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Investigation on Photocatalytic Efficiency of TiO2
Photocatalysts under Visible Illumination
D09404009
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I
2007 11
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II
()
400700 nm
Kubelka-Munk
(2.98eV)
(2.88eV)(2.63eV) Langmuir-Hinshelwood
/
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III
ABSTRACT KeywordsTitania nanoparticle, Hydrothermal treatment, Visible-light
photocatalysis, Methylene blue
In this dissertation, a hydrothermal treatment was employed to doping three types
of metal ions (Fe, Co, and Ni) into commercial TiO2 photocatalysts for improving the
photocatalytic reactivity of methylene blue (MB) under visible light irradiation.
Nitrogen physisorption measurement indicated that surface areas and porosities of
metal-doped titania powders still maintain an identical value, comparing to the starting
material. The diffuse reflection spectra of metal-doped titania reflected a light
absorption edge, shifting to the visible light range of ca. 400700 nm. According to
Kubelka-Munk plot, the optical band gaps were found to have the following order
Fe-doping (2.98 eV) > Co-doping (2.88 eV) > Ni-doping (2.63 eV), based on the fixed
dopant concentration. A Langmuir-Hinshelwood model was used to investigate the
photocatalytic activity for removing MB from liquid phase. It was found that the
decreasing optical band gap is accompanied by increasing photo degradation activity of
MB. This result can be attributed to a fact that metal-doped titania photocatalyst with
the narrowest band gap is capable of generating better redox ability of electronhole
pairs under visible light, thus leading to the greatest photocatalytic activity.
According to the results, the visible-light-derived photocatalysts prepared by the
above hydrothermal synthesis exhibit an excellent photocatalytic capability in
decomposing organic dyes. In practical operation, we employed ceramic tile and toast
as substrates for evaluating the photocatalytic ability under visible illumination.
Experimental results indicated that the metal-doped titania photocatalysts enable to
prevent the growth of E. coli, thus extending the anti-spoiled period of toast. After
coating them onto ceramic tile, the prepared tile leads to keep a cleaner surface than the
tile coated with commercial photocatalysts after two weeks. This fascinating effect
proves that this fabrication technique is an efficient method in preparing
visible-light-derived photocatalysts that can be extensively used in a variety of
applications such as indoor decoration, ceramic tile, glass, house furnishings, and so on.
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IV
.......................................................................................1
1.1 ............................................................................1
1.2 ............................................................................2
1.3 ............................................................................3
1.4 ............................................................................4
1.5 ............................................................................5
...................................................................6
2.1 ....................................................6
2.1.1 .............................................................8
2.1.2 ..................................................8
2.1.3 ......................................9
2.2 .........................................................................12
2.2.1 ...............................................................13
2.2.2 ...............................................................13
2.2.3 ........................14
2.3 .....................................................17
2.3.1 ....................................18
2.3.2 ....................................21
.............................................................26
3.1 ..................................................26
3.2 ..............................................31
3.3 TiO2 .........................................32
3.4 TiO2 .............................36
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V
3.5 TiO2 .............................41
.................................................................................43
4.1 .........................................................................43
4.2 .................................................................44
4.3 .........................................................................45
4.4 .........................................................................46
4.5 .....................................................47
4.5.1 ................................47
4.5.2 ........................................49
4.5.3 ........................................51
4.5.4 ...................................................54
4.5.5 ........................................55
.................................................................58
5.1 TiO2 .........................................58
5.1.1 TiO2 ..................58
5.1.2 TiO2 ..................................60
5.1.3 TiO2 ..................................62
5.2 TiO2- ................................64
5.3 TiO2 .............................69
5.4 .........................................................................74
TiO2.........................................75
6.1 .........................................................................75
6.2 .........................................................................76
