansson, G., 1960. On the crystal structures of some basic aluminium salts. Acta Chem.
Scand., 14: 771.
Jones, J.R. and Purnell, J.H., 1993. Synthesis and characterisation of alumina pillared
Texas montmorillonite and determination of the effective Keggin ion charge.
Catalysis Letters, 18: 137-140.
Kloprogge, J.T., 1998. Synthesis of smectites and porous pillared clay catalysts: a review.
J. Porous Mater., 5(1): 5-41.
Kloprogge, J.T., Booy, E., Jansen, J.B.H. and Geus, J.W., 1994. The effect of thermal
treatment on the properties of hydroxy-Al and hydroxy-Ga pillared
montmorillonite and beidellite. Clay Minerals., 29(2): 153-67.
Kloprogge, J.T., Duong, L.V., Frost, R.L. and Wood, B.J., 2008. Baseline studies of the
Clay Minerals Society Source Clays: X-ray photoelectron spectroscopy. Clays
and clay minerals.
Kloprogge, J.T., Evans, R., Hickey, L. and Frost, R., 2002. Characterisation and Al-
pillaring of smectites from Miles, Queensland (Australia). Applied Clay Sciencce,
20: 157- 163.
142
Kloprogge, J.T., Fry, R. and Frost, R.L., 1999. An infrared emission spectroscopic study
of the thermal transformation mechanisms in Al-13-pillared clay catalysts with
and without tetrahedral substitutions. Journal of Catalysis, 184(1): 157-171.
Malla, P.B. and Komarneni, S., 1993. Properties and characterization of alumina and
silica-titania pillared saponite. Clays Clay Miner., 41(4): 472-83.
Plee, D., Borg, F., Gatineau, L. and Fripiat, J.J., 1985. High-resolution solid-state
aluminum-27 and silicon-29 nuclear magnetic resonance study of pillared clays. J.
Am. Chem. Soc., 107(8): 2362-9.
Purnell, J.H., 1990. Pillared clays-retrospect, prospect and action. Pillared Layered
Struct.: Curr. Trends Appl., [Proc. Workshop]: 107-13.
Siegbahn, K. et al., 1967. Electron Spectroscopy for Chemical Analysis. Atomic,
Molecular and Solid State Structure Studies by Means of Electron Spectroscopy.
Almquist and Wiksells, Uppsala.
Statement of Contribution
The authors listed below have certified* that: 1. they meet the criteria for authorship in that they have participated in the conception,
execution, or interpretation, of at least that part of the publication in their field of expertise; 2. they take public responsibility for their part of the publication, except for the responsible
author who accepts overall responsibility for the publication; 3. there are no other authors of the publication according to these criteria; 4. potential conflicts of interest have been disclosed to (a) granting bodies, (b) the editor or
publisher of journals or other publications, and (c) the head of the responsible academic unit, and
5. they agree to the use of the publication in the student’s thesis and its publication on the
Australasian Digital Thesis database consistent with any limitations set by publisher requirements.
In the case of this chapter:
XPS STUDY OF BASIC ALUMINUM SULPHATE AND BASIC ALUMINIUM NITRATE
Loc V. Duong, Barry J. Wood and J.Theo Kloprogge*
Published in Materials Letters. 2005, 59, 1932-1936
Contributor Statement of contribution*
Loc Duong wrote the manuscript, designed experiments, conducted experiments, data analysis, data interpretation
Date
Barry Wood aided with data analysis and interpretation
Theo Kloprogge Supervision, editing
Principal Supervisor Confirmation I have sighted email or other correspondence from all Co-authors confirming their certifying authorship and. _______________________ ____________________ ______________________ Name Signature Date
144
CHAPTER 5
5.0 XPS STUDY OF BASIC ALUMINUM SULPHATE
AND BASIC ALUMINIUM NITRATE
Loc V. Duong, Barry J. Wood and J.Theo Kloprogge*
Published in Materials Letters. 2005, 59, 1932-1936
Loc Duong, Inorganic Materials Research Program, School of Physical and Chemical
Sciences, Queensland University of Technology, GPO Box 2434,
Brisbane, Qld 4001, Australia
Barry J. Wood, Brisbane Surface Analysis Facility, University of Queensland, Brisbane,
Qld 4072, Australia
Theo Kloprogge, Inorganic Materials Research Program, School of Physical and
Chemical Sciences, Queensland University of Technology, GPO Box
2434, Brisbane, Qld 4001, Australia
145
5.1 Abstract
Basic aluminium sulphate and nitrate crystals were prepared by forced hydrolysis of
aluminium salt solution followed by precipitation with a sulphate solution or by
evaporation for the basic aluminium nitrate. X-ray Photoelectron Spectroscopy (XPS)
confirms the chemical composition determined by ICP-AES in earlier work. High
resolution XPS scans of the individual elements allows the identification of both the
central IVAlO4 group and the twelve aluminium octahedra in the
[IVAlO4AlVI(OH)24(H2O)12] building unit by two Al 2p transitions with binding energies of
73.7 and 74.2 eV in both the basic aluminium sulphate and nitrate. Four different types of
oxygen atoms were identified in the basic aluminium sulphate associated with the central
AlO4, OH, H2O and SO4 groups in the crystal structure with transitions at 529.4, 530.1,
530.7 and 531.8 eV, respectively.
Keywords: Al13, basic aluminium nitrate, basic aluminium sulphate, Characterisation
methods, Keggin structure, X-ray techniques
146
5.2 Introduction
One of the most important aluminium complexes in solution is the so-called Al13, a
Keggin-type cage structure in which a central AlIVO4 is surrounded by 12
AlVI(OH)24(H2O)12. Forced hydrolysis of Al3+ solutions by the addition of a base like
sodium carbonate or sodium hydroxide or homogeneous hydrolysis by the decomposition
of urea is known to result in the formation of this large aluminium (oxo)hydroxide
complex. The structure of this complex was first studied by X-ray diffraction after
precipitation in the form of two different basic aluminium sulphates in which the Al13
structure is retained [1-4].
Johansson and coworkers [1-4] described the precipitation of basic aluminium
sulphates containing the Al13 building unit linked by hydrogen bonding to the oxygen
atoms of the sulphate groups. The sodium-containing aluminium sulphate crystallised in
the cubic system whereas the sodium-free sulphate crystallised in the monoclinic system.
In earlier work we [5, 6] reported the precipitation of monoclinic basic aluminium
sulphate with a small amount of sodium and a trace of nitrate and of basic aluminium
nitrate. Based on the chemical analyses by ICP-AES a chemical composition per unit cell
of Na0.1[AlO4Al12(OH)24(H2O)12](SO4)3.55.9H2O was reported for the sulphate. 27Al
Solid-state Magic-Angle Spinning Nuclear Magnetic Resonance spectroscopy showed
that the Al13 units were still present in the crystal structure.
Kloprogge et al. [5, 7] and Teagarden et al. [8] have described the infrared spectrum
and near infrared spectrum [9] of the monoclinic basic aluminium sulphate. The spectrum
of basic aluminium sulphate is dominated by two strong water bands at 3247 and 1640
147
cm-1, a strong Al-OH stretching band at 3440 cm-1. The infrared spectrum was further
dominated by the ν1 and ν3 bands at 981 and 1051 cm-1 of the sulphate group in the Al13
sulphate structure. Furthermore the band at 724 cm-1 is assigned to an Al-O mode of the
polymerised Al-O-Al bonds in the Al13 Keggin structure [10]. The Raman spectrum
showed the ν2 and ν4 SO42- triplets at 446, 459 and 496 cm-1 and 572, 614 and 630 cm-1.
The ν1 was observed as a single band at 990 cm-1, partly overlapped by the ν3 triplet at
979, 1009 and 1053 cm-1 [11, 12].
To date there are no publications available on the X-ray Photoelectron Spectroscopy
(XPS) of the basic aluminium sulphate and nitrate complexes. The objective of this report
is to describe in detail the high-resolution XPS spectra of basic aluminium sulphate and
compare those with the spectra of basic aluminium nitrate order to get more insight in the
structure of this complex aluminium salt. As such this paper forms a continuation of our
earlier work on infrared, infrared emission and Raman spectroscopy of these basic
aluminium salts.
5.3 Experimental
5.3.1 Basic aluminium sulphate and nitrate
The synthesis and characterisation of the monoclinic basic aluminium sulphate used in
this study has been extensively described by Kloprogge et al. [5-7, 10, 13]. The
tridecameric aluminium polymer was obtained by forced hydrolysis of a 0.5 M
aluminium nitrate solution with a 0.5 M sodium or potassium hydroxide solution until an
OH/Al molar ratio of 2.2 was reached. Next, the basic aluminium sulphate was
precipitated by the addition of the appropriate amount of 0.5 M sodium sulphate and aged
148
for 42 days before removal from the solution. Crystals collected from the wall of the
container were shown by XRD and SEM to be phase pure (Fig. 5.1). The basic
aluminium nitrate was prepared from the same hydrolysed aluminium solution followed
by very slow evaporation of the excess water at room temperature. This sample was
shown to have an impurity in the form of KOH.
5.3.2 XPS analysis
The basic aluminium nitrate and sulphate samples were analyzed in freshly powdered
form in order to prevent surface oxidation changes. Prior to the analysis the samples were
out gassed under vacuum for 72 hours. The XPS analyses were performed on a Kratos
AXIS Ultra with a monochromatic Al X-ray source at 150 W. Each analysis started with
a survey scan from 0 to 1200 eV with a dwell time of 100 milliseconds, pass energy of
160 eV at steps of 1 eV with 1 sweep. For the high resolution analysis the number of
sweeps was increased, the pass energy was lowered to 20 eV at steps of 100 meV and the
dwell time was changed to 250 milliseconds.
Band component analysis was undertaken using the Jandel ‘Peakfit’ software package,
which enabled the type of fitting function to be selected and allows specific parameters to
be fixed or varied accordingly. Band fitting was done using a Lorentz-Gauss cross-
product function with the minimum number of component bands used for the fitting
process. The Gaussian-Lorentzian ratio was maintained at values greater than 0.7 and
fitting was undertaken until reproducible results were obtained with squared correlations
of r2 greater than 0.995. Band width and shape of the O and Al transitions were set prior
149
to the band component analysis, based on the analysis of standard aluminium compounds
corundum, α-Al2O3 and boehmite, AlOOH.
5.4 Results and discussion
The basic aluminium sulphate crystals exhibit a clear tetrahedral morphology. Some
surface cracks are visible probably due to partial dehydration (Fig.5.1). Calcination of the
basic aluminium sulphate does not significantly alter the morphology, although some
minor powder formation can be observed on the surface. Energy dispersive X-ray
analyses showed no change in the overall composition.
Fig. 5.2 shows the XPS survey scan of the basic aluminium sulphate, clearly showing
the presence of sodium, aluminium, oxygen and sulphur. In addition there is a minor
amount of N present as well. The chemical composition based on the survey scans of the
basic aluminium sulphates at room temperature and after calcination at 200 and 400°C do
not show any significant differences (Table 5.1).
25°C 200°C 400°C Al13 nitrate O 1s 72.2 71.2 68.7 64.4 Al 2p 18.3 18.9 21.9 14.3 S 2p 4.9 7.2 3.4 - N 1s 2.3 - - 11.2 Na 1s 2.4 2.7 6.1 -
Table 5.1. Chemical composition (in atom%) from the XPS analyses of the basic aluminium sulphate at room temperature and after calcination at 200 and 400°C and basic aluminium nitrate
150
The composition is very close to the composition reported earlier based on ICP-AES
analysis of this compound, although the sodium content is somewhat higher [5]. This can
probably be explained by the fact that ICP-AES of the redissolved basic aluminium
sulphate crystals is less sensitive for sodium than XPS of the solid crystals. The basic
aluminium nitrate shows a similar composition to that of the basic aluminium sulphate
but is characterised by slightly lower oxygen content, due to the fact that the SO4 groups
have been replaced by NO3 groups in the crystal lattice and the presence of the KOH
impurity.
The high resolution scans of the different elements present in the basic aluminium
sulphate crystals at room temperature and after calcination at 200 and 400°C are similar
in both intensities and binding energies within the experimental error of the instrument
(Table 5.2), confirming the general observations discussed above. For sodium a single 1s
transition is observed with a binding energy of 1073 eV, indicating a single position in
the basic aluminium sulphate crystal, which is in accordance with the crystal structure
described by Johansson [1-4]. Similarly the sulphur is only present as a single type of
sulphate in the structure as shown by the presence of only one S 2p ½ and one S 2p 3/2
transitions (Fig 5.2).
151
Fig 5.1 SEM images of a basic aluminium sulphate crystal at room temperature and after calcination at 400°C
152
Fig. 5.2 XPS survey scan of basic aluminum sulphate
25°C 200°C 400°C
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
020040060080010001200
Binding energy (eV)
Inte
nsity
(CPS
)
O 1s
Na 1sC 1s
N 1s Al 2pS 2p
153
Table 5.2. Binding energies (in eV) of the basic sulphate at room temperature and
after calcination at 200 and 400°C
Much more informative though are the high resolution scans of aluminium and oxygen
(Fig 5.2). The aluminium high resolution scans show two overlapping bands associated
with two different Al 2p transitions with binding energies of 74.2 and 73.7 eV at room
temperature. The ratio of the two types of aluminium is in the order of 11:1 which is very
close to the 1:12 ratio observed in the Al13 complex where a central IVAl is surrounded by
twelve VIAl. Therefore the 74.2 eV transition is interpreted as being due to the twelve
aluminium octahedra in the Keggin structure, while the 73.7 eV transition is associated
with the central AlO4 tetrahedron. Similar values are observed for the Al 2p transitions in
the basic aluminium nitrate.
