interplay between texture, structure, and reactivity … · metal-organic frameworks (mofs) (chem....

INTERPLAY BETWEEN TEXTURE, STRUCTURE, AND REACTIVITYIN DEFECTIVE METAL ORGANIC FRAMEWORKS

DEFECTS

TEXTURE REACTIVITY

STRUCTURE

Rifan Hardian

Supervisors:M.-Vanessa CouletPhilip L. Llewellyn

Aix-Marseille Université, CNRS,

MADIREL-UMR 7246

PhD Day, MADIREL Lab, 06-07-17, Marseille

Introduction to MOFs

Metal-Organic Frameworks (MOFs)

(Chem. Soc. Rev., 2014, 43, 5750-5765)

porous materials, metal ions/clusters, organic linkers

J. Karra, 2011, Thesis: Georgia Institute of Technology

Potential applications:➢ Gas storage and separation➢ Catalytic processes➢ Drug delivery➢ Sensing (indicated by color change)➢ Nano spring/dampers➢ Etc …

UiO-66 MIL-100(Fe) ZIF-8

MIL-53 Cu-BTC

Outline

Defective MOFs:“ the missing and incorrectly located atoms generate vacancies and dislocations in materials”

IDEAL MOFs

Intrinsic defects

Metal impregn

ation

Missing linkers

Disorder

Heterogeneity

(Z. Fang, B. Bueken, D.E. De Vos, R.A. Fischer. Angew.Chem.Int. Ed. 2015, 54,7234 –7254)

Defective MOFs

“ the missing and incorrectly located atoms generate vacancies and dislocations in materials”(Z. Fang, B. Bueken, D.E. De Vos, R.A. Fischer. Angew.Chem.Int. Ed. 2015, 54,7234 –7254)

IDEAL MOFs

Intrinsic defects

Metal impregn

ation

Missing linkers

Disorder

Heterogeneity

Fe source(Fe2+ / Fe3+)

BTC

XRD

XRD reveals different crystallinity between synthesized/MIL-100(Fe) and commercial/Basolite F300

1. Intrinsic defects in MIL-100(Fe)

PDF analysis reveals less connectivity in commercial Basolite F300

Pair Distribution Function

M.R. Torrente, R. Hardian, M.-V. Coulet, P.L. Llewellyn, et.al.(to submitted)

MIL-100(Fe)

Defective MOFs


IDEAL MOFs

Intrinsic defects

Metal impregn

ation

Missing linkers

Disorder

Heterogeneity

2. Metal impregnation in amorphous and crystalline MIL-100(Fe)

50

90

130

170

210

250

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1N

2ad

s (

cm

³/g

)p/p0

Pd/MIL100 (Fe)

Pd/Basolite F300

N2 physisorption at 77K

Sample BET area (m2/g)

MIL-100(Fe) 1038

Basolite F300 685

Pd/MIL-100(Fe) 244

Pd/Basolite F300 193

MeOH sorption isotherm at 298K

Sample MeOH uptake(cm3/g)

Henry’s constant

MIL-100(Fe) 253 4.2 x 10-6

Basolite F300 149 2.2 x 10-6

Pd/MIL-100(Fe) 258 3.5 x 10-4

Pd/Basolite F300 167 3.8 x 10-4

Conclusions:• MIL-100(Fe) material has higher surface area and methanol uptake as well as more hydrophilic• Pd impregnation reduced significantly the surface area but did not affect methanol uptake, indicating pore

blocking is compensated by the creation of new adsorption site for methanol

Defective MOFs


IDEAL MOFs

Intrinsic defects

Metal impregn

ation

Missing linkers

Disorder

Heterogeneity

3. Missing linkers in UiO-66 system

S. Dissegna, R. Hardian, M.-V. Coulet, P.L. Llewellyn, et.al. CrystEngComm, 2017, Advance Article, DOI: 10.1039/C7CE00224F

Zr4++

UiO-66

Conclusion No average structural changes are observable from XRD (no long-range disorder)

metal

Ligand (BDC)

Modulator(acetic acid)

X-Ray Diffraction

Thermogravimetry analysis

Modulator Proposed formula

16 AA Zr6O4(OH)4 (BDC)5.98(AA)0.02

100 AA Zr6O4(OH)4 (BDC)5.7(AA)0.3

Missing linker amount can be estimated


Modulator(tri-fluoro-AA)



3. Missing linkers in UiO-66 system

Conclusions:modulators = surface area, water uptake, and hydrophilicity for defective materials

N2 physisorption at 77K

Modulator(mol eq)

BET (m2/g)