6.3 ..........................................................................77
6.4 ...........................................78
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VI
.............................................................................93
7.1 .................................................................................93
7.2 ..............................................................95
................................................................................................97
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VII
3.1 ...............................................................35
3.2 ............................................41
4.1 ...................................................................43
4.2 .......................................................................43
4.3 ...................................................................................44
5.1 . .......................59
5.2 . 73
6.1 ...................................................................75
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VIII
1.1 .................................................................................5
2.1 .............................................................................9
2.2 ...............................................................10
2.3 ................................................12
3.1 (a)(b) ...............................28
3.2 ...................................................................30
3.3 ...................................................................31
3.4 ........................33
4.1 ....................................46
4.2 FE-SEM ....................................................................48
4.3 ................................................50
4.4 (a)BET (b)
...................................................................................53
4.5 X .......................................................................54
4.6 - ..............................................55
4.7 -(Varian Cary100) .......................57
5.1 .....61
5.2 XRD..........................................63
5.3 . ...................................65
5.4 KM. ..........................................68
5.5 . ........70
6.1 TiO2 ......................77
6.2 (a)(b)................79
6.3 (a)(b) ........80
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IX
6.4 TiO2 ..........................82
6.5
..................................................................................................83
6.6 .....85
6.7 TiO2 ...................87
6.8 ............................................89
6.9 ............................90
6.10 .................91
7.1 ....................................96
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1
1.1
WTO
(2006~2008 ) 60
( 17%)
(
SARS)
(TiO2)
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2
1.2
(TiO2)(ZnO)
(NOx)
[1,2]
N(energy band gap)
3.2 eV 385 nm
[2] 45%
3-4
( 400-700 nm)
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3
1.3
(Pt)(V)(Ni)(Mn)(Cr)(Fe)
[3](N)[2]
(TiO2)
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4
1.4
(sol-gel method)[3](DC plasma)[4]
(hydrothermal or solvthermal)[5]
110 150 24
(Fe)
(Co) (Ni)
135 1
(pseudo first-order)
(methylene blue, MB)
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5
1.5
1.1
1.1
TiO2
TiO2 TiO2 TiO2
BET
XRDTEM
SEM
UV-Visible
TiO2
TiO2 TiO2 TiO2
BET
XRDTEM
SEM
UV-Visible
TiO2
TiO2 TiO2 TiO2
BET
XRDTEM
SEM
UV-Visible
TiO2
TiO2 TiO2 TiO2
BET
XRDTEM
SEM
UV-Visible
TiO2
TiO2 TiO2 TiO2
BET
XRDTEM
SEM
UV-Visible
TiO2
TiO2 TiO2 TiO2
BET
XRDTEM
SEM
UV-Visible
TiO2
TiO2 TiO2 TiO2
BET
XRDTEM
SEM
UV-Visible
TiO2
TiO2 TiO2 TiO2
BET
XRDTEM
SEM
UV-Visible
TiO2
TiO2 TiO2 TiO2
TiO2
TiO2 TiO2 TiO2
BET
XRDTEM
SEM
UV-Visible
TiO2
TiO2 TiO2 TiO2
BET
XRDTEM
SEM
UV-Visible
TiO2
TiO2 TiO2 TiO2
BET
XRDTEM
SEM
UV-Visible
TiO2
TiO2 TiO2 TiO2
BET
XRDTEM
SEM
UV-Visible
TiO2
TiO2 TiO2 TiO2
BET
XRDTEM
SEM
UV-Visible
TiO2
BET
XRDTEM
SEM
UV-Visible
TiO2
TiO2 TiO2 TiO2
BET
XRDTEM
SEM
UV-Visible
TiO2
TiO2 TiO2 TiO2
BET
XRDTEM
SEM
UV-Visible
TiO2
TiO2 TiO2 TiO2
BET
XRDTEM
SEM
UV-Visible
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6
2.1
(Nanotechnology)
(Richard Feynman) 1959
McKeownNario Taniguchi
1974 Nanotechnology[6]
0.1 nm- 100 nm
(Top-down)1982 (Scanning
Tunneling Microscope, STM)
1989 Foresight Stanford University
1990(Baltimore) STM
2000
National Nanotechnology
Initiative (NNI)
[7]
Research and technology development at the atomic, molecular or
macromolecular levels, in the length scale of approximately 1 - 100
nanometer range, to provide a fundamental understanding of phenomena
and materials at the nanoscale and to create and use structures, devices
and systems that have novel properties and functions because of their small
and/or intermediate size. The novel and differentiating properties and
functions are developed at a critical length scale of matter typically under
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100 nm. Nanotechnology research and development includes manipulation
under control of the nanoscale structures and their integration into larger
material components, systems and architectures. Within these larger scale
assemblies, the control and construction of their structures and
components remains at the nanometer scale. In some particular cases, the
critical length scale for novel properties and phenomena may be under 1
nm (e.g., manipulation of atoms at ~0.1 nm) or be larger than 100 nm (e.g.,
nanoparticle reinforced polymers have the unique feature at ~ 200-300 nm
as a function of the local bridges or bonds between the nano particles and
the polymer).