The oxygen high resolution scans are rather complex and contain a number of
overlapping transitions. Band component analysis indicate the presence of four transitions
at 531.6, 530.8, 530.1 and 529.5 eV associated with roughly 8, 40, 36 and 15 percent of
the total amount of oxygen present in the crystal structure. Related work in our laboratory
Al 2p VIAl 74.2 74.2 74.6 Al 2p IVAl 73.7 73.5 73.8 S 2p 1/2 171.0 171.3 171.7 S 2p 3/2 169.9 170.1 170.5 O 1s SO4 531.8 531.7 531.9 O 1s H2O 530.7 531.0 531.1 O 1s OH 530.1 530.3 530.4 O 1s O 529.4 529.5 529.7 Na 1s 1072.9 1073.1 1073.3
154
on aluminium (oxo-)hydroxides and oxides such as gibbsite, boehmite and corundum
have shown that in general there is a clear distinction between oxygen atoms, hydroxyl
groups and water with a shift in the binding energy towards higher values. Oxygen in
these minerals is generally observed around 530.7 eV, which is close to the value of
529.4 eV in the basic aluminium sulphate. Similarly, hydroxyl groups in gibbsite and
boehmite are identified by an oxygen 1s transition around 531.8 eV and water around 533
eV. Following an analogues interpretation of the oxygen transitions in the basic
aluminium sulphate the four transitions are interpreted as being due to the central O
around the IVAl, hydroxyl group around the VIAl, water in both around the VIAl and as
crystal water and finally as oxygen in the sulphate groups. This last transition with a
transition at 531.6 eV is similar to the value of 532.4 for oxygen in Al2(SO4)3 [14], 532
eV for CaSO4 [15] or 531.7 eV for CdSO4 [16]. Further evidence for this interpretation
stems from the relative ratios of these transitions. Based on the chemical composition of
the basic aluminium sulphate one would expect an atom concentration of about 7% for
oxygen, 38% for the oxygen atoms in the hydroxyl groups, 34% for oxygen atoms in
water molecules and 22% for oxygen atoms in the sulphate groups. These values are
close to the observed values. No details can be obtained from the O 1s high resolution
spectrum of the basic aluminium nitrate due to interference of the KOH impurity.
In summary this work has shown that XPS is not only a strong tool for obtaining
chemical information of materials, but high resolution XPS will also give detailed
information on the local environment of the different atoms in the structure. As such this
technique forms an important additional analytical tool to the more common techniques
155
such as X-ray Diffraction, Infrared spectroscopy, Raman spectroscopy and solid-state
Nuclear Magnetic Resonance Spectroscopy.
Fig 5.3a Al 2p high resolution spectrum of basic aluminium sulphate
0
50
100
150
200
250
300
350
400
707172737475767778
Binding energy (eV)
Inte
nsity
(CPS
)
IVAl
VIAl
156
Fig.5.3b O 1s high resolution spectrum of basic aluminium sulphate
0
500
1000
1500
2000
2500
3000
529530531532533534535536
Binding energy (eV)
Inte
nsity
(CPS
)
O
OH
H2O
SO4
Fig 5. 3c S 2p high resolution spectrum of basic aluminium sulphate
0
50
100
150
200
250
300
350
166167168169170171172173
Binding energy (eV)
Inte
nsity
(CPS
) S 2p 1/2S 2p 3/2
157
5.5 Acknowledgements
The authors wish to thank the Inorganic Materials Research Program, Queensland
University of Technology, Brisbane, for the financial support
158
5.6 References
1. G. Johansson, Ark. Kemi. 20 (1963) 321.
2. G. Johansson, Acta Chem. Scand. 14 (1960) 771.
3. G. Johansson, G. Lundgren, L. G. Sillén and R. Söderquist, Acta Chem. Scand. 14
(1960) 769.
4. G. Johansson, Acta Chem. Scand. 16 (1962) 403.
5. J. T. Kloprogge, J. W. Geus, J. B. H. Jansen and D. Seykens, Thermochim. Acta
209 (1992) 265.
6. J. T. Kloprogge, P. J. Dirkin, J. B. H. Jansen and J. W. Geus, J. Non-Cryst. Solids
181 (1994) 151.
7. J. T. Kloprogge and R. L. Frost, Thermochim. Acta 320 (1998) 245.
8. D. L. Teagarden, J. F. Kozlowski and J. L. White, J. Pharm. Sci. 70 (1981) 758.
9. J. T. Kloprogge, H. Ruan and R. L. Frost, J. Mater. Sci. 36 (2001) 603.
10. J. T. Kloprogge, R. L. Frost and R. W. P. Fry, in 16th International Conference on
Raman Spectroscopy, Cape Town, South Africa, 1998, pp. 700.
11. J. T. Kloprogge and R. L. Frost, J. Mater. Sci. 34 (1999) 4367.
12. J. T. Kloprogge and R. L. Frost, J. Mater. Sci. 34 (1999) 4199.
13. J. T. Kloprogge, D. Seykens, J. W. Geus and J. B. H. Jansen, J. Non-Cryst. Solids
142 (1992) 94.
14. K. Arata and M. Hino, Appl. Catal. 59 (1990) 197.
15. A. B. Christie, J. Lee, I. Sutherland and J. M. Walls, Appl. Surf. Sci. 15 (1983)
224.
159
16. J. Riga, J. J. Verbist, P. Josseaux and A. K. Mesmaeker, Surf. Interface Anal. 7
(1985) 163.
160
CHAPTER 6
6.0 SUMMARY AND SUGGESTIONS FOR
FUTURE WORK
6.1 Summary
This chapter summarises the results of this study presented in chapter two to chapter
five. A more complete picture of Al- and Ga-pillared clays has been obtained by studying
the preparation of the Al13 and Ga13 complexes and their intercalation in montmorillonite,
including a new method applying ultrasonic treatment. The relationship of the Al and Ga
pillars with the silicate structure of the pillared montmorillonite has been studied in detail
using electron microscopy, X-ray microanalysis, and X-ray photoelectron spectroscopy
(XPS).
Pillared clays have been developed since 1955 with the hope to produce a new type of
catalyst with relatively large pore sizes (in comparison to zeolites) to use for hydrocarbon
cracking. The Al13 Keggin or cage complexes have since the early 1970s been the most
popular pillars to use in producing pillared clays. Johansson and coworkers described the
precipitation of basic aluminium sulphates containing the Al13 building unit linked by
hydrogen bonding to the oxygen atoms of the sulphate groups (Johansson, 1960). The
basic sulphate and aluminum nitrate from these complexes have been studied by NMR by
a number of authors (see under section review of pillared clays).
161
The relationship between the Al and Ga pillars and the silicate structure was discussed
in chapter 2. Detailed structures of the pillared Al and Ga montmorillonite (SWy-2 and
Miles) have been studied by TEM. Ga has similar chemical properties as Al but gives
excellent stable pillared clays under the electron beam. The author has developed a
method for the preparation of cross sections of clay samples perpendicular to the layers
for TEM studies, which provided very good results. (Duong et al., 2005a). This method
uses Spurr resin (Spurr, 1969) for embedding clay samples, which are then cut in the
correct orientation with a diamond knife. These sections are very stable under the
electron beam in TEM. Formulae of the Ga13 and Al13 pillared montmorillonites
calculated from EDS results show that the atomic fractions of the total intercalated
species to silicon were 0.273, 0.235 and 0.235 for the Al13, Al12Ga and Ga13 pillared clays
respectively. It was shown that 0.89 Ga atoms are present per formula unit, which
indicates that there are 20 silicate rings consisting of 6 tetrahedral each per Ga13 pillar.
The average distance between the pillars has been calculated to be 44 Å in agreement
with pore size measurements.
The relationships between the Ga, Al and GaAl pillars and the silicate layers in cross
section indicated that all the pillars intercalated very homogeneously at relatively low
magnification as evidenced by an X-ray map and EDS results. However, at high
magnification differences in pillar density and basal spacing was observed.
An improved route for the preparation of pillared montmorillonite by using ultrasonic
treatment was described in chapter 3. In comparison to the commonly applied exchange
times in the order of hours, short ultrasonic treatment of 5-10 minutes produced very
good results, even without prior Na exchange. Atomic force microscopy showed no
162
evidence of any pillars on the outside of the clay particles. Furthermore, there were
indications that the distribution of the Al 13 pillars may not be as homogeneous as is often
thought, in agreement with the TEM results of the previous chapter. The new method of
preparing intercalated clays by ultrasonic treatment has proved to be successful in
providing pillared clays with similar properties to the conventional method without
loosing catalytic activity. The short ultrasonic treatment time without the process of
extensive washing and sodium exchange make this method very attractive for up-scaling
from the laboratory to large commercial scale production.
The internal structure of pillared clay has been further examined in chapter 4 by XPS.
Chemical analysis of Wyoming montmorillonite SWy-2 and its pillared equivalents
shows that 2.01 Ga and 2.76 Al is present in the clay interlayer per formula unit of
Al4(Si7.38Al0.62)O20(OH)4 (Duong et al., 2005b). The calculation from starting
montmorillonite layer charge showed that the charge of the Ga13 complex has been
reduced from 7+ in solution to around 3 to 4+ for the complex intercalated in the
montmorillonite. The excess water in pillared montmorillonite represented as a band
around 534.38 eV present in the sample after calcinations process. The amount of Ga
observed in the XPS is significantly higher than in the TEM analyses. This is a reflection
of the inhomogeneous distribution of the Ga in the clay sample. In the TEM single
particles were analysed while in XPS a significantly larger volume of sample was
irradiated with X-rays. The higher Ga content can either be due to a higher but
inhomogeneous pillar density in the pillared clay or by the presence of gallium oxide
particles in between the clay particles. Based on the TEM observations of differences in
163
basal spacings and the absence of clear oxide particles the first hypothesis seems to be the
most acceptable.
In chapter 5 of this study the binding energies of Al, O and S in these complexes was
examined for the first time by XPS. The chemical composition of the Keggin structure
from the work of Kloprogge using ICP-AES has been confirmed. The high resolution Al
2p scans showed both Al IV at 73.7 eV and AlVI at 74.2 eV present in the structure with
the ratios of 1:12 which is identical to the ideal structure of the Al13 with one central Al
tetrahedron surrounded by 12 Al octahedra. The high resolution scans of the O 1s
identified 4 types of oxygen: AlO4 associated with the four oxygen atoms in the central
tetrahedron, OH and H2O in the 12 octahedra and SO4. Calcination of the basic aluminum
at 200 and 400 0C showed no change in the high resolution scans.
6.2 Suggestion for future work
Although this study has added some useful information about the relationship between
the Al13 pillars and the montmorillonite structure, more work is needed to determine the
exact bonding between these pillars and the montmorillonite tetrahedral sheets. In
addition, further study is necessary with respect to different starting materials, in
particular the effects of different layer charges and the origin of the layer charge
(octahedral versus tetrahedral) on the pillaring mechanisms. Also the exact structure of
the pillar itself after calcinations is still unknown, although some information has been
obtained from vibrational spectroscopy, solid state NMR and XPS. Heating stage XPS
will be most useful to study the calcination processes and the behavior of the hydroxyl
groups in the pillars in situ, in particular when this is combined with other thermal
164
techniques such as infrared emission spectroscopy (IES) and thermogravimetric and
differential scanning calorimetry (TG and DSC).
Finally, since most of the work so far has focused on Al, other metal pillared clays
deserve further attention. In future studies the role of Atomic force microscope, XPS,
neutron diffraction and Synchrotron X-ray radiation techniques can play an important
part in providing further information about the pillared clay structures.
Synchrotron techniques are currently being developed in Australia. This will allow
further study using Neutron diffraction to further elucidate the pillar structure, while
EXAFS can provide detailed chemical and structural information about a specific
absorbing element whether it is a major component of a solid phase or trace component
of the bulk phase, a soluble species. The EXAFS can be used to identify the charges of
the local element in the silicate structure.
165
6.3 References
Duong, L., Bostrom, T., Kloprogge, T. and Frost, R., 2005a. The distribution of Ga in Ga-pillared montmorillonites: A transmission electron microscopy and microanalysis study. Microporous and Mesoporous Materials, 82(1-2): 165-172.
Duong, L., Kloprogge, T., Frost, R. and Wood, B., 2005b. The structure of Al13 and Ga13 pillars in pillared montmorillonites., The 13th International Clay Conference. Oral presentation, Waseda University Tokyo Japan.
Johansson, G., 1960. On the crystal structures of some basic aluminium salts. Acta Chem. Scand., 14: 771.
Spurr, A.R., 1969. Journal of Ultrastructural Research, 26: 31-43.
166
CHAPTER 7
7.0 ADDITIONAL SUPPORT PAPERS
7.1 Review of the synthesis and Characterization of
pillared clays and related porous materials for
cracking of vegetable oil to produce biofuels
Kloprogge, J.T., Duong, L.V. and Frost, R.L. (2005)
Published in. Environmental Geology, 47(7), 967-981.
7.2 X- ray photoelectron spectroscopic study of the
major minerals in Bauxite: Gibbsite, Bayerite and
(pseudo-) boehmite
J. Theo Kloprogge1, Loc V. Duong1, Barry J. Wood2, and Ray L. Frost1
Published in Journal of Colloid and Interface Science 296 (2) : pp 572-
576
7.3 A X-ray photoelectron spectroscopy study of
HDTMAB distribution within organoclays
Frost, Ray.L and He, Hongping and Zhou, Qin and Kloprogge, J.Theo,
Duong, Loc and Wood, Barry. (2007)
Published in Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy
167
A review of the synthesis and characterisation of
pillared clays and related porous materials for cracking of
vegetable oils to produce biofuels
J.Theo Kloprogge*, Loc V. Duong and Ray L. Frost
Inorganic Materials Research Program, School of Physical and Chemical
Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Qld
4001, Australia
Corresponding author: phone +61 7 3864 2184, fax +61 7 3864 1804, E-
mail [email protected]
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Abstract This paper presents an overview of the modification of clay minerals by propping
apart the clay layers with an inorganic complex. This expanded material is converted
into a permanent two-dimensional structure, known as pillared clay or shortly PILC,
by thermal treatment. The resulting material exhibits a two-dimensional porous
structure with acidic properties comparable to that of zeolites. Synthetic as well as
natural smectites serve as precursors for the synthesis of Al, Zr, Ti, Fe, Cr, Ga, V, Si
and other pillared clays as well as mixed Fe/Al, Ga/Al, Si/Al, Zr/Al and other mixed
metal pillared clays. Biofuels form an interesting renewable energy source, where
these porous catalytically active materials can play an important role in the
conversion of vegetable oils, such as canola oil, into biodiesel. Transesterification of
vegetable oil is currently the method of choice for conversion to biofuel. The second
part of this review focuses on the catalysts and cracking reaction conditions used for
the production of biofuel. A distinction has been made in three different vegetable
oils as starting materials: canola oil, palm oil and sunflower oil.
Key words: Canola oil, Cracking reaction, Pillared clay, PILC
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Introduction Escalating crude oil prices and environmental awareness have increased interest in
the use of renewable fuel sources. One area of attention is the upgrading of vegetable
oils for use as a fuel or fuel additive. Besides being a renewable source, the use of
vegetable oils has benefits economically and environmentally. Such oils are CO2
neutral and contain little, if any sulfur, nitrogen and metals, which are major
pollutants in current fuel emissions (Katikaneni and others 1998). The possibility also
exists for the reuse of current vegetable oil wastes such as wastes from fast food
restaurants. As such, oils come from plants that can be easily grown; its production
can be localized and adjusted according to demand. The conversion of the oil to fuel
can therefore bring benefits to the community economically as well as making them
no longer reliant on outside sources.