0 1068

16 AA 1131

33 AA 1191

67 AA 1314

100 AA 1334

1 TFA 1100

10 TFA 1567

Water adsorption at 25°C

Henry’s constant

Water uptake

2.04*10-5 495

1.52*10-5 519

2.49*10-5 556

2.27*10-4 603

7.58*10-4 650

3.52*10-4 528

7.12*10-4 740





Defective MOFs


IDEAL MOFs

Intrinsic defects

Metal impregn

ation

Missing linkers

Disorder

Heterogeneity

4. Disorder in ZIF-8 induced by ball-milling

ZIF-8

Zn2++

C-CC-N

N-Zn

C-ZnN-Zn

Zn-Zn

XRD PDF

High energy ball-milling induces amorphizationLow energy liquid assisted ball-milling retains the crystallinity

0

0.2

0.4

0.6

0.8

1

1.2

0 0.2 0.4 0.6 0.8 1

wat

er a

dso

rbed

(m

mo

l/g)

p/p°

water adsorption at 25°C

z8-0

z8-3

z8-30

0

5

10

15

20

25

0.00001 0.0001 0.001 0.01 0.1 1

nit

roge

n a

dso

rbed

(m

mo

l/g)

log p/p°

nitrogen adsorption at 77K

Z8-0Z8-1Z8-3

0

10

20

30

40

50

60

70

80

90

100

0

500

1000

1500

2000

2500

0 5 10 15 20 25 30 35

deg

ree

of

crys

talli

nit

y (%

)

BET

su

rfac

e ar

ea

(m2 /

g)

Milling time (minutes)

surface area and crystallinity

0

500

1000

1500

2000

2500

0.E+00

5.E-07

1.E-06

2.E-06

2.E-06

3.E-06

3.E-06

4.E-06

0 10 20 30 40

He

nry

’s c

on

stan

t

milling time (minutes)

surface area and hydrophilicity

KH

BET BET

su

rfac

e ar

ea

(m2 /

g)

Surface area is proportional to the crystallinity and inversely proportional to the hydrophilicity

4. Disorder in ZIF-8 induced by ball-milling

Defective MOFs


IDEAL MOFs

Intrinsic defects

Metal impregn

ation

Missing linkers

Disorder

Heterogeneity

5. Heterogeneity in Ni-BTC systems

Context:• the formation of polymorphisms (with different coordinated water molecules)

are controlled by synthesis procedures.

• Enable to convert one phase to another by post-treatment will allow one to obtain the desired phase(s) from the existing phase(s) while avoiding synthesis from the starting reactants.

• Application-wise, different phase is expected to show different performance, ex: CO2 or water adsorption properties

+BTCNi2+, Cu2+

Cu-BTC

Questions:• Are Cu-BTC and Ni-BTC structurally similar?• How are the connectivity (long/short-range order) that govern

the different phases?• How are the performances of different phases?

XRD Synchrotron data

Structure refinement

Profile matching

Structure model & visualization

PDF analysis (Mo source)

Amorphous phase retains the connectivity only until 5Å

Connectivity assessment

PDF generation

Profile matching

Dynamic structural transitions in Ni-BTC MOFs

amorphous

Crystalline 1 Crystalline 2


10.7Å Ni1-Ni3

6.9Å Ni1-Ni2

2.01Å Ni-O Cu-BTC

PDF of Ni-BTC.18H2O monoclinic generated by PDFGui

Ni-O2.01

5.1

6.910.7

1423.8

17.120.3

28.7

30.5

PDF of Cu-BTC cubic generated by PDFGui

Ni-BTC


≠ Cu-BTCThe structure of Ni-BTC is different from Cu-BTC Ni-BTC

Conclusions

• Defects in MOFs induces deviation in texture, structure, and reactivity (performance) from ideal MOFs

• Better control in defect creation and concentration could lead to better control in MOFs’ properties

Defect type MOF system Texture Structure Reactivity

Intrinsic defect MIL-100(Fe)Basolite F300

↑ BET↓ BET

↑ crystallinity↓ crystallinity

≈ hydrophilicity≈ hydrophilicity

Metalimpregnation

MIL-100(Fe)Basolite F300

↓ BET↓ BET

≈ crystallinity≈ crystallinity

↑ hydrophilicity↑ hydrophilicity

Missing linkers UiO-66 ↑ BET ≈ crystallinity ↑ hydrophilicity

Disorder(amorphization)

ZIF-8ZIF-8 + liquid

↓ BET↓ BET

↓ crystallinity≈ crystallinity

↑ hydrophilicity?

Heterogeneity:Mixed phasesMixed metal

Ni-BTCNi-X-BTC

??

dynamic?

??

Future works

• Characterization on low energy milling ZIF-8• Characterizations of mixed phase and mixed metal in Ni-BTC systems• More works …

interplay between texture, structure, and reactivity … · metal-organic frameworks (mofs) (chem....

Documents