1 nm 100 nm
1 nm-100 nm(Mesoscopic)
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2.1.1
nanometer (nm)1
(nm)=10-3()=10-9(m) 110
[8]
2.1.2
///
[/ (Carbon Nanotube, CNT)]/
(Supermolecule) /
/
(Single Electron Transistors)
(Spintronics) (Magnetic Random Access Memory,
MRAM) Terabyte
//
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9
2.1.3
(structure)
(properties) (process)
(top-down) 2.1
2.1
1 nm 10 nm 20 nm 100 nm 1m
Bottom up
(Self-assembly
process)(Supramolecule)
Top Down
1 nm 10 nm 20 nm 100 nm 1m
Bottom up
(Self-assembly
process)(Supramolecule)
Top Down
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10
2.2
2.2
1990
1990 1994
1994
nanostructured assembling system
I IIII I1990 1994
:
(nanocrystalline or nanophase)
(0D-0D) (0D-3D)(0D-2D)
(nanostructuredassembling system)
1D2D3Dnano-patterning
STM
I IIII I1990 1994I IIIIIII II I1990 1994
:
(nanocrystalline or nanophase)
(0D-0D) (0D-3D)(0D-2D)
(nanostructuredassembling system)
1D2D3Dnano-patterning
STM
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(hard
materials)
(soft materials)
(flexibility)
[9]
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2.2
100
/
2.3
/()-
[10]
2.3
/
/
/
/
/
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2.2.1
(
)
1 nm""
20 nm 105
[10]
2.2.2
100 nm
(Sphere Equivalent)
6000~9000 nm() 2000~3000 nm
400~760 nm
1~100 nm
103~105()
(1 nm~100 nm)
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(tunneling
effect)
[10]
2.2.3
(Quantum Size Effect)
(sintering temperature)
(Pb) 600K
20 nm Pb 288K (Ag) 373K
Ag 1173K
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(Al2O3) 2073~2173K
Al2O3 1423~1773K
99.7%[10]
()
[11]
() ()
[10]
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16
(Magnetic Domains)
Hc(Coercive Field)
Hc(Superparamagnetic
Phase)
FeCoNi
Pd
[12]
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17
2.3
(Top-Down)
(High Energy Mechanical Milling)
/
60
(Oxide-dispersion Strengthened)
/
(Bottom-up)
(Gas Phase Condensation GPC)
(Liquid Phase Chemical Precipitation) (Sol-Gel)
(Hydrothermal) (Vapor Phase Chemical Reaction)
(Spray Conversion Process SCP)
(Self-assembly)
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Bottom-up
[12]
2.3.1
0.01~0.05m
1 mm 1~2m
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1m 20%
2m 90%
0.5m 70
(300~500 m/s)(300~450 )
80
Alpine
1~5m
1m
0.1m
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20
5 nm~100
nm
[10]