Over the years, vegetable oils have been substituted for diesel for use in engines but
this has led to problems such as carbon deposits, oil ring sticking and gelling of the
lubricating oil (Ma and Hanna 1999). Because of such problems, research in this area
has been centered on the conversion of these oils to a form that is similar to current
fuels. One such fuel, which is currently gaining much attention, is biodiesel. This is a
variety of ester-based oxygenated fuels made from vegetable oils or animal fats.
There are several methods for the conversion of vegetable oils to biodiesel of which
the most common is the transesterification process, in which an alcohol is reacted
with the oil to form esters and glycerol (Ma and Hanna 1999). The esters are
separated and commonly used as a mixture with petroleum diesel (20:80) to minimize
engine modification requirements. Altin and others (2001), showed that vegetable oil
methyl esters gave performance and emission characteristics close to petroleum
diesel. The main problems associated with the increased use of this fuel are the costs
of the oil and its processing. Also, the marketing of this product is limited to diesel
engine applications.
Another method for the conversion of vegetable oils to a useable fuel product is by
catalytic cracking reactions. This is currently used in the petroleum and
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petrochemical industry to convert high molecular weight oil components to lower
molecular weight ones which can be used directly or blended for use as fuel (Thomas
and Thomas 1997). The reaction process usually involves the mixing of catalysts with
the oil feed at high temperature in a fluid catalytic cracker (FCC) unit. Here the
hydrocarbon product is collected and the spent catalyst is directed to a regenerator
which oxidizes the coke that has collected on it, to CO, CO2 and H2O, to then be
reused (Venuto and Habib 1979).
Acid-treated clay of the montmorillonite type was the catalyst commonly used for
initial cracking reactions in the 1930s (Thomas and Thomas 1997). Such catalysts
were replaced after World War II with a more stable synthetic silica-alumina type
which also gave better product distribution (Thomas and Thomas 1997). The
emergence of zeolites in the 1960s revolutionized the process mainly because of their
high activity, selectivity and resistance to collapse when treated at high temperatures
(Venuto and Habib 1979). Their use is commonplace now with ZSM-5 and Y types
being some of the most popular catalysts. The interest now is in producing a catalyst
with a larger pore size compared to zeolite (∼8 Å) to handle the cracking of heavier
crude oil. The use of pillared clays has received considerable attention because of
their ability to achieve large pore sizes, but factors such as thermal stability and
coking properties still need to be overcome.
It is common knowledge that vegetable oils can be cracked into lighter fuel fractions
by the use of such catalysts. There are, however, a number of problems associated
with this process with cost being one of the major ones. Altin and others (2001) noted
that at present vegetable oils are more expensive than diesel fuels. However he
suggests that with an increase in consumption should come an increase in production
and this would lead to more mechanised farming methods which would probably
translate into a decrease in cost.
Another problem with the use of vegetable oils for conversion to fuels is that the
composition of such oils varies drastically between types. This means that a particular
set of reaction conditions and catalyst type will give different products according to
the starting oil.
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Smectites
Clays are phyllosilicates or layer silicates with a layer lattice structure in which two-
dimensional oxoanions are separated by layers of hydrated cations. The oxygen
atoms define upper and lower sheets enclosing tetrahedral sites and a central sheet
having the brucite or gibbsite structure enclosing octahedral sites. Smectites have
two tetrahedral sheets around the central octahedral sheet in each layer, hence the
name 2:1 phyllosilicate. These layers have a positive charge deficiency resulting from
isomorphous substitutions (e.g Si4+ by Al3+ at tetrahedral sites or Al3+ by Mg2+ at
octahedral sites). These negative layer charges are balanced by exchangeable
hydrated interlayer cations such as Na+, K+ or Ca2+. The charge deficiency and the
origin of this deficiency (octahedral vs tetrahedral) result in different physical and
chemical properties, such as, thermal stability and swelling behaviour. Layer charges
related to tetrahedral substitutions lead to a localised charge distribution, while layer
charges related to octahedral substations are more distributed over the complete
oxygen framework.
Pillared Interlayered Clays (PILCs)
As a consequence of increasing oil prices, PILCs were improved in the mid-1970s to
optimise the catalytic cracking of crude oil. To increase the yield of lighter fractions
from heavy crude oil, catalysts were required that had larger pore size and good
thermal and hydrothermal stability (Ding and others 2001; Frost and others 1998;
Kloprogge 1998). This was research focussed on the use of inorganic hydrated
polyoxocations as pillaring agents. Such pillaring agents, when calcined, dehydrate
and dehydroxylate to form a fixed metal oxide pillar with a high thermal stability and
high surface area. The use of the Al13 polyoxocation was favoured as it had been
extensively researched and reported previously and was easily prepared (Gil and
Gandía 2000).
The first step in the pillaring process is to prepare a pillaring agent. In the case of the
Al13 polyoxocation, two methods are commonly used: 1) mixing of aqueous AlCl3
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with Al to form a chlorohydrate which is also commercially available, and 2) addition
of a base to AlCl3 or Al(NO3)3 solutions with OH/Al3+ ratios up to 2.5. The
polyoxocation complex produced has been analysed and is thought to be the
tridecamer [AlO4Al12(OH)24(H2O)12]7+, also referred to as the Keggin ion (Kloprogge
1998; Kloprogge and others 1992).
The next step is the mixing of a clay suspension with this polyoxocation solution.
This allows the interlayer cations in the clay to exchange with the polyoxocation in
solution through cation exchange reaction or intercalation (Gil and Gandía 2000).
After the intercalation process is complete, the clay is separated, washed and then
calcined. The property of the stable pillared structure obtained is greatly affected by
factors such as clay used, mixing and drying conditions and polycation/s used.
Vegetable oil
Vegetable oils are predominantly made up of triacylglycerols with a small amount of
minor compounds (2-5%) (Cert and others 2000). Triacylglycerols are made up of
one glycerol molecule joined to 3 fatty acids by an ester link. As shown in Figure 1,
the type and concentration of fatty acid varies considerably from one vegetable oil to
another. Hence, it is important to be aware of the composition of the vegetable oil
used for the choice of the catalyst, as it will determine the type of reactions that are
probable. The four major vegetable oils produced today are palm oil, soybean oil,
sunflower oil and rapeseed oil. The production of palm oil has increased at a great
rate over the past 5 years. One report estimates that the world trading of palm oil has
grown 32% since 1997-98 (Anonymous 2001). This has led to a decrease in prices
with the Malaysian average palm oil prices in 1999-00 falling to $314 per metric
tonne a decrease of around 35% from 1998-99 (Guzman 2001). This reduction in
price and high availability makes it ideal as a fuel source.
Oil is extracted from the fruit of the oil palm which is usually grown in areas within
10o of the equator (Gunstone and Society of Chemical Industry (Great Britain) 1987).
It produces two types of oil, one from the flesh (palm oil) and another from the kernel
(palm kernel oil) of the fruit. These oils can then be separated into a high-melting
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fraction (stearin) and a low-melting fraction (olein) (Gunstone 1996). The yield is
about 4-5 tonnes/hectare of palm oil and 0.5 tonnes/hectare of palm kernel oil.
The main use of soybean is the protein rich meal obtained after extraction of the oil.
This is used for animal feed and makes up between 50-70% of its value (Gunstone
1996). Soybean oil prices are currently at the lowest they have been since 1986-87
(Guzman 2001). It is mainly produced in USA, China, Brazil and Argentina
(Gunstone 1996). Soybean oil is highly unsaturated with linoleic and linolenic acid
comprising over 60%. The remainder is predominantly oleic and palmitic acid.
The sunflower plant is mainly grown in the former Soviet Union, the European
Union, Argentina, China, USA, and Eastern Europe (Gunstone 1996). It too is at its
lowest price since 1986-87 (Guzman 2001). The seed oil is also highly unsaturated,
containing mostly linoleic and oleic acid.
Rapeseed oil source has received the most attention with considerable research
performed on the altering of the plants by breeding techniques and genetic
modification. Such changes have been made to give the plant specific qualities such
as tolerance to broad-spectrum herbicides (Friedt and Lühs 1998). The project is of
interest for the possibility of modifying the fatty acid composition of the oil by using
these techniques. Not only can the length of the fatty acid be altered, but also
properties such as the degree of unsaturation, stereochemistry and position of double
bonds (Friedt and Lühs 1998). It may be possible therefore to modify the plant to
grow in a particular climate and produce oil that has the properties necessary for
optimum cracking reactions.
According to Friedt and Lühs (1998), rapeseed oil is ideal for non-food applications
because of qualities such as relatively homogeneous composition, high degree of
refinement, freedom from contaminants and also biodegradability. This is evidenced
by the relatively large number of studies that have used canola oil, a modified
rapeseed oil, to investigate cracking reactions.
Unmodified rapeseed oil is high in erucic, oleic and linoleic acid. The composition
varies greatly among plant variety with some oil products being high in the saturated
lauric acid. It is mainly produced in northern Europe, China, India and Canada.
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Australia has recently increased its production with estimates of about 300,000 tonne
now achieved annually (Department of Natural Resources and Environment 2001).
Although coconut oil is not produced on as large a scale as the oils mentioned
previously, it would be of interest to study the cracking reactions associated with this
oil as it is quite high in lauric acid. This makes it highly saturated oil and it would be
expected that any major differences in reaction products could be largely attributed to
this fact.
Pillared clays as cracking catalysts
As noted previously, a major problem associated with the use of pillared clays as
catalysts has been their lack of thermal and hydrothermal stability above roughly 600
to 700°C depending on the pillar and clay used. Because of this, many studies have
focussed on methods of improving such stability while also retaining, or increasing,
its catalytic properties. Current research has examined how the introduction of
various pillaring species alters the PILC properties (see e.g. review Kloprogge 1998).
Another way of changing the property of PILCs has been to alter preparation
techniques. This is usually examined after the pillaring species has been optimised so
as to maximise the desired properties of the PILC. Each method has had various
degrees of success and will be further discussed.
Various pillaring species
This usually involves intercalation with one easily pillared cation, such as Al, and
then the addition of another cation to give the PILC a specific property. Some cations
that are used are Ce, Cr, Ga, La, Si, Ti, and Zr. Because there are a large number of
cations available, extensive study has been carried out in this area and a few will be
discussed here for an overview.
Gallium This cation has a number of chemical properties (eg. ionic radius) that are similar to
Al3+, making it ideal for pillaring. Bradley and others (1990a) have shown that the
Ga13 and GaAl12 pillaring agents that can be formed by hydrolysis, are similar in
175
structure to the Al13 Keggin-ion species. The d001 spacing of the Ga13 species was
around 5.6% larger than Al13. This correlated well with their estimate of 5.7% for a
Keggin-like structure. The pillaring solutions prepared were tested for thermal
stability by allowing each to reflux until a precipitate formed. It was found that the
GaAl12 solution could be refluxed for over 3 weeks, over 5 times longer than the Al13
solution. Using NMR techniques, such stability was attributed to the overall increase
in symmetry of the pillar owing to the better fit of the Ga3+ ion in the central position
of the modified Keggin structure (Bradley and others 1990b). Further MAS NMR, IR
and XRD studies confirmed that the GaAl12 structure is structurally analogous to the
Al13 species (Bradley and others 1992, 1993).
Bradley and Kydd (1991) were also able to demonstrate how the thermal stability of
the GaAl12 PILC was markedly better than Al13 and Ga13. They found that the surface
area of the GaAl12 pillared clay dropped from 277 to 196 m2/g over a temperature
range of 200 to 700oC whereas the other two PILCs dropped to less than 115 m2/g.
This correlated with the stability of the ions in solution. In a further article they
examined the Brönsted acidic character of these pillared clays and concluded that the
GaAl12 pillared clay had the highest abundance (Bradley and Kydd 1993).
González and others (1992) also produced thermally stable GaAl PILCs that retained
70% of its surface area when heated to 700oC. In a later study (Hernando and others
1996), they examined how modifying this PILC with cerium effected its thermal
stability and catalytic properties. They determined that although the presence of Ce
decreased the surface area of the PILC, it also increased the Brönsted acid site density
making it more selective toward cracking reactions.
González and others (1999), also studied the catalytic properties of GaAl PILCs with
respect to the cracking of heavy oils. They produced thermally stable PILCs that
retained around 85% of its surface area and micropore volume when heated to 700oC.
As shown in Table 1, the GaAl PILC was the only one to exhibit a basal spacing by
XRD at 700oC (17.3 Å). The results from their fixed-bed reactor at 482oC indicated
that, although the GaAl PILC had the highest activity, it formed more gaseous
product and had a higher coke formation than the Al PILCs. The gasoline product
formed by the GaAl PILC did however have a higher octane number, which
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somewhat compensates for lack of quantity. This higher octane number was
attributed to the dehydrogenating effect of the Ga, which resulted in the production of
more alkenes.
Lenarda and others (1999) also produced PILCs using a solution containing an Al/Ga
ratio of 12/1. They further treated the PILC with NH3 vapours and repeated the
pillaring process. The re-pillared clays had a similar XRD pattern to the standard
PILC but had a decrease in surface area from 383 to 323 m2/g and an increase in
pillar density of 30%. This was due to the re-pillaring process in which more pillars
diffuse into the interlayer space and/or unpillared or partially pillared areas are
completed (Fig. 2). They too found that the GaAl12 species retained its structure up to
700oC.
Domínguez and others (1998) examined the hydrolysis of various mixed solutions
and concluded that for the Al-Ga system, the formation of GaAl12 species was more
probable in the pH range of 4 - 5, after which the Al13 species was more likely to
form.
Lanthanum and Cerium Sterte (1991) assessed lanthanum as a rare earth cation that, "most readily formed a
complex with aluminium suitable for pillaring". This author was able to produce
LaAl pillared montmorillonite with basal spacings of around 26Å and surface areas
of 300-500 m2/g. The pillaring solution was prepared by either refluxing mixtures of
aluminium chlorohydrate and lanthanum chloride for to up to 120 hours or by treating
the solution in an autoclave at 120o-160oC for 12-96 hours. He determined that a
La/Al ratio of at least 1/5 was needed to produce large pore structures. From XRD
analysis it was shown that between 72 and 96 hours of refluxing was required for
maximum basal spacings while only 12 hours was needed for solutions autoclaved at
160oC.
Booij and others (1996) also attained, by hydrothermal treatment, large pore LaAl
and CeAl PILCs with basal spacings around 25Å and surface areas of about 430m2/g.
They concluded that the La/Al or Ce/Al molar ratio can be as low as 1/30 as the
formation of the initial polyoxocation is favoured by high Al concentrations. They
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attributed the stability of the pillared structure to the higher Altetrahedral/Aloctahedral ratio
compared to the normal Keggin structure.
