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
“ 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
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
“ 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
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(acetic acid)
Modulator(tri-fluoro-AA)
Modulator(acetic acid)
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
Modulator(acetic acid)
Modulator(tri-fluoro-AA)
Modulator(acetic acid)
Modulator(tri-fluoro-AA)
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
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
“ 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
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
5. Heterogeneity in Ni-BTC systems
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
5. Heterogeneity in Ni-BTC systems
≠ 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 …