(Precursor)
(Cluster)
(Cold-trap)
[13]
(1980 )
(1 Pa)102~103 Pa
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[10]
2.3.2
--
-
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A () B () + C () (2.1)
Fe(CO)5SiH4Si(NH)2
A () + B ()C () + D () (2.5)
SiH4NH3C2H4 CO2
Fe(CO)5(g) Fe(s) + 5CO(g)
SiH4 Si(s) + 2H2
3[Si(NH)2] Si3N4(s) + 2NH3(g)
Fe(CO)5(g) Fe(s) + 5CO(g)
SiH4 Si(s) + 2H2
3[Si(NH)2] Si3N4(s) + 2NH3(g)
Fe(CO)5(g) Fe(s) + 5CO(g)
SiH4 Si(s) + 2H2
3[Si(NH)2] Si3N4(s) + 2NH3(g)
Fe(CO)5(g) Fe(s) + 5CO(g)
SiH4 Si(s) + 2H2
3[Si(NH)2] Si3N4(s) + 2NH3(g)
(2.2)
(2.3)
(2.4)
Fe(CO)5(g) Fe(s) + 5CO(g)
SiH4 Si(s) + 2H2
3[Si(NH)2] Si3N4(s) + 2NH3(g)
Fe(CO)5(g) Fe(s) + 5CO(g)
SiH4 Si(s) + 2H2
3[Si(NH)2] Si3N4(s) + 2NH3(g)
(2.6)
(2.7)
(2.8)
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(precursor)
1 m
[14]
pH
pH
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100~350
(dialysis)
(autoclave)
[10,15]
(ZrO2)(Al2O3)
(Fe2O3)
-
-
1 nm
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25
-
pH
[10]
Hydrolysis()
Ti-OR+H2O Ti-OH+ROH
Condensation oxolation (dehydration)()
Ti-OH+HO-Ti Ti-O-Ti +HOH
Alcoxolation (dealcoholation)()
Ti-OH+RO-Ti Ti-O-Ti +ROH
Polymerization()
O O
Ti-O-Ti + Ti-O-Ti O-Ti-O-Ti-O
O O
Hydrolysis()
Ti-OR+H2O Ti-OH+ROH
Condensation oxolation (dehydration)()
Ti-OH+HO-Ti Ti-O-Ti +HOH
Alcoxolation (dealcoholation)()
Ti-OH+RO-Ti Ti-O-Ti +ROH
Polymerization()
O O
Ti-O-Ti + Ti-O-Ti O-Ti-O-Ti-O
O O
(2.9)
(2.10)
(2.11)
(2.12)
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26
1972Fujishima et al.[16]
(TiO2)
[17]
3.1
(catalyst)
[18]
A+BAB
A B AB
AB
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A+BAB (3.1)
ABAB (3.2)
A+[Cat.] A[Cat.] (3.3)
A[Cat.]+BAB[Cat.] (3.4)
AB[Cat.] AB+[Cat.] (3.5)
(TiO2ZnONb2O5WO3SnO2ZrO2
KTaO3CdSZnSCdSeGaPCdTeMoSe2WSe2 )
(Semiconductor, SC)(Insulator)(Conductor)
(band gap)
3.1(a)
(Shells) 3.1(a)
(Valence Shell)
(Free Electron)
(
3.1b)
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3.1(a)
3.1(b)
, Ev
, Ec
, Eg
, Ev
, Ec
, Eg
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(Conducting Band)
(Valence Band)
(1 eV)(1V)
4 eV
1.1 eV 0.67 eV 3.2[19]
[20]
A P
(B) A N (P)
(As)(Sb)(Carrier)
()
N
(Donor)(Hole)
P
(Acceptor)[20]
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3.2[19]
V-2.0
-1.0
0
1.0
2.0
3.0
4.0
TiO2 Nb2O5ZnO Fe2O3 WO3SnO2
SrTiO3CdSeCdS KTaO3
KTa0.77Nb0.2303SiGaP ZrO2
2.2
eV
1.1
eV
5.0
eV
2.5
eV 3.2
eV
3.4
eV
3.2
eV