Valverde and others (2000) synthesized PILCs by mixing 0.05M solutions of
La(NO3)3 or Ce(NO3)3 with a bentonite clay suspension that had already been
allowed to react with an Al polyoxocation solution. Basal spacings of 16 to 20Å were
recorded with surface areas from 239 to 347 m2/g. Although these pillared clays were
similar in structure and acid properties to Al PILCs, they showed an increase in
thermal and hydrothermal stability. They concluded that the cations were not part of
the pillar and that they delayed the dehydroxylation of the PILC with Ce being more
effective than La. They suggested that this delaying effect was due to the cation either
blocking the hexagonal cavities in the tetrahedral layer or somehow strengthening the
bonding of the Al pillars.
Various montmorillonites from different localities were pillared with Ce and Al by
Pires and others (1998). They found that by changing the total metal concentration of
the pillaring solution they could regulate the interlayer pore size. Basal spacings up to
22.2Å were recorded at 500oC with specific surface areas being as high as 300 m2/g
at 700oC. They observed that the extent of octahedral substitution in the parent clay
had a large influence on the thermal stability of the PILC produced.
Silicon By using two industrially produced silanes, 3-aminopropyltrimethoxysilane
(APTMS) and 2-(2-trichlorosilylethyl)pyridine (TCSEP) as pillaring solutions, Fetter
and others (1994) where able to produce pillared clays having good thermal stability.
The PILC intercalated with TCSEP gave a number of interlayer spacings (up to 10Å),
which were attributed to the range of polymeric species present in the solution. It had
however, poor thermal stability with its structure almost collapsing at 700oC. The use
of APTMS gave a more homogenous interlayer spacing of around 7Å and was stable
up to 700oC. This PILC also maintained a large microporosity and some acidity at
700oC. A further study (Fetter and others 1995) used competitive ion exchange of Al-
polyoxocations and TCSEP to produce a pillared clay exhibiting good thermal
stability with an acidity comparable to that of HY zeolites. The SiAl PILC produced
had a basal spacing of 17.4Å and a surface area of 278 m2/g when calcined at 600oC
178
(the temperature necessary to burn off the organic moiety). With further calcination at
700oC, the surface area only decreased to 244 m2/g with a basal spacing of 17.2Å.
XRD patterns showed that the structure collapses at around 800oC.
Sterte and Shabtai (1987) produced hydroxy-SiAl pillaring solutions by two methods:
(1) by mixing orthosilicic acid with AlCl3 and then treating with aqueous NaOH and
allowing to age and (2) by ageing an Al13 solution and then combining with
orthosilicic acid. The SiAl pillared montmorillonite produced by the first method
gave basal spacings around 19Å (table 3) and were not affected by the Si/Al ratio in
the pillaring solution. The surface area did drop substantially as the Si/Al ratio
increased. The same trend occurred for the PILCs prepared by the second method
except the basal spacings were lower (∼17Å). The decrease in surface area was
attributed to the increase in substitution of -OH groups by the bulkier -OSi(OH)3
groups in the pillaring species. They also examined the thermal stability of the PILCs
and noted a rapid decrease in surface area for Si/Al ratio of 0.53 as it was heated to
600oC whereas it was slower for Si/Al ratios of 1.04 and 2.08.
Zhao and others (1992) also prepared SiAl PILCs by methods similar to Sterte and
Shabtai (1987) and they found that the structure of the PILCs produced by both
methods were similar but the SiO2 content of the PILC produced by method (2) was
higher than that from method (1). This led them to likewise conclude that Si was
incorporated into the Al pillars and 27Al-NMR was used to confirm that the pillar
structure was similar to the Keggin structure in Al PILCs. Hence, they suggested two
reactions occurring in solution:
[Al13O4(OH)23(H2O)12]7+ -OH + HO-[Si(OH)2]n-OH [1]
[Al13O4(OH)23(H2O)12]7+-O-[Si(OH)2]n-OH + H2O
13AlCl3 + 28OH- + 9H2O-[Si(OH)2]n-OH [2]
[Al13O4(OH)23(H2O)12]7+-O-[Si(OH)2]n-OH
Thus a structure was proposed similar to that of Sterte and Shabtai (1987) and is
depicted in Figure 3. Sterte and Shabtai (1987) also found that the SiAl PILCs had
179
more Brönsted and Lewis acid sites compared to Al-pillared species and a lower
Lewis/Brönsted ratio. This was attributed to the presence of acidic silanol groups in
the pillars. The cumene cracking ability of the SiAl PILC was examined and they
found an increase in activity due to the incorporating of silica into the aluminium
pillars.
Zirconium Farfan-Torres and others (1992) describe two methods of preparing Zr PILCs. Both
methods involve the mixing of zirconyl chloride (ZrOCl2) solution to a clay
suspension with one having an extra step of refluxing at 100oC to force
polymerization of the Zr complex. The non-refluxed solution produces a square
planar complex that can then polymerize to give Zr8 and Zr12 units and upon
calcination at 500oC, give PILCs with basal spacings of 16Å. This method has the
disadvantage of being time consuming whereas the refluxed solution is quicker but
produces PILCs with disordered layer structure and basal spacings around 15Å. This
led them to investigate how parameters such as time of reaction, temperature of
reaction and concentration all affect the degree of polymerization. They found that
although heating of the ZrOCl2 solution and higher contact time assisted the
polymerisation process, it also causes the pH to drop which led to degradation of the
clay structure. The pH drop is due to the zirconyl ion, present as the tetramer
[(Zr(OH)2.4H2O)4]8+, hydrolysing to form the tetramer [Zr4(OH)14.10H2O]2+ and H+.
Although the authors do not examine the stability of the pillared clay above 500oC,
they do show that the introduction of Zr enhances the acidic properties of the solid.
Ohtsuka (1993) intercalated sodium fluoride tetrasilic mica with ZrOCl2 solutions of
various concentrations at room temperature and at an elevated temperature. He
produced intercalated clays having interlayer spaces of 7, 12 and 14 Å according to
the degree of polymerization of the zirconium tetramer. The dimension of this
tetramer was given as 8.98 Å wide and 5.82 Å thick. This was given as the major
species responsible for producing the 7 Å interlayer distances with two and three two-
dimensional layers being responsible for the 12 and 14 Å species respectively.
Halogens in solution (Cl-, Br-) were shown to form part of the zirconium tetramer
and, if present in high concentrations, had an effect on the extent of polymerisation.
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The PILC formed from the 14Å species has an homogenous pore structure and
exhibited good thermal stability with the interlayer spacing falling to only 10Å upon
heating to 700oC and the surface area reaching a maximum at 600oC.
Gandía et al. (1999) pillared saponite and montmorillonite using, what they term, a
non-aggressive method in which a commercial solution of zirconium in acetic acid
was used. The intercalation step was performed with pH=3.3 at room temperature
while the calcination was performed at 500oC. This method produced basal spacings
of 14-24 Å with surface areas up to 300 m2/g. In a further study (Gill and others
2000), they found that upon calcination the Zr PILC actually increased in surface
area. This increase was attributed in part to the decomposition of acetate ligands thus
giving access to the porous network of the PILC.
A comparison of the properties of the Zr PILC to the ZrAl species was made by
Cañizares and others (1999). They prepared the Zr-PILC using a ZrOCl2 solution
mixed with bentonite. They tried three methods to produce the ZrAl PILC: (1)
impregnating an Al-PILC with Zr, (2) mixing the ZrOCl2 solution to previously
intercalated Al clay slurry and (3) mixing of Al and Zr pillaring solutions, addition of
a basic solution to give OH/Al ratio of 2 and then ageing for 16 hours. The first
method gave products which could not be calcined higher than 200oC before
structural collapsed. The products of the second method could be calcined
successfully but resulted in low basal spacings. The third method gave acceptable
PILCs and was used for further analysis. They only analysed the PILCs up to 500oC
but were able to conclude that, “the surface acidity, methane adsorption and thermal
stability were increased by incorporating aluminium into the single oxide pillars”. It
was also shown that the structure of the pillar varied with Al concentration with the
Keggin structure predominating at higher Al/Zr ratios.
Chromium A solution of CrCl3 and AlCl3 in Na2CO3 was used by Zhao and others (1995) to
produce a CrAl PILC. Basal spacings of around 18 Å were achieved when calcined at
500oC with surface areas around 230 m2/g. The thermal stability was found to be
greater than that of Cr PILC as well as possessing more acid sites. Toranzo and others
(1997) stated that Cr3+ can form the trimer [Cr3(OH)4(H2O)9]5+, the dimer
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[Cr2(OH)2(H2O)8]4+ or no polymerization occurs depending on the Al3+/Cr3+ ratio in
the solution. They also found that CrAl PILCs were more stable thermally than Cr
PILCs.
Titanium Del Castillo and Grange (1993) determined that Ti(OEt)4 (titanium tetraethoxide)
gave a polycationic precursor that gave a PILC of regular structure and was stable at
600oC. Regulating the pillar size and distribution was difficult as it depended greatly
on solution pH and reaction temperature. The acidity of the Ti PILCs produced were
determined to be mainly of the Lewis kind.
Swarnakar and others (1996) prepared a TiAl pillaring solution by hydrolysis of
AlCl3 and Ti(OEt)4 for pillaring of beidellite and montmorillonite. From XRD
analysis it was determined that the pillared beidellite was thermally more stable than
the pillared montmorillonite with a peak seen at 700oC.
Tantalum The intercalation of montmorillonite using niobium and tantalum was performed
early on by Christiano and others (1985). They produced PILCs with basal spacings
around 18 Å but they were only stable to 400oC. Guiu and Grange (1994, 1997)
examined ways to produce more stable Ta PILCs. They prepared a pillaring solution
by controlling the hydrolysis of Ta(OC2H5)5 in an ethanolic acidic solution. The PILC
had a basal spacing of 26 Å and was stable to 600oC. A pillar precursor structure was
proposed as [Ta8O10(OR)20], R= H, C2H5. The pillaring of Ta was shown to produce
stronger Lewis sites and new Brönsted sites.
Preparation techniques Altering the preparation of a PILC can have dramatic effects on properties such as
thermal stability and acidity. This area also has received considerable attention with
many authors who are looking at ways to economise the process for commercial
viability. Current problems in preparation are time and energy costs, water usage and
mixing of clay solutions. Some of these issues, along with property changes, have
been addressed and will now be discussed briefly.
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Intercalation step Mixing of the clay suspension with the pillaring solution over a time period with heat
is the standard method for intercalation of clays. This process can take up to 6 hours
to complete as the pillaring solution is added drop-wise and the mixture is stirred for
at least 2 hours with heat supplied. Although this method has had success in
laboratory synthesis of pillared clays, it is not an ideal preparation technique for large
scale production because large amounts of water and heat are necessary.
The use of ultrasonics in this step was reported by Katdare and others (2000). They
intercalated a Ca-montmorillonite using ultrasonic treatment over a number of time
periods. The most intense and sharpest peaks on XRD patterns were for the calcined
sample that had been left in the ultrasonic bath for 20 minutes. They than varied the
pillaring solution and determined the optimum Al3+/clay ratio as being 20 meq/g.
This PILC (PILCUS) had a basal spacing of 19.2 Å and a BET surface area of 281
m2/g. To test the thermal and hydrothermal stability of the PILCUS, they heated it to
900oC in 200o steps as well as to 750oC with 100% steam for 8 hours. A similar
treatment was given to a PILC (PILCONV) intercalated by the conventional method.
The results showed that the structure of PILCONV collapsed at around 700oC while
the PILCUS still had some structure at 900oC. The hydrothermal results were the
same with the PILCUS still having a basal spacing of 18.1 Å and a surface area of
189 m2/g. The stability was attributed to the uniform pillaring obtained by the use of
ultrasonics. They also reported how the use of ultrasonics did not alter properties
such as acidity and catalytic activity.
The same authors, in a later study (Katdare and others 2000), looked at how the
exchangeable ions present in the starting clay affected the ultrasonic treatment. They
converted the Ca-montmorillonite to Na+ and La3+ forms by ion exchange. This gave
exchangeable cations with valencies of +1, +2 and +3. They found that the optimum
times for ultrasonic treatment were 5 minutes for the Na form, 20 minutes for the Ca
form and 80 minutes for the La form. The increase in time was due to the higher
charge ions being more tightly bound to the clay layers. They also concluded that the
role of ultrasound is to accelerate the [Al13]7+ diffusion within the clay layers.
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This method of intercalation has a number of advantages that help to make large-
scale production of pillared clays more viable. First, it reduces the time needed from
several hours to less than 30 minutes. It also requires no heat for the process, thus
saving in costs and reducing the safety risks, although some safety issues arise with
ultrasonics that would need to be addressed. Finally, the clay suspension required can
be more concentrated compared to conventional methods, thus using less water and
space.
Fetter and others (1996) also looked at a way to speed up the intercalation step by
using microwave irradiation. They made up a 10 wt% clay solution and added
aluminium chlorohydrate to it making an Al/clay ratio of 5mmol/g. The sample was
sealed and subjected to microwave irradiation for various time periods and then
pillared by conventional methods. The samples prepared using microwaves gave
surface areas some 20-30% higher than samples prepared by the conventional method
(ie. mixing for 18 hours). They also found that the irradiation time had little effect on
the surface area with a maximum of 347 m2/g being attained after only 5 minutes. In
a later study, Fetter and others (1997) were able to similarly prepare a pillared clay
using microwave irradiation for 7 minutes but with a more concentrated starting clay
slurry of 50 wt%. They achieved a surface area of 331 m2/g, some 87 m2/g higher
than the sample they prepared by the conventional method.
Separating and Washing
This step serves to remove any excess ions that are present in preparation for the
calcining of the intercalated clay. The separation can be done by filtration or, for a
faster result, centrifugation. The washing procedure is more time consuming, as it
usually requires the re-suspension of the separated clay in deionised water with
stirring for a time period. This process is done a number of times, usually until the
filtrate is free of chloride ions as determined by the AgNO3 test. All of this is time
consuming and would be hard to scale-up as vast amounts of water would be
required.
Thomas and Occelli (2000) examined the effect that washing had on an Al
intercalated montmorillonite. They examined samples of the intercalated clay after
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each washing up to 4 times with 400 cm3 of deionised water as well as a sample
without any washing. The XRD results showed a broad weak peak for the unwashed
sample, which then shifted to 18.9 Å for the first washing, and this reflection became
sharper with subsequent washing. They conclude that the initial cations present in the
interlayer space were not Keggin ions but that they were formed, "in situ by base
hydrolysis of the different oligomers present". Hence, the washing procedure is
necessary to form stable PILCs as their stability is related to the formation of these
Keggin ions.
Aceman and others (2000) examined how allowing the clay to age in the pillaring
solution and how the use of dialysis compared to conventional washing methods.
They also determined that initially aluminium is adsorbed into the interlayer space
either in a monomeric state or as small oligomers. Several days were needed for these
species to undergo hydrolytic oligomerization to form Keggin-like ions. This could
only occur however, if the excess Al, Na and Cl ions had been removed by washing
or by dialysis. For dialysis they put the intercalated sample in a Visking dialysis bag
dipped in double-distilled water for one week at room temperature. For laponite and
hectorite samples, the dialyzed and non-dialysed samples showed similar poor
thermal stability. For montmorillonite, the dialyzed sample was comparable to the
sample washed four times. For beidellite and saponite, the dialyzed samples gave the
best thermal stability results with XRD peaks being more intense and sharper than
those of the washed sample.
Introduction of organic molecules The use of organic molecules, such as surfactants, in the pillaring solution to act as a
swelling has also been examined. This helps to reduce significantly the amount of
water required while also making the clay easier to filter. It involves the introduction
of an organic molecule into the interlayer along with the pillaring species. The
organic molecule, of known shape and size, can later be removed by heat to leave a
more regular pore structure. By investigating how such organic molecules affect the
pillaring process, specific pore sizes can be designed.
185
Michot and Pinnavaia (1992) incorporated a nonionic surfactant of general formula
C12-14H25-29O(CH2CH2O)5 with the usual Al-pillaring solution. The resultant PILC
had a more uniform micropore distribution and a sharper, more symmetrical 001
reflection compared to one prepared without surfactant. The basal spacing was
however smaller than normal (15.3 Å) but this was attributed to the surfactant
limiting the condensation of Al13 units within the interlayer space. The surface area
(305 m2/g) was also slightly larger than the conventional PILC (279 m2/g) and
contained more mesopores. An important feature of this method is that the
intercalated product is easily filtered and could be washed free of excess ions using
two thirds less water than that required by the conventional method.
Galarneau and others (1995) converted a Li-fluorohectorite to a quaternary-
ammonium exchanged form and then mixed with a solution of neutral amine and
tetraethylorthosilicate (TEOS). The interlayer space was swollen which allowed the
TEOS to enter and hydrolyse. The surfactants were then removed by calcining at
600oC leaving a rigid silica framework between the layers. The basal spacings of the
PILC ranged from 14.9 to 23.4 Å, depending on the chain length of the neutral amine
used.
Suzuki and others (1988) were able to use polyvinyl alcohol as a pre-swelling agent
for pillaring of montmorillonite with Al13. Hectorite was similarly (Suzuki and others
1991) and they showed how the presence of polyvinyl alcohol provided favourable
conditions to allow smaller Al cations to hydrolyse into larger ones. As they
increased the concentration of aluminium chlorohydroxide in the pillaring solution,
the basal spacings increased, as did the pillar concentration. This was not the case
with the PILC prepared without polyvinyl alcohol. Cracking of vegetable oil As mentioned earlier, transesterification of vegetable oil is currently the method of
choice for conversion to a useable fuel. Many studies have however been done on the
upgrading of such oils using various catalysts and reaction conditions. These studies
have examined the products obtained by the cracking processes and have tried to
correlate the effect that these variables have on the final producs. The problem with
186
any research done in this field is that because the starting material (vegetable oil) is a
complex mixture that changes drastically between types, it is difficult to extrapolate
or replicate the results. Hence, the reporting of any results in this review must be used
as a guide only and can not be expected to extend totally to the anticipated outcome
of this project.
Canola oil Katikaneni and others (1995a) used a number of catalysts, including Al- PILC, to
convert canola oil to fuel using a fixed bed reactor. They examined how each catalyst
performed with respect to organic liquid product (OLP) yield, selectivity and coke
formation. They found that HZSM-5 gave the highest yield of OLP of 63 mass %
with the pillared clay being third giving a 55 mass % yield. The OLP of the PILC
contained more aliphatic hydrocarbons than the other catalysts and the least amount
of aromatic hydrocarbons. Their results showed that as the pore size of the catalyst
was increased, the conversion of canola oil, the coke formation and the selectivity for
aliphatics increased while the yield of hydrocarbons and the selectivity for aromatics
decreased. This led them to the conclusion that medium pore catalysts enhanced the
initial cracking and deoxygenation reactions needed for an optimum fuel yield. They
were also able to propose a reaction pathway for conversion by looking at the
products formed (Fig. 4). After the initial cracking occurs (step 1) further reaction
steps were proposed for the heavy hydrocarbons and oxygenates formed. Both are
thought to undergo secondary cracking (steps 2 and 5) to form gas products. The
heavy oxygenates can also be deoxygenated (step 4) to form CO, CO2, methanol and
acetone while the heavy hydrocarbons undergo aromatization (step 3) to form C9+
aromatic hydrocarbons. The authors suggest that the initial cracking occurs in the
inter-planar space and then diffuses into the pores of the clay sheets where further
reactions proceed. One of these reactions is polymerization, which leads to coke
formation and a clogging of the inter-planar space.
A further study by these authors (Katikaneni and others 1995b) showed how co-
feeding with steam during the reaction helps to increase olefin formation as well as
increase the catalyst life by decreasing coke formation.
187
Vonghia and others (1995) suggested that the initial cracking reaction occurred via
two mechanisms: β-elimination and γ-hydrogen transfer (Fig. 5). Both are initiated by
the bonding of a carbonyl oxygen to a Lewis acid site on the catalyst. It is possible
for both reactions to occur on a triacylglyceride molecule but β-elimination can only
happen once.
The effect that acidity, basicity and shape selectivity of a catalyst had on the
conversion of canola oil was examined by Idem and others (1997). The various
catalysts and their properties are listed in table 3. An empty reactor run was
performed to evaluate the contribution of each catalyst, and the products of this run
led them to the conclusion that initial decomposition of the oil to heavy hydrocarbons
and heavy oxygenates was independent of catalyst properties.
The effect shape selectivity had on the product was evaluated by comparing HZSM-5
and silicalite against the empty reactor run. These catalysts gave a higher OLP yield
along with a lower gas yield. This led them to the conclusion that only limited
secondary cracking was allowed because of the long molecules diffusing through the
pore structure with minimal C-C bond scission. The OLP from the two catalytic runs
had a higher fraction of C7-C9 aromatic hydrocarbons. This was attributed to an
increase in cyclization and aromatisation reactions (eg. Diels-Alder and
dehydrogenation) that are allowed to occur within the pores of the catalyst.
HZSM-5, silica-alumina and γ-alumina were compared to evaluate the role of catalyst
acidity in conversion products. Product distribution for runs using silica-alumina and
γ-alumina were very similar to the empty reactor run with yields being slightly
higher. As both of these catalysts contain Brönsted and Lewis acid sites, it was
suggested that the acidity of the catalyst did not determine the product selectivity.
The increase in OLP yield and total aromatic hydrocarbons obtained by using HZSM-
5 was attributed mainly to its shape selective properties, not acidity.
To examine how basicity affected the product yield, they used calcium oxide and
magnesium oxide as catalysts. The results showed that the presence of basic centres
inhibited secondary cracking and produced large amounts of residual oil.
Katinkaneni and others (1998), in a later study, looked at the conversion products
using HZSM, HS-mix and silica-alumina catalysts but they carried out the reactions
188
in a fluidised bed reactor. This involved the continuous flow of argon through the
catalyst bed, which assists in catalyst regeneration. They summarized the reaction
sequence (below) proposed from previous studies and related the catalyst properties
to the conversion products by means of this sequence.
Canola oil ⇒ long-chain CxHy + long-chain [1]
oxygenated CxHy (thermal)
long-chain oxygenated CxHy ⇒ long-chain [2]
CxHy + H2O + CO2 + CO (thermal + catalytic)
long-chain CxHy ⇒ paraffins + olefins [3]
(short and long-chain)
(thermal + catalytic)
short-chain olefins ⇒ C2-C10 olefins (catalytic) [4]
C2-C10 olefins ⇔ aliphatic CxHy + [5]
aromatic CxHy (catalytic)
canola oil ⇒ coke (thermal) [6]
n(aromatic CxHy) ⇒ coke (catalytic) [7]
The Brönsted acidity of the catalyst can enhance the reactions that occur in steps 2-4
and this was confirmed by their results which showed that canola oil conversion
increased as the reaction temperature and catalyst acid site density was increased.
Such conversions were also enhanced by a decrease in fluidising gas velocity, as
there was a greater contact time with the catalyst. The selectivity for OLP in a
fluidised bed reactor was lower than that achieved in a fixed bed reactor. This too was
189
related to the shorter contact time in the fluidised-bed reactor, which did not allow the
formation of additional OLP from C2-C5 olefins in steps 4 and 5.
Palm oil Leng and others (1999) used a fixed bed reactor to crack palm oil over HZSM-5
catalyst. The maximum formation of gasoline range hydrocarbons was achieved at
400oC with a low space velocity. The conversion of palm oil was low (40-70%)
compared to those using canola oil (Idem and others 1997) where conversions up to
100% were achieved. This was attributed to the fact that palm oil contains more
saturated fatty acids (palmitic acids) than canola oil and these have a greater stability
than unsaturated fatty acids. A similar reaction pathway (Fig. 6) to that shown for
canola oil was proposed for palm oil conversion over HZSM-5, with deoxygenation
and primary cracking being the initial reactions. Likewise, secondary reactions were
controlled by catalyst properties (eg. acidity and pore structure) as well as the
reaction conditions (eg. temperature and flow rate).
Twaiq and others (1999) also looked at palm oil conversion using HZSM-5 as well as
zeolite β and ultrastable Y (USY) zeolites. They were able to achieve conversions of
up to 99 wt % with gasoline yields of 28 wt%. They concluded that HZSM-5 was the
best catalyst for conversion, gasoline yield, selectivity for aromatic and lower coke
formation.
Sunflower oil A study by Dandik and others (1998) examined the products of the conversion of
used sunflower oil with HZSM-5 using a special fractionating pyrolysis reactor. A
conversion of 96.6% was achieved at 420oC with an OLP yield of 33%. The length of
the fractionating column on the reactor had an effect on the OLP content with an
increase in length giving a significant increase in n-alkene content. This is given as a
variable that can be adjusted to optimise the fuel product.
Acknowledgements
190
The authors wish to thank the Inorganic Materials Research Program, School of
Physical and Chemical Sciences, Queensland University of Technology, for the
infrastructural and financial support.
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Toranzo R, Vicente MA, Banares-Munoz MA (1997) Pillaring of a saponite with aluminum-chromium oligomers. Characterization of the solids obtained. Chem. Mater. 9: 1829-1836
Twaiq FA, Zabidi NAM, Bhatia S (1999) Catalytic conversion of palm oil to hydrocarbons: Performance of various zeolite catalysts. Ind. Eng. Chem. Res. 38: 3230-3237
Valverde JL, Cañizares P, Kou MRS, Molina CB (2000) Enhanced thermal stability of Al-pillared smectites modified with Ce and La. Clays and Clay Minerals 48: 424-432
Vassallo AM, Cole-Clarke PA, Pang LSK, Palmisane A (1992) Infrared emission spectroscopy of coal minerals and their thermal transformation. J. Applied Spectroscopy 46: 73-78
Venuto PB, Habib JET (1979) Fluid catalytic cracking with zeolite catalysts. 156 Marcel Dekker, Inc New York
Vonghia E, Boocock DGB, Konar SK, Leung A (1995) Pathways for the deoxygenation of triglycerides to aliphatic hydrocarbons over activated alumina. Energy & Fuels 9: 1090-1096
Zhao D, Yang Y, Guo X (1992) Preparation and characterization of hydrosilicoaluminium pillared clays. Inorganic Chemistry 31: 4727-4732
Zhao D, Yang Y, Guo X (1995) Synthesis and characterization of hydroxy-CrAl pillared clays. Zeolites 15: 58-66
194
Table 1 - Basal spacings, (Å) at different temperatures (González and others
1992)
195
Table 2- Properties of SiAl PILCs produced by 2 methods (Sterte and Shabtai 1987) Method of
preparation
Si/Al ratio in hydroxy-
SiAl solutions Surface area (m2/g) d(001)(Å)
1 0.0 458 19.2
1 0.53 369 19.3
1 1.04 324 19.5
1 2.18 278 19.0
2 0.0 499 17.6
2 0.5 498 17.7
2 1.0 460 17.2
2 2.0 343 17.0
196
Table 3- Characteristics of catalysts used by Idem and others (1997).
Catalyst
type
Acidic,
basic or
neutral
Type of
acidity
Si/Al
ratio
Strength
of acid
or basic
sites
Pore
structure
Pore
size
(nm)
Surface
area
(m-1g-1)
Shape
selectivity
HZSM-5 Acidic Mostly B 56 Strong Crystalline 0.54 329 V. high
Silicalite Neutral None No Al N/A Crystalline 0.54 401 V. high
Silica Neutral None No Al N/A Amorphous 11.46 211 None
γ-alumina Acidic B and L 0 Moderate Amorphous 14.93 241 None
Silica-
alumina Acidic B and L 0.79 Moderate Amorphous 3.15 321 None
Calcium
oxide Basic None N/A Strong Amorphous 11.86 7 None
Magnesium
oxide Basic None N/A Weak Amorphous 15.22 27 None
Empty
reactor neutral none N/A N/A N/A N/A None None
197
Figure captions
Fig. 1 Compositions of the most common vegetable oils.
Fig. 2 Schematic representation of the repillaring process
Fig. 3 Schematic model of the SiAl pillaring complex (modified after Sterte and
Shabtai, 1987)
Fig. 4 Reaction pathway for canola oil conversion using pillared clay catalysts as
proposed by Katikaneni and others (1995a,b).
Fig. 5 Two possible pathways for cracking reactions via β-elimination and γ-
hydrogen transfer.
Fig. 6 Proposed reaction pathway for cracking of palm oil over HZSM-5 (Leng and
others 1999).