3.0
eV
3.4
eV
1.7
eV
2.5
eV
2.2
eV
3.2
eV
3.5
eV
H2/H2O
O2/H2O
pH=0
(
)
V-2.0
-1.0
0
1.0
2.0
3.0
4.0
TiO2 Nb2O5ZnO Fe2O3 WO3SnO2
SrTiO3CdSeCdS KTaO3
KTa0.77Nb0.2303SiGaP ZrO2
2.2
eV
1.1
eV
5.0
eV
2.5
eV 3.2
eV
3.4
eV
3.2
eV
3.0
eV
3.4
eV
1.7
eV
2.5
eV
2.2
eV
3.2
eV
3.5
eV
H2/H2O
O2/H2O
V-2.0
-1.0
0
1.0
2.0
3.0
4.0
TiO2 Nb2O5ZnO Fe2O3 WO3SnO2
SrTiO3CdSeCdS KTaO3
KTa0.77Nb0.2303SiGaP ZrO2
2.2
eV
1.1
eV
5.0
eV
2.5
eV 3.2
eV
3.4
eV
3.2
eV
3.0
eV
3.4
eV
1.7
eV
2.5
eV
2.2
eV
3.2
eV
3.5
eV
V-2.0
-1.0
0
1.0
2.0
3.0
4.0
TiO2 Nb2O5ZnO Fe2O3 WO3SnO2
SrTiO3CdSeCdS KTaO3
KTa0.77Nb0.2303SiGaP ZrO2
V-2.0
-1.0
0
1.0
2.0
3.0
4.0
V-2.0
-1.0
0
1.0
2.0
3.0
4.0
TiO2 Nb2O5ZnO Fe2O3 WO3SnO2
SrTiO3CdSeCdS KTaO3
KTa0.77Nb0.2303SiGaP ZrO2
2.2
eV
1.1
eV
5.0
eV
2.5
eV 3.2
eV
3.4
eV
3.2
eV
3.0
eV
3.4
eV
1.7
eV
2.5
eV
2.2
eV
3.2
eV
3.5
eV
H2/H2O
O2/H2O
pH=0
(
)
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3.2
-
3.3[21]
--
O2-OH
[22]
3.3 [21]
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3.3 TiO2
(Photonic crystal)
(Gas senser)(Wave guide)(Ceramics membrane)
[23,24]
(Anatase)(Rutile)(Brookite)
[23]
600~700
TiO2
edge-sharing
corner-sharing
3.4[25]
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3.4
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N
1200
Anatase Anatase
Rutile Rutile
Anatase Rutile
Anatase Anatase
Rutile 3.1 [26]
Anatase(3.79 3.04 )(3.57 2.96 )
(1.949 1.980 )(1.934 1.980
)(mass density, )(band
structure) Anatase 3.9 g/cm3
3.2 eV Rutile 4.23 g/cm3 3.0 eV
[27,28]
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3.1 [26]
79.9 79.9
(g/cm3) 4.23 3.9
a () 4.58 3.78
c () 2.95 9.49
2.71 2.52
() 6.0 ~ 7.0 5.5 ~ 6.0
(eV) 3.0 3.2
114 31
1858 600
(HCl)
(NaOH)
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3.4 TiO2
385 nm
OH O2-
TiO2
[29]
1240 / Ebge (3.6)
(nm)
Ebge (band gap energy (eV))
TiO2 3.2 eV
385 nm TiO2
TiO2 UV
TiO2
6[30]
TiO2
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TiO2
(H2O/O2)
TiO2
O2- OH
OH O2-
TiO2
[31]
TiO2 (anatase) + h TiO2(h+) + TiO2 (e-) (3.7)
TiO2(h+) + H2O H+ + OH (3.8)
TiO2(e-) + O2 O2- (3.9)
e-+ O2 O2- HO2 (3.10)
2HO2 O2 + H2O2 OH +OH- + O2 (3.11)
OH + Ared Aoxd (3.12)
H+
O2-
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[32]
(Direct photolysis)
A+ hA (3.13)
AD1 + D2 (3.14)
A
h
A
D1, D2
290 nm
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(Indirect photolysis)
A+ hA (3.13)
A+BA+B (3.15)
BD1 + D2 (3.16)
A
(
)
1.
2.
3.
4.