198
Palm Oil
Soybean Oil
Sunflower Oil
Rapeseed Oil
14%75%
7%
Linoleic Oleic
P almitic
22%
54%
8%
11%Linoleic
Oleic
Linolenic
Palmitic
10%
38%47%
1%
PalmiticOleic
Linoleic
Myristic
17%
13%5%4%
46%
10%
Erucic
Myristic
Oleic
Linoleic
Palmitic Linolenic
5%3%
8%
48%17%
LauricMyristic
PalmiticLinoleic
Oleic
Coconut Oil
Fig. 1
199
Fig. 2
200
Fig 3
201
6
Deoxygenation
CO + CO2 + Methanol + Acetone
Coke
Aromatic Hydrocarbons
Canola Oil
Heavy Hydrocarbons + Heavy Oxygenates
Deoxygenation and Cracking
Aromatization
C1-C6 Hydrocarbon Gases
1
7
2
3
4 5
Cracking
Polymerization
Fig. 4
202
Fig. 5
CH2
C
CH2
O
O
O
H
C
C
C
O
O
R1
O
R1
CH2
CH2
CH H R2
CH2
C
CH2
O
O
C
C
OH
R1
O
CH2
H O C R1
O
CH2 CH - R2 ++
γ-hydrogen transfer
β-elimination
203
Palm Oil
Light olefins + Light paraffins (gasoline) + CO2 + alcohol + CO + H2O
Coke
Deoxygenation and cracking
Heavy hydrocarbons + Oxygenates
Olefins + paraffin (gasoline, diesel & kerosine)
Polymerisation
Aromatic hydrocarbons
Oligomerisation Aromatisation, Alkylation
Isomerisation
Secondary cracking + deoxygenation
Gases (light olefins, paraffins, CO, CO2, H2O)
Fig. 6
204
XPS STUDY OF THE MAJOR MINERALS IN BAUXITE:
GIBBSITE, BAYERITE AND (PSEUDO-) BOEHMITE
J. Theo Kloprogge1, Loc V. Duong1, Barry J. Wood2, and Ray L. Frost1
1 Inorganic Materials Research Program, Queensland University of Technology, 2
George Street, GPO Box 2434, Brisbane, Q 4001, Australia
E-mail: [email protected]
2 Brisbane Surface Analysis Facility. The University of Queensland, Brisbane, Qld
4072, Australia
205
Abstract
Synthetic corundum (Al2O3), gibbsite (Al(OH)3), bayerite (Al(OH)3), boehmite
(AlOOH) and pseudoboehmite (AlOOH) have been studied by high resolution XPS.
The chemical composition based on the XPS survey scans were in good agreement
with the expected composition. High resolution Al 2p scans showed no significant
changes in binding energy, with all values between 73.9 and 74.4 eV. Only bayerite
showed two transitions, associated with the presence of amorphous material in the
sample. More information about the chemical and crystallographic environment was
obtained from the O 1s high resolution spectra. Here a clear distinction could be made
between oxygen in the crystal structure, hydroxyl groups and adsorbed water. Oxygen
in the crystal structure was characterised by a binding energy of about 530.6 eV in all
minerals. Hydroxyl groups, either present in the crystal structure or on the surface
exhibited binding energies around 531.9 eV, while water on the surface showed
binding energies around 533.0 eV. A distinction could be made between boehmite and
pseudoboehmite based on the slightly lower ratio of oxygen to hydroxyl groups and
water in pseudoboehmite.
Keywords: Bauxite, Bayerite, Boehmite, Corundum, Gibbsite, XPS
Introduction
Bauxite forms a major resource of aluminium in Australia and especially in
Queensland. For that reason research on the mineralogy of these bauxites are of
importance to the mining industry. The major aluminum phases recognised in
206
bauxites and laterites are gibbsite also known as hydrargillite (γ-Al(OH)3), and
boehmite (γ-AlOOH).
Gibbsite is the main mineral in bauxites formed in areas characterized by a
tropical climate with alternating rainy and dry periods (monsoon). Bauxites with
primarily boehmite appear to be more constrained to the subtropical areas
(Mediterranean type bauxite). Thermal action or low-grade metamorphism mostly
favors diaspore formation. Furthermore, diaspore is formed as a minor constituent in
many types of bauxite in addition to gibbsite and boehmite [1-3]. For comparative
reasons bayerite (β-Al(OH)3)and corundum (Al2O3) have been incorporated in this
study. The thermal behaviour and spectroscopy of these bauxite minerals has been
reported in earlier work by our group [4-7].
X-ray Photoelectron Spectroscopy (XPS) is widely used for determining the
surface composition of solid materials, including aluminium. Although XPS has
become a powerful tool to identify different phases, it has been so far less successful
in determining subtle changes in aluminum oxide/hydroxide minerals. Although the
binding energies of the core lines (i.e. Al 2p, Al 2s, O 1s, O 2s) are easily measured,
the differences in binding energy of Al among the aluminium oxides, hydroxides and
oxyhydroxides are very small, generally in the order of 0 to 0.5 eV, which is in the
same order of magnitude as the experimental precision of XPS [10-13]. Some limited
work has been done on the use valence band XPS to distinguish these minerals
[14,15]. The oxygen core lines may however be more sensitive to changes in the
crystal chemistry. This paper therefore reports on the possible use of high resolution
XPS for the identification of the major aluminium oxide/hydroxide/oxyhydroxide
minerals.
207
Structure of the aluminum (oxo)hydroxides
Gibbsite Al(OH)3
Gibbsite is monoclinic (P21/n, a = 8.684 Å, b = 5.078 Å, c = 9.736 Å, β =
94.54°) with mostly a tabular pseudohexagonal habit. The structure can be visualized
as sheets of hcp layers with open packing between successive sheets. In the lateral
extension of the hexagonal closed packed sheets each Al cation is octahedrally
coordinated by 6 OH groups and each hydroxyl group is coordinated by two Al
cations with one octahedral site vacant [16,17]. This can also be visualized as double
layers of OH groups with Al cations occupying two thirds of the interstices within the
layers. Each double layer is positioned in such a way that the upper and lower
neighboring layers have their hydroxyl groups directly opposite to each other and not
in the position of the closest packing. This type of layer structure explains the perfect
cleavage of gibbsite parallel to the basal plane (001).
Bayerite Al(OH)3
Bayerite is monoclinic (P21/a, a = 5.0626 Å, b = 8.6719 Å, c = 9.4254 Å, β =
90.26°) forming mostly very fine fibers in radiating hemispherical aggregates and
sometimes flaky to tabular crystals to about 0.1 mm. The crystal lattice of bayerite is
composed of layers of hydroxyl groups similar to those in gibbsite. These layers,
however, are arranged in an AB-AB-AB sequence; in other words the hydroxyl
groups of the third layer lie in the depressions between the hydroxyl positions of the
second layer.
208
Boehmite AlOOH
Boehmite has the same structure as lepidocrocite (γ-FeO(OH)). The structure
of boehmite consists of double layers of oxygen octahedra partially filled with Al
cations [18]. Boehmite is orthorhombic with space group Amam (a = 3.6936 Å, b =
12.214 Å, c = 2.8679 Å) [17,19]. The stacking arrangement of the three oxygen layers
is such that the double octahedral layer is in cubic closed packing. Within the double
layer one can discriminate between two different types of oxygen. Each oxygen atom
in the middle of the double layer is shared by four other octahedra, while the oxygen
atoms on the outside are only shared by two octahedra. These outer oxygen atoms are
hydrogen-bonded to two other similarly coordinated oxygen atoms in the neighboring
double layers above and below. The stacking of the layers is such that the hydroxyl
groups of one layer are located over the depression between the hydroxyl groups in
the adjacent layer.
Experimental
Mineral samples
The aluminium phases used in this study are synthetic gibbsite produced in our
laboratory, synthetic gibbsite (γ-alumina) produced by Baikowski International
Corporation (Charlotte, NC), pseudoboehmite synthesised by P. Buining [20],
boehmite synthesized by Ray Frost, synthetic bayerite synthesized by Comelco. The
samples were analysed for phase purity by X-ray diffraction prior to the XPS analysis.
209
X-ray diffraction has shown that the gibbsites, bayerite and the boehmites are pure.
For comparative reasons synthetic corundum produced by Baikowski International
Corparation (Charlott, NC) was used.
XPS analysis
The minerals were analyzed in freshly powdered form in order to prevent
surface oxidation changes. Prior to the analysis the samples were out gassed under
vacuum for 72 hours. The XPS analyses were performed on a Kratos AXIS Ultra with
a monochromatic Al X-ray source at 150 W. Each analysis started with a survey scan
from 0 to 1200 eV with a dwell time of 100 milliseconds, pass energy of 160 eV at
steps of 1 eV with 1 sweep. For the high resolution analysis the number of sweeps
was increased, the pass energy was lowered to 20 eV at steps of 100 meV and the
dwell time was changed to 250 milliseconds.
Band component analysis was undertaken using the Jandel ‘Peakfit’ software
package, which enabled the type of fitting function to be selected and allows specific
parameters to be fixed or varied accordingly. Band fitting was done using a Lorentz-
Gauss cross-product function with the minimum number of component bands used for
the fitting process. The Gaussian-Lorentzian ratio was maintained at values greater
than 0.7 and fitting was undertaken until reproducible results were obtained with
squared correlations of r2 greater than 0.995.
210
Results and discussion
For all minerals XPS survey spectra and high resolution core line spectra (O 1s
and Al 2p) were obtained. Table 1 gives an overview of the chemical composition of
the minerals analysed based on the XPS survey scans. In addition to the elements
belonging to the mineral one always observes the presence of carbon, the so called
advantageous or rubbish carbon. The C 1s transition of this carbon is used to correct
for charging, which results in a shift of all other transitions. The amount of carbon is
variable but can be as high as 22 atom %. The ratio of oxygen to aluminium for
corundum is slightly higher than expected based on the composition of Al2O3. The
reason for this becomes apparent from Fig. 1 where the O1 s spectrum shows the
presence of three different oxygen species. In addition to the bulk oxygen with a
binding energy of 530.7 eV from the crystal structure the surface of corundum
contains hydroxyl groups with an O 1s binding energy of 532.1 eV and a minor
amount of adsorbed water with an O 1s binding energy of 532.9 eV. All three signals
have similar FWHM of about 1.4 eV (Table 2). Only one Al 2p transition is observed
at 74.1 eV (Fig. 2).
For gibbsite and bayerite the ratio O to Al should be equal to 3 to 1 based on a
compositon of Al(OH)3, which is exactly what is observed for gibbsite. For the
bayerite however the ratio is slightly lower than expected but within experimental
error. For gibbsite and bayerite only two O 1s transitions are observed at 531.8 and
533.2 eV and at 531.9 and 533.4 eV, respectively, associated with the hydroxyl
groups in the crystal structure and absorbed water on the surface. Gibbsite and
bayerite both show one major Al 2p transition at 74.3 and 74.4 eV respectively. In
addition, bayerite shows a second transition at 75 eV. XRD showed that this bayerite
211
sample had a very low crystallinity and possibly some amorphous content. It might
well be that this second transition is associated with this amorphous phase.
The difference between boehmite and pseudoboehmite has been a matter of
discussion for a long time. In general there is some consensus that the unit cell of
pseudoboehmite is slightly larger than that of boehmite. It has been indicated in the
literature that this would be due to the incorporation of water in the crystal structure.
In this study two boehmite samples were analysed, one of which was thought to be
pseudoboehmite based on the slightly different XRD pattern. The chemical analyses
clearly show a difference in composition. Boehmite in its purest form has a chemical
formula of AlOOH and therefore an O to Al ratio of 2 to 1 has to be expected. The
boehmite sample has significantly less oxygen than expected whereas the
pseudoboehmite has more oxygen than expected plus a trace amount of chlorine. The
Al 2p transitions are slightly different, although still within the experimental error.
The same is the case for the O 1s transitions, but again the values for the
pseudoboehmite are slightly higher than for boehmite. The high resolution O 1s
spectrum of boehmite shows a nearly 1:1 ratio of oxygen and hydroxyl groups as
expected in boehmite. The amount of water in this sample is minimal. In the
pseudoboehmite the amount of hydroxyl groups and water are both slightly higher
than in boehmite. This may explain the slightly larger unit cell, where a small amount
of the oxygen atoms has been replaced by hydroxyl groups and maybe even water
molecules.
It is well known, and this study confirms this, that it is very difficult to
unambiguously determine any chemical shifts in the Al 2p binding energies among
the oxides, hydroxides and oxohydroxides, as these shifts are generally in the order of
0.2 to 0.5 eV, which is not much more than the typical precision of the XPS
212
instrument [10-13]. In general a chemical shift is caused by changes in the
electrostatic potential field experienced by the core electrons. Oxidation number,
ligand type and coordination (e.g tetrahedral vs. octahedral) can all change the
chemical shift of the Al 2p line. This work shows that the differences in these
parameters are very small for aluminium in the bauxite minerals.
The O 1s peaks show a slightly larger chemical shifts (up to 0.6 eV) than the
Al 2p peaks. In addition the O 1s peak allows one to distinguish between oxygen,
hydroxyl groups and water in the crystal structure and can therefore be used as a
technique to identify within the different bauxite minerals the difference between
gibbsite and bayerite on one hand and boehmite and diaspore on the other hand.
However, due to the very small chemical shifts no distinction can be made between
minerals with the same chemical composition such gibbsite and bayerite.
Refererences
[1] Schoen, R., Roberson, C. E., American Mineralogist 55 (1970) 43-77.
[2] Newman, A. C. D. Chemistry of clay and clay minerals, Longman Scientific &
Technical, Harlow, UK (1987) 480.
[3] van der Marel, H. W., Beutelspacher, H. Atlas of infrared spectroscopy of clay
minerals and their admixtures, Elsevier: Amsterdam (1974) 396.
[4] Ruan, H. D., Frost, R. L., Kloprogge, J. T., Journal of Raman Spectroscopy 32
(2001) 745-750.
[5] Ruan, H. D., Frost, R. L., Kloprogge, J. T., Applied Spectroscopy 55 (2001)
190-196.
213
[6] Ruan, H. D., Frost, R. L., Kloprogge, J. T., Duong, L., Spectrochim. Acta, Part
A 58 (2002) 265-272.
[7] Kloprogge, J. T., Ruan, H. D., Frost, R. L., Journal of Materials Science 37
(2002) 1121-1129.
[8] Frost, R. L., Kloprogge, J. T., Russell, S. C., Szetu, J. L., Applied
Spectroscopy 53 (1999) 423-434.
[9] Frost, R. L., Kloprogge, J. T., Russell, S. C., Szetu, J. L., Applied
Spectroscopy 53 (1999) 423-433.
[10] Strahlin, A., Hjertberg, T., Applied Surface Science 74 (1994) 263-275.
[11] Tsuchida, T., Takahashi, T., J. Mater. Res. 9 (1994) 29219-2224.
[12] Nylund, A., Olefjord, I., Surface and Interface Analysis 21 (1994) 283-289.
[13] Strohmeier, B. R., Surface and Interface Analysis 15 (1990) 51-56.
[14] Thomas, S., Sherwood, P. M. A., J. Chem. Soc., Faraday Trans. 89 (1993)
263-266.
[15] Thomas, S., Sherwood, P. M. A., Anal. Chem. 64 (1992) 2488-2495.
[16] Megaw, H. D., Zeitschrift für Kristallographie 87A (1934) 185-204.