(Homogeneous Photo- catalysis)
(Hetergeneous Photocatalysis)[33]
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(TiO2(ZnO)(CdS)
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3.5 TiO2
3.2
3.2
1994 M. R.
Hoffmann
[34]
1995 N. Serpone CdS
[28]
1995 K.
Vinodgopal
SnO2TiO2
[35]
1999 H. D.
Breuer
CrMo
[36]
2001 R. Asahi N
[37]
2002 T.
Umebayashi
S
[38]
2003 D. W. Park Si Fe
[24]
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3.2
2003 H. Kisch C
[39]
2004 L. Miao N2/H2 RF
[40]
2004 H. Luo Br Cl
[41]
2004 S.
Sakthivel
N
[42]
2005 J. C. Yu S
[43]
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4.1
4.1 4.2
4.1
potassium
hydroxide KOH R.D.H. ACS
(P25,
20-40 nm)
Titanium
Dioxide TiO2 Degussa Co. 99%
Nickel nitrate Ni (NO3) 2 R.D.H. ACS
Cobalt nitrate Co (NO3) 2 R.D.H. ACS
Iron nitrate Fe (NO3)3 R.D.H. ACS
4.2
() (g/mol)
(nm)
Methylene Blue (C16H18ClN3S)
319.8 664 280
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4.2
4.3
4.3
()
Precisa XB220A(4)
Power Sonic 420
DSC158
pH Hanna Instrument pH211
Heldolph MR3001
EYELA VOS-201SD(493K)
DENG YNG DH400(773K)
50 mm () x 100 mm (L)
(1473K)
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4.3
20-40 nm TiO2(P25,
Degussa Co.)
X-ray [3,5]
(Anatase)(Rutile)
TiO2 0.01 M
() 10 M KOH
TiO2 1g 50 ml
TiO2 1 %
50 mm 100 mm(SUS 306)
135 TiO2
TiO2
pH 6
400
TiO2
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4.4
4.1
1g 50 ml A
30 min
50 mL 135 1 hr
pH 6
4001 hr
A 10 M 0.01M(Fe(NO3)3 Ni(NO3)2Co(NO3)2)
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4.5
4.5.1
(field emission scanning electron
microscopy, FE-SEM, LEO 1530)
( 4.2)
FE-SEM(emissive- mode)
CRT(cathode radiation tube)
CRT
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4.2 FE-SEM
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4.5.2
(HR-TEM High
resolution transmission electron microscopyJEOL 2010)
( 4.3)
( 1 )
HR-TEM
X
100
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4.3
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4.5.3
BET(Brunauer-Emmett-Teller)
Langmuir equationBJH t-plot
BET
77 K Point B P/P0 = 0.05
~ 0.1 isotherm ( 4.4 a) BET Langmuir equation
molecular crossing area
BET equation
V P
Vm
P
P0
C
P
V(P0-P) VmCP0
(C-1)1
VmC= +
P
V(P0-P) VmCP0
(C-1)1
VmC= + (4.1)
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P/P0( 4.4 b)Kelvin equation
Kelvin equation
Rk Kelvin
R
T
VL
Rk=(-2VL)/RT ln(P/P0)Rk=(-2VL)/RT ln(P/P0) (4.2)
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(a) (b)
4.4 (a) BET ;
(b)
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4.5.4
X (X-ray diffraction XRDPhilip PW
1700) X
4.5 X
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4.5.5
(methylene blue) 664 nm
Beer-Lambert Law
20 mg/L
-(UV-visible spectrometerShimadzu UV-2550)
( 4.6)
-
4.6 -
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Beer-Lambert Law
Iin
Iout Iin Iout
(Transmittance)T
(4.3)
A(Absorbance)(-1)
(4.4)
Beer-Lambert Law
A=lc (4.5)
l c
A olar absorptivity)
20 mgL-1 0.2
wt.% TiO2 13 W 750
Wcm-2
(Newport FSQ-GG 400)
-( 4.7) (Varian Cary100)
TiO2 /
200 800 nm
T=Iin
IoutT=
Iin
Iout
A=-logT= -logIin
Iout=log
Iin
IoutA=-logT= -log
Iin
Iout=log
Iin
Iout
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/
-
4.7-(Varian Cary100)
(diffuse reflection)
Kubelka-Munk
S
R
F(R)
F(R)=(1-R)2
2R=
SF(R)=
(1-R)2
2R=
S(4.6)
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5.1 TiO2
5.1.1 TiO2
-196
TiO2
5.1 TiO2
( TiP) 46 m2/g
TiO2( Fe-TiPCo-TiP Ni-TiP)
TiO2
TiO2 TiO2
5.1 TiO2
79-86%
(mesopore)
TiO2
TiO2
TiO2
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5.1
Sample SBET a Vt b Pore size distribution Mean pore
type (m2g-1) (cm3g-1) Vmicro c (%) Vmeso d (%) size, D e ().
TiP 46 0.123 0.020 (16) 0.103 (84) 4
Fe-TiP 56 0.141 0.020 (14) 0.121 (86) 42
Co-TiP 55 0.130 0.023 (18) 0.107 (82) 41
Ni-Tip 58 0.151 0.023 (15) 0.128 (79) 43
a SBET BET b Vt 0.98 c Vmicro Dubinin-Radushkevish d Vmeso e D Barrett-Joyner-Halenda
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5.1.2 TiO2
CoTiO2FE-SEMHR-TEM
5.1(a)(b)TiO2
20-40 nm
5.1(b) TiO2
5.1(b) 4.757
(anatase) TiO2
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5.1
(a) FE-SEM(b) HR-TEM
(a)
(b)
100 nm
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5.1.3 TiO2
TiO2
5.2XRD TiO2
400
5.2(a) TiO2(P25)
rutile anatase anatase
(2) 25.28 rutile
(2) 27.44 [14]
TiO2 rutile
anatase TiO2
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20 30 40 50 60 702
Inte
nsity
(arb
. uni
t)
(a)
(b)
(c)
(d)
: anatase: rutile
(degrees)
5.2 XRD (a)(b)
(c)(d)
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5.2 TiO2-
TiO2 (diffuse
reflection spectra) 5.3
TiO2 385 nm
TiO2
5.3 400-700 nm
TiO2
TiO2 (band gap)
TiO2
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5.3 (Diffuse reflection
spectra)
200 300 400 500 600 700 800Wavelength (nm)
0
1
2
3D
iffus
e R
efle
ctan
ce,
Fe-TiPCo-TiP
Ni-TiP
F(R)
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135
TiO2 Ti-O-Ti Ti-O-K
Ti-OH [14]
Ti-O-M TiO2
TiO2
[5] 0
10% 3.2eV 2.3eV[44]
TiO2
5.3 TiO2
TiO2
Ni TiO2
475 nm 730 nm Fe TiO2
485 nm Co TiO2 605
nm TiO2
Kubelka-Munk(KM)
[45-47] R KM
(5.1)
S
KM
[48][F(R)hv]1/ hv
KM hv
F(R)=(1-R)2
2R=
SF(R)=
(1-R)2
2R=
S
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[46]
KM ( =2)
( 5.4)
(Co-TiP(2.88 eV)>Ni-TiP(2.63 eV) TiO2(3.2 eV)
(1)
(2)
Ti-O-M
(M=Fe, Co, Ni)
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5.4 KM
2.0 2.5 3.0 3.5 4.0(eV)
0
1
2
3
4
hv
h
v1/2
Fe-TiP
Ni-TiP
F(R)
Co-TiP
[
]
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5.3 TiO2
5.5
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5.5
Langmuir-Hinshelwood
0 20 40 60 80 100 120 140 160 180 200Visible light irradiation (min)
0
10
20
30
40
50
60R
emov
al e
ffic
ienc
y (%
)Ni-TiP
Co-TiP
Fe-TiP
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(e-)-(h+)[4]
(5.2) TiO2
(OH)(5.3) TiO2
(O2-)(5.4)
(5.5)(5.7)
(MB+)
(5.8)
5.5
Ni-TiP(59.3 %) >Co-TiP(54.6 %)>
Fe-TiP(49.8 %)
TiO2
Ni-TiPNi-TiP
Ni-TiP 2.63 eV
TiO2 -(5.2)
TiO2 + h e + h+ (5.2)
H2O + h+ OH + H+ (5.3)
O2 + e O2 (5.4)
O2 + H+ HO2 (5.5)
2 HO2 H2O2 + O2 (5.6)
H2O2 + O2 OH + O2 + OH (5.7)
OH + MB+ colorless compound (5.8)
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Langmuir-Hinshelwood(LH)
[49,50]
-(OH)
LH
ra C
k ()
K Ci
(Ci=20 mgL-1=6.2510-5 molL-1) KC
tka(pseudo first-order)
(5.10)
Ct t
ra=k=kKC
1+KCra=k=
kKC
1+KC(5.9)
ra= -dC
dt=kKC=kaCra= -
dC
dt=kKC=kaC (5.10)
lnCi
Ct
=katlnCi
Ct
=kat(5.11)