[17] Ramos-Gallardo, A., Vegas, A., Zeitschrift für Kristallographie 211 (1996)
299-303.
[18] Milligan, W. O., McAtee, J. L., Journal of Physical Chemistry 60 (1956) 273-
277.
[19] Christoph, G. G., Corbato, C. E., Hofmann, A., Tettenhorst, R. T., Clays and
Clay Minerals 27 (1979) 81-86.
[20] Buining, P. A., Pathmamanoharan, C., Jansen, J. B. H., Lekkerkerker, H. N.
W., Journal of the American Ceramic Society 74 (1991) 1303-1307.
214
Table 1. Chemical compositions (atom %) of the alumina phases based on the
XPS analyses
corundum gibbsite bayerite boehmite pseudoboehmite O 48.56 62.50 60.19 59.44 62.54 Al 30.25 20.93 20.95 35.58 27.29 Na* bd 2.32 4.23 bd bd N* bd bd 1.56 bd bd Cl* bd bd 0.58 bd 1.35 C** 21.18 14.26 12.48 4.98 8.82 * Impurities ** Advantageous carbon bd - below detection limit
215
Table 2 Binding energies (in eV) of the alumina phases (FWHM in parenthesis).
Al 2p Al 1 Al 2 Corundum 74.1 - Gibbsite 74.4 - Bayerite 74.3 75.0
Boehmite 73.9 - Pseudoboehmite 74.3 -
O 1s O OH H2O Corundum 530.7 (1.4) 532.1 (1.4) 532.9(1.4) Gibbsite - 531.8 (1.5) 533.2 (1.5) Bayerite - 531.9 (1.7) 533.4 (1.7)
Boehmite 530.5 (1.5) 531.8 (1.5) 533.0 (1.5) Pseudoboehmite 530.8 (1.6) 532.2 (1.6) 533.5 (1.6)
216
0
2000
4000
6000
8000
527528529530531532533534535536537
Binding energy (eV)
Inte
nsity
(CPS
)
O 530.7 eV
OH 532.1 eV
H2O 532.9 eV
Fig. 1a O 1s corundum
0
500
1000
1500
2000
527528529530531532533534535536537
Binding energy (eV)
Inte
nsity
(CPS
)
OH 531.8 eV
H2O 533.2 eV
Fig 1b O 1s gibbsite
217
0
200
400
600
800
1000
1200
1400
1600
527528529530531532533534535536537
Binding energy (eV)
Inte
nsity
(CPS
)OH 531.9 eV
H2O 533.4 eV
Fig 1c O 1s bayerite
0
100
200
300
400
500
600
700
527528529530531532533534535536537
Binding energy (eV)
Inte
nsity
(CPS
)
O 530.5 eVOH 531.8 eV
H2O 533.0 eV
Fig. 1d O 1s boehmite
218
0
100
200
300
400
500
600
700
800
900
527528529530531532533534535536537
Binding energy (eV)
Inte
nsity
(CPS
)
O 530.8 eVOH 532.2 eV
H2O 533.5 eV
Fig. 1e O 1s pseudoboehmite
219
0
500
1000
1500
2000
2500
3000
7071727374757677787980
Binding energy (eV)
Inte
nsity
(CPS
)
74.1 eV
Fig. 2a Al 2p corundum
0
50
100
150
200
250
300
350
400
450
7071727374757677787980
Binding energy (eV)
Inte
nsity
(CPS
)
74.4 eV
Fig 2b Al 2p gibbsite
220
0
50
100
150
200
250
7071727374757677787980
Binding energy (eV)
Cou
nts
75.0 eV
74.3 eV
Fig. 2c Al 2p bayerite
0
50
100
150
200
250
7071727374757677787980
Binding energy (eV)
Inte
nsity
(CPS
)
73.9 eV
Fig. 2d Al 2p boehmite
221
0
100
200
300
400
500
7071727374757677787980
Binding energy (eV)
Inte
nsity
(CPS
)
74.3 eV
Fig. 2e Al 2p pseudoboehmite
222
A X-ray photoelectron spectroscopy study of HDTMAB distribution
within organoclays
Hongping He a,b, Qin Zhou a,c, Ray L. Frost b, Barry J. Wood d, Loc V. Duong b, J.
Theo Kloprogge b,*
a Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
b Inorganic Materials Research Program, School of Physical and Chemical Sciences,
Queensland University of Technology, GPO Box 2434, Brisbane, QLD 4001, Australia
c Graduate University of the Chinese Academy of Sciences, Beijing 100039, China d Brisbane Surface Analysis Facility, University of Queensland, Brisbane, QLD 4072,
Australia Corresponding author: [email protected]
223
Abstract X-ray photoelectron spectroscopy (XPS) in combination with X-ray diffraction
(XRD) and high-resolution thermogravimetric analysis (HRTG) has been used to investigate the surfactant distribution within the organoclays prepared at different surfactant concentrations. This study demonstrates that the surfactant distribution within the organoclays depends strongly on the surfactant loadings. In the organoclays prepared at relative low surfactant concentrations, the surfactant cations mainly locate in the clay interlayer whereas the surfactants occupy both the clay interlayer space and the interparticle pores in the organoclays prepared at high surfactant concentrations. The former adopts a lateral arrangement for the intercalated surfactants within the interlayer while the latter has a paraffin arrangement. This can well explain the dramatic surface area and pore volume decrease of organoclays compared to those of starting clays. XPS survey scans show that, at low surfactant concentration (< 1.0 CEC), the ion exchange between Na+ and HDTMA+ is dominant whereas both cations and ion pairs occur in the organoclays prepared at high concentrations (> 1.0CEC). High-resolution XPS spectra show that the modification of clay with surfactants has prominent influences on the binding energies of the atoms in both clays and surfactants, and nitrogen is the most sensitive to the surfactant distribution within the resultant organoclays. Keywords: X-ray photoelectron spectroscopy; X-ray diffraction; Organoclay; Surfactant distribution; Surfactant loading
224
1. Introduction Organoclays represent a family of materials with hydrophobic surfaces,
synthesized by modifying swelling clays with various surfactants. During the last 50 years, organoclays have attracted great interest in a number of applications, such as adsorbents for organic pollutants [1-4], rheological control agents [5], reinforcing fillers for plastics [6], clay-based nanocomposites7, and precursors for preparing mesoporous materials [8, 9].
Up to now, a large variety of organoclays have been synthesized using different surfactants [1-4,10-12] and their structures have been characterized using various techniques, including X-ray diffraction (XRD) [11,12], Fourier transform infrared spectroscopy (FTIR) [13-15], Raman spectroscopy [16], thermogravimetric measurement (TG) [17-21], magic-angle-spinning nuclear-magnetic-resonance (MAS NMR) [22,23] and transmission electron microscopy (TEM) [24-26]. In these cases, the detailed information about the interlayer structure, the conformation of the intercalated surfactant and thermal stability of the resultant organoclays rather than the surface characteristics was obtained. However, in various applications of organoclays, the surface characteristics of the resultant organoclays is of high importance since the affinity between the organoclays and the matrix depends strongly on the surface characteristics of the organoclays. Unfortunately, the aforementioned techniques provide little information about the surface characteristics of the organoclays.
X-ray photoelectron spectroscopy (XPS) has been demonstrated to be a powerful technique to investigate the surface characteristics of various materials, including clay minerals and related products [27-30]. XPS can provide elemental analysis for essentially the entire periodic table. Because the electrons whose energies are analyzed arise from a depth of no greater than about 2 – 5 nm, the technique is surface-sensitive and suitable to investigate the surface characteristics of clays and the resultant organoclays.
With the increase of applications in various fields, the study of organoclay surface characteristics will attract great interest. Zhu and coworkers [2] proposed that the various sorption mechanisms of organoclays for pollutants might result from the different distributions of surfactant within the organoclays. Recently, our study demonstrated that washing the organoclays with solvents resulted in the change of surface energy of the resultant organoclays, resulting from the removal of physically adsorbed surfactant [31]. Both of the abovementioned cases suggest that the distribution of surfactant have a significant effect on the surface property of the organoclays and a consequent influence on their applications.
Unfortunately, to date, there is no publication available on XPS of organoclays, which can provide convincing evidence about the distribution of surfactant within organoclays. The objective of this report is to determine the surfactant distribution within the organoclays using XPS, in conjunction with X-ray diffraction (XRD) and high-resolution thermogravimetric analysis (HRTG). This study demonstrates that the distribution of surfactant (in the interlayer space and outside clay layer) depends strongly on the surfactant loading within organoclays and N 1s spectra are most
225
sensitive to the surfactant distribution. This is of high importance to well understand the microstructure of organoclays and for their applications. 2. Experimental 2.1 Materials
Ca-montmorillonite (Ca-Mt) was obtained from Hebei, China. The sample was purified by sedimentation and the <2 µm fraction was collected and dried at 90 °C. The sample was ground through a 200 mesh sieve and sealed in a glass tube for use. Its cation exchange capacity (CEC) is 90.8 meq/100g, determined by NH4
+ method as described in the literature [32]. Its chemical formula can be expressed as Ca0.19Mg0.06Na0.01(Si3.96Al0.04)(Al1.44Fe0.09Mg0.47)O10(OH)2·nH2O, calculated from the chemical analysis result. The surfactant used in this study is hexadecyltrimethylammonium bromide (HDTMAB) with a purity of 99%, provided by YuanJu Chem. Co. Ltd., China.
2.2 Preparation of organoclays Before synthesis of HDTMA+ intercalated montmorillonites, sodium montmorillonite (Na-Mt) was prepared from Ca-Mt as follows: 10 g of the mixture of Ca-Mt and Na2CO3 in the ratio of 94:6 was added into 100 ml of deionized water and stirred at 80 °C for 3 h. During the stirring, several drops of HCl were added into the suspension to dissolve the CO3
2-. Na-Mt was collected by centrifugation and washed with deionized water until the solution was free of chloride (titration with AgNO3). The Na-Mt was dried at 105 °C, ground through a 200 mesh sieve and kept in a sealed bottle.
The syntheses of HDTMA+ intercalated montmorillonites were performed by the following procedure: 2.5 g of Na-montmorillonite was first dispersed in 300 ml of deionized water and then a desired amount of HDTMAB was slowly added. The concentrations of HDTMA+ varied from 0.5 CEC to 2.5 CEC of montmorillonite. The reaction mixtures were stirred in a water bath for 9 h at 80 oC. All products were washed free of bromide anions (titration with AgNO3), dried at 60 oC and ground in an agate mortar to pass through a 200 mesh sieve. The HDTMA+ modified montmorillonite prepared at the concentration of 0.5 CEC was denoted as 0.5CEC-Mt and the others were marked in the same way. 2.3 Characterization
X-ray diffraction (XRD) patterns of the samples were recorded between 1.5 and 20° (2θ) at a scanning speed of 2°/min, using Rigaku D/max-1200 diffractometer with Cu Kα radiation (30 mA and 40 kV).
High-resolution thermogravimetric analysis (HRTG) was performed on a TA Instruments Inc. Q500 thermobalance. Samples were heated from room temperature to 1000 °C at a heating rate of 10 °C/min with a resolution of 6 oC under N2 atmosphere (80 cm3/min). Approximately 30 mg of finely ground sample was heated in an open platinum crucible.
N2 adsorption-desorption isotherms were gained at liquid nitrogen temperature
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with a Micromeritics ASAP 2010 gas sorption analyzer (Quantachrome Co., USA). Before measurement, the samples were pre-heated at 80 oC under N2 for ca. 24 h. The specific surface area was calculated by the BET equation and the total pore volumes were evaluated from nitrogen uptake at relative pressure of ca. 0.99.
The X-ray photoelectron spectroscopy (XPS) analyses were performed on a Kratos AXIS Ultra with a monochromatic Al X-ray source at 150 W. Each analysis started with a survey scan from 0 to 1200 eV with a dwell time of 100 ms, pass energy of 160 eV at steps of 1 eV with 1 sweep. For the high-resolution analysis, the number of sweeps was increased, the pass energy was lowered to 20 eV at steps of 100 meV and the dwell time was changed to 250 ms. Band component analyses were undertaken using using the Jandel ‘Peakfit’ software package, which enabled the type of fitting function to be selected and allows specific parameters to be fixed or varied accordingly. Band fitting was done using a Lorenz-Gauss cross-product function with the minimum number of component bands used for the fitting process [33]. 3. Results and discussion 3.1 X-ray diffraction (XRD)
Figure 1 shows the XRD patterns of montmorillonites and the resultant organoclays. The basal spacing of Na-Mt is 1.24 nm, which is a characteristic d value for Na-montmorillonite. However, after modification with surfactant, the interlayer height of montmorillonite is obviously increased. With an increase of surfactant concentration in the preparation solution, the basal spacings of the resultant organoclays increase in the following order: 1.24 nm (Na-Mt) → 1.48 nm (0.5CEC-Mt) → 1.78 nm (0.7CEC-Mt) → 1.95 nm (1.0CEC-Mt) → 2.23 nm (1.5CEC-Mt) → 3.61 nm (2.0CEC-Mt) → 3.84 nm (2.5CEC-Mt). Here, it can be understood that there are five different HDTMA+ arrangements adopted within the montmorillonite interlayer space, i.e., lateral monolayer in 0.5CEC-Mt, lateral bilayer in 0.7CEC-Mt, pseudotrilayer in 1.0CEC-Mt, paraffin monolayer in 1.5CEC-Mt and paraffin bilayer in 2.0CEC-Mt and 2.5CEC-Mt, respectively, in agreement with previous experimental and molecular modeling reports [11,12,34-36]. Figure 2(I) is the schematics of the organoclays with different surfactant arrangement models. 3.2 XPS characterization
Figure 3 displays the XPS survey scans of HDTMAB, Na-Mt and the representative organoclays (0.7CEC-Mt and 2.5CEC-Mt). The XPS results clearly show that the presences of carbon, nitrogen and bromine in HDTMAB and sodium, aluminum, silicon, oxygen, magnesium and iron in Na-Mt. The XPS result is in an excellent agreement with our chemical analysis result of montmorillonite. In addition, there is a minor amount of oxygen in HDTMAB and carbon in Na-Mt, resulting from adsorbed CO2 [37]. The XPS survey scans show the presence of calcium in Ca-Mt (not shown) whereas in Na-Mt only sodium was observed (Fig. 3), indicating that the preparation of sodium montmorillonite from calcium montmorillonite in this study was successful.