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ln(Ci/Ct)(t)
ka TiO2 ka 5.2
Ni-TiP
Ni TiO2
-
( OH)
[50] 5.1
TiO2
TiO2
5.2
Sample type ka102 (min-1)
Fe-TiP 1.37
Co-TiP 1.61
Ni-TiP 1.92
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5.4
TiO2
(Fe, Co Ni) TiO2
TiO2
KM
Fe-TiP(2.98 eV)>Co-TiP(2.88 eV)>Ni-TiP(2.63 eV)
NiTiO2
Ni-TiP(59.3 %) >Co-TiP(54.6 %)> Fe-TiP(49.8 %)
TiO2
Ni
-
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TiO2
6.1
6.1
6.1
Ni-TiP(20-40
nm)
Nickel-doped Titanium Dioxide
Ni-TiO2 99%
Titanium Dioxide TiO2
99%
Acetone C3H6O Echo
37%
Alcohol C2H5OH
95%
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6.2
Ni-TiP
TiO2
0.5 g 50 ml 10
ml 20
2 ml
(Escherichia coli E. Coli) 0.5
ml
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6.3
6.1
6.1 TiO2
2ml
0.5 ml E. Coli
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6.4
(O2)
(O2-)(H2O)
( OH)
/ 6.2 6.3
/
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6.2 (a)(b)
(a)
(b)
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6.3 (a)(b)
(a)
(b)
(a)
(b)
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6.4
E. Coli/E. Coli
Ni-TiP
Ni-TiP
6.5
Ni-TiP E. Coli
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6.4 TiO2(a)(b)
(c)
(d)(e)(f)
(a)
(b)
(c)
(d)
(e)
(f)
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6.5
Aspergillus niger BCRC31512
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6.6
(
) TiO2
/
Ni-TiP
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6.6 (a)
(b)(c) TiO2
(d)(e)(f)
(a)
(b)
(c)
(d)
(e)
(f)
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Ni-TiP
Ni-TiP 6.7
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6.7 TiO2(a)(b)
(a)
(b)
(a)
(b)
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6.8
Ni-TiP
6.9
6.10
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6.8 (a)
(b)
(a)
(b)
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6.9 (a)
(b)
(a)
(b)
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6.10
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/
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7.1
/
P25
() XRD anatase
rutile
UVVisible
() TiO2
KM
Fe-TiP (2.98 eV) > Co-TiP (2.88 eV) > Ni-TiP
(2.63 eV)NiTiO2
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()
Ni-TiP (59.3 %) >
Co-TiP (54.6 %) > Fe-TiP (49.8 %)
TiO2
Ni
-
/
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7.2
(Dye sensitized
solar cellDSSC) 7.1
(1)( FTO
TiO2)(2) I/I3
(3) (Counter Electrode)
DSSC
DSSC
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7.1
Light
Electrolyte( S+ / S )
( S+ / S* )
( A / A- )
Load
Anchored dye
Counter electrode
TCO
h V e-
e-
e-
e-
e-
e-
cb
vb
n-SC( TiO2 )
-0.9
2.5
0.8
0.2
-0.7
V, vs SCE
Pt-loaded CNT arrays
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