The ratios of the elemental atomic concentrations in montmorillonite and the
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resultant organoclays are summarized in Table 1, deduced from the corresponding XPS analyses. This calculation shows that the content of surfactant within the organoclays increases in the order of 0.5CEC-Mt → 0.7CEC-Mt → 1.0CEC-Mt → 1.5CEC-Mt → 2.0CEC-Mt → 2.5CEC-Mt. This is in accordance with our previous studies using other techniques and the reports in the literature [11-25]. Meanwhile, the Al/Si ratio deduced from the XPS analysis (0.36) is in good agreement with the chemical analysis (0.37). However, the Al/Si ratio in the resultant organoclays decreases with the intercalation of surfactant as shown in Table 1. This results from the increase of the interlayer distance with the intercalation of surfactant, which leads to a decreasing possibility for detecting the Al-O(OH) octahedral sheets sandwiched between the two Si-O tetrahedral sheets of the montmorillonite.
In the XPS survey scans of the resultant organoclays, prominent peaks corresponding to magnesium and a trace to iron are always recorded whereas that of sodium disappears. This reflects that both magnesium and iron are in the montmorillonite structure rather than in the interlayer. This is in agreement with our formula calculation. Meanwhile, the disappearance of the peak corresponding to sodium results from the exchange of sodium ions by surfactant cations.
There is no peak corresponding to bromine recorded in the XPS survey scans of 0.5CEC-Mt, 0.7CEC-Mt and 1.0CEC-Mt whereas it is recorded in the XPS scans of 1.5CEC-Mt, 2.0CEC-Mt and 2.5CEC-Mt. The surfactant contents (in term of CEC) in the resultant organoclays, deduced from the thermogravimetric measurements (not shown), are shown in Table 1. Our calculation indicates that there is more than one CEC of surfactant in 1.5CEC-Mt, 2.0CEC-Mt and 2.5CEC-Mt. Here, it can be understood that, at relative low surfactant concentration (≤ 1 CEC in the present case), the intercalation is dominant and the surfactants enter into the clay interlayer space as cations. On the other hand, the surfactants exist within the organoclays in both formats of cations and molecules when the loaded surfactants are more than 1 CEC [38]. This concept is further supported by the high-resolution XPS scans.
3.3 High-resolution XPS 3.3.1 C 1s spectra The C 1s spectrum of HDTMAB is characterized by two transitions centered at 284.7 and 285.7 eV, corresponding to the C-C bond in the long chain and C-N, respectively (Fig. 4). The C 1s spectra of organoclays show a significant broadening with slight changes in binding energy, indicating more than one type of surfactant-clay interaction. The change trends of binding energy for C-C and C-N as function of CEC are different as shown in Figure 5. For the spectra corresponding to C-C, there is a significant binding energy decrease from HDTMAB to 0.5CEC-Mt and the binding energies for 0.7CEC-Mt and 1.0CEC-Mt are similar to that of 0.5CEC-Mt. However, there is a significant increase from 1.0CEC-Mt to 1.5CEC-Mt, then to 2.0CEC-Mt and finally to 2.5CEC-Mt. The C 1s binding energies of 2.0CEC-Mt and 2.5CEC-Mt are higher than that of HDTMAB. However, the C 1s binding energies of the resultant organoclays, corresponding to the C-N bond, are similar. Here, the C 1s spectra of organoclays show that the local molecular
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environment of the surfactant has a prominent effect on the binding energy. Molecular modeling [34-36] demonstrates that in all arrangements of surfactant within the clay interlayer, the headgroups (nitrogen) of the alkyl chains will be close to the clay surface due to the strong electrostatic interaction between the negative clay surface and the positive headgroups of the alkyl chains. This can well explain the similar binding energy of C 1s in C-N for the organoclays with different surfactant arrangements.
Previous reports [13-16,34-36] have shown that, in the organoclays with lower surfactant packing density, the alkyl chains within the interlayer space are parallel within the interlayer space and are individually separated. In this case, the repulsive interaction between the hydrocarbon chain ─ silicate surface is dominant whereas the interaction among the hydrocarbon chains is very weak. The local environment of the intercalated surfactant is absolutely different from those in bulk state. With the increase of surfactant packing density, the interchain interaction among the surfactants becomes the dominant force and the orientation of the hydrocarbon tail changes from parallel to the silicate surface within the interlayer space to parallel but at an angle to the silicate surface as shown by XRD and FTIR results [11-15]. The interaction among alkyl chains will increase with the increase of the surfactant packing density [11,12,21] and this will result in the ordered packing of the alkyl chains as indicated by FTIR and Raman spectroscopy [13-16]. The local environment of the surfactant within the resultant organoclays strongly depends on their loaded amounts, resulting in a variation of the C 1s binding energy associated with the C-C bond in the alkyl chains. 3.3.2 N 1s spectra
The high resolution scans of nitrogen in HDTMAB and the representative organoclays are displayed in Figure 4. For HDTMAB, a single 1s transition is observed with a binding energy of 401.9 eV, which is similar to that reported in a previous study [39]. The high resolution scans of nitrogen in 0.5CEC-Mt, 0.7CEC-Mt and 1.0CEC-Mt show a single 1s transition with a slight increase of the binding energy (ca. 0.5 eV) and full-width-at-half-maximum (FWHM), indicating the local environment of the intercalated surfactant is different from that in bulk state. This is in accordance with the conclusion deduced from the C 1s spectra.
However, the nitrogen high resolution scans of organoclays with a surfactant loading more than one CEC show two overlapping bands related to two different N 1s transitions. The N 1s spectrum of 2.5CEC-Mt is shown in Figure 4, in which two bands at ca. 403.6 and 402.6 eV, respectively, were recorded, reflecting two different local environments for the surfactant within the organoclay. The band with a bonding energy (402.6 eV) similar to that in 0.5CEC-Mt, 0.7CEC-Mt and 1.0CEC-Mt, should be attributed to the intercalated surfactant while the other one (ca. 403.6 eV) should be attributed to the surfactant outside the clay layers. This assumption is supported by the pore volume analyses of these samples.
The nitrogen adsorption-desorption isotherms of Na-Mt and the resultant organoclays show that there are “ink-bottle” like pores in these clays, which could be
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described as a “house of cards” structure [40,41]. Meanwhile, the pore volumes of these samples (Table 1) show that there is a dramatic decrease of the BET-N2 surface area from Na-Mt to 0.5CEC-Mt, followed by a smooth decrease till 1.0CEC-Mt, then a more pronounced decrease till 2.0CEC-Mt. The dramatic pore volume decrease of the organoclays with less than one CEC can be explained as the intercalation of the HDTMA+ cations into the clay interlayer space. And the significant pore volume decrease from 1.0CEC-Mt to the organoclays with a surfactant loading more than one CEC is resulted from the occupation of surfactant in the interparticle pores. This also has been elucidated by thermal analysis of organoclays [21]. 3.3.3 Br 3d spectra
As indicated by the survey scans of the resultant organoclays (Fig. 3), a very weak Br 3d transition begins to occur in the XPS spectrum of 1.5CEC-Mt. The intensity of the Br 3d transition obviously increases in the spectra of 2.0CEC-Mt and 2.5CEC-Mt. Figure 6 displays the high resolution Br 3d scans of HDTMAB, 2.0CEC-Mt and 2.5CEC-Mt.
The Br 3d spectrum of HDTMAB displays two well-resolved transitions centered at 67.1 and 68.2 eV, corresponding to Br 3d5 and 3d3, respectively. In comparison to the XPS spectrum of HDTMAB, both 2.0CEC-Mt and 2.5CEC-Mt show a broad peak with low intensity and poor resolution for the two transitions. This reflects that the content of bromine in the organoclays is limited and disordered, and ion exchange between HDTMA+ and interlayer cations (Na+) is dominant [38]. 3.3.4 O 1s and Si 2p spectra
The high-resolution O 1s scan of Na-Mt and the simulated curves (Fig. 7a) show that it is difficult to distinguish O and OH in montmorillonite. This is different from the previous study about basic aluminum sulphate and basic aluminum nitrate, in which O and OH in the corresponding materials were clearly identified [33]. There is a small amount of water (ca. 2.39%) remaining in Na-Mt after exposure to ultra high vacuum (10-9 – 10-10 Torr), as shown by the simulated curves (Fig. 7a). The oxygen in motmorillonite structural sheets corresponds to a binding energy of 532.1 eV while that in water is ca. 535.0 eV. These values are in accord with those reported in the literature [33,42]. However, the high-resolution O 1s scans of the resultant organoclays (Fig. 7) do not show any transition corresponding to H2O, resulting from the hydrophobicity of the organoclays and high vacuum (10-9 Torr) in the detection chamber. Compared to Na-Mt, it can be seen that there is a slight decrease (ca. 1 eV) of the O 1s binding energy in the organoclays. The binding energy change of Si 2p transition from Na-Mt to the resultant organoclays is similar to that of O 1s (Fig. 7 d-f). The binding energy of Si 2p in Na-Mt is 103.0 eV while that for the resultant organoclays increases to 101.9 eV, with a decrease of 1.1 eV. Both the decreases of O 1s and Si 2p binding energies result from the change of the interlayer environment. This is in agreement with the proposal deduced from MAS NMR study of organoclays, which indicates that modifying clays with surfactant results in a measurable shielding of 29Si nuclei in clays [43].
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During the intercalation, the prominent change for montmorillonite is that the exchangeable interlayer hydrated cations are replaced by the surfactant cations. As shown by the O 1s XPS spectrum (Fig. 7a), there is a minor amount of H2O in Na-Mt, corresponding to the strongly bound water of the interlayer cations rather than the surface adsorbed water [44,45]. This part of water links to the oxygen on the clay surface (Si-O tetrahedral sheet) through hydrogen bond [46,47]. After the interlayer hydrated cations are replaced by the intercalated surfactant, the main interaction between the clay and surfactant includes both the electrostatic attract between the positively charged headgroups (nitrogen) of the alkyl chains and the negatively charged clay surfaces, and a repulsive force between alkyl chain and clay surface as demonstrated by molecular modeling [34-36].
On the basis of abovementioned experimental results, the schematics for the structural evolution from Na-Mt to the resultant organoclays are built as shown in Figure 7(II). Obviously, two basic organoclay types are formed when modifying clay with surfactant due to the different surfactant distributions: 1) the surfactant mainly occupies the clay interlayer and 2) both the clay interlayer space and external surface are modified by surfactant. Our recent sorption experiments indicate that both surface sorption and partition are involved in the sorption mechanisms for 0.5CEC-Mt, 0.7CEC-Mt and 1.0CEC-Mt to p-nitrophenol whereas partition is dominant for 1.5CEC-Mt, 2.0CEC-Mt and 2.5CEC-Mt. This is a convincing evidence supporting our assumption of the surfactant distribution within organoclays. 4. Conclusions
In this study, a series of organoclays with different surfactant arrangements within the clay interlayer were prepared. The surfactant distribution within the resultant organoclays was investigated by XPS in combination with XRD and HRTG. In the organoclays prepared at relative low surfactant concentrations (< 1.0CEC), the surfactant cations mainly occupy the clay interlayer with lateral arrangements (lateral monolayer, lateral bilayer and pseudotrilayer). However, when the surfactant concentrations are higher than 1.0CEC, the surfactants occupy both the clay interlayer space and the interparticle pores and paraffin type arrangements of surfactants (paraffin monolayer and paraffin bilayer) are adopted in the clay interlayer spaces. This gives excellent explanations about the dramatic surface area and pore volume decrease of organoclays and different sorption mechanisms (surface sorption and partition) involved in organoclay sorption experiments as reported in the literature.
XPS survey scans show that the peaks corresponding to magnesium and iron are identical in all samples, reflecting these atoms in montmorillonite structure rather in the interlayer or impurities. The peaks corresponding to bromine only appear in the organoclays prepared at high surfactant concentrations (> 1.0CEC). This suggests that both surfactant cations and ion pairs occur in these organoclays, corresponding different interactions between surfactants and clays. The former relates with ion exchange and the latter with sorption.
Generally, modifying clays with surfactants results in a decrease of binding energy of atoms in both clays and surfactants and broadening of the peaks. However,
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with the increase of surfactant loadings, the FWHM of the related peaks decreases, suggesting the organoclay structure becomes more ordered. This study shows that nitrogen is the most sensitive to the surfactant distribution within the resultant organoclays and the C 1s binding energy of C-C bond in alkyl chain is sensitive to the local environment of surfactants in organoclays with different arrangements. Acknowledgments
The financial and infra-structural support from the National Natural Science Foundation of China (Grant No. 40372029 and International Cooperation Research Program), and the Inorganic Materials Research Program, Queensland University of Technology are gratefully acknowledged.
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Table 1 Surfactant loadings and the ratios of atomic concentrations in
montmorillonite and the resultant organoclays based on TG and XPS analyses.
Sample Na-Mt 0.5CEC-Mt 0.7CEC-Mt 1.0CEC-Mt 1.5CEC-Mt 2.0CEC-Mt 2.5CEC-Mt
a SL (%) - 9.73 16.73 22.13 28.19 38.73 44.17 b SL (vs CEC) - 0.33 0.61 0.86 1.19 1.9 2.4
c C/Si - 2.08 2.28 2.69 3.41 5.79 6.58 d Al/Si 0.36 0.34 0.32 0.33 0.33 0.28 0.30
VP (cm3/g) 0.107 0.061 0.060 0.056 0.037 0.011 0.007 a: surfactant loading within the corresponding organoclay, evaluated from high-resolution
thermogravimetric analysis. b: surfactant loading expressed in CEC of montmorillonite (100 g). c: the ratios of carbon and silicon atomic concentrations in the organoclays. d: the ratios of aluminun and silicon atomic concentrations in Na-montmorillonite and the
organoclays.. VP: pore volume determined by BJH method from N2 desorption isotherm.
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Figure 1 XRD patterns of montmorillonite and the resultant organoclays.
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Figure 2 The schematics of organoclays with different arrangements (I), and the schematics of
Na-Mt and the resultant organoclays (II). A: lateral monolayer; B: lateral bilayer; C: pseudotrilayer; D: paraffin monolayer; E: paraffin bilayer.
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Figure 3 XPS survey scans of HDTMAB, Na-Mt and the representative organoclays.
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Figure 4 C 1s and N 1s high resolution XPS spectra of HDTMAB and the representative organoclays. thin solid line: experimental curve; thick solid line: deconvolution curve; dash line: fitting curve.
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Figure 5 The C 1s binding energy change of C-C and C-N in the resultant organoclays.
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Figure 6 Br 3d high resolution XPS spectra of HDTMAB, 2.0CEC-Mt and 2.5CEC-Mt. thin solid line: experimental curve; thick solid line: deconvolution curve; dash line: fitting curve.
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Figure 7 O 1s and Si 2p high resolution XPS spectra of Na-Mt and the representative organoclays. thin solid line: experimental curve; thick solid line: deconvolution curve; dash line: fitting curve.