Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2010
Enhancing the Stability of Metal-Organic Frameworks in Humid Air by
Incorporating Water Repellent Functional Groups
Electronic Supplementary Information (ESI)
Tianjiao Wu, Lingjuan Shen, Matthew Luebbers, Chunhua Hu, Qingmei Chen, Zheng Ni* and
Richard I. Masel*
Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign,
Urbana, Illinois 61801,United States. E-mail: [email protected] , [email protected]
All starting reagents, Zinc nitrate hexahydrate (Aldrich), 2-trifluoromethoxy terephthalic
acid, N,N-Diethylformamide (TCI America) were used as purchased without further
purification.
Microwave Synthesis of Banasorb-22: Exact amount of zinc nitrate hexahydrate (0.15
g, 0.504 mmol) and 2-trifluoromethoxy terephthalic acid (0.0946 g, 0.378 mmol) were
dissolved in 10 mL N,N-diethylformamide (DEF). The solution was then sealed in a
reaction tube and heated with CEM Discover Labmate Microwave Synthesizer at 150W
for a reaction time of 80 seconds. The crystals are yellow in cubic shape, with size
ranging from 4 to 7 microns (see Figure 1).
SEM Pictures
Figure 1 Microwave synthesized Banasorb-22.
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2010
(a)
(b)
(c)
(d)
Figure 2 SEM pictures of MOFs before and after water vapour exposure: (a) Banasorb22 before; (b) Banasorb-22 after; (c) IRMOF-1 before; (d) IRMOF-1 after.
Structure of Banasorb-22
(a)
(b)
Figure 3 (a) Coordination structure of Banasorb22; (b) Unit cell of Banasorb22.
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2010
Table 1 Crystallographic data of Banasorb22.
Compound reference
Chemical formula
Formula Mass
Crystal system
a/Å
b/ Å
c/ Å
α/°
β/°
γ/°
Unit cell volume/ Å3
Temperature/K
Space group
No. of formula units per unit cell, Z
No. of reflections measured
No. of independent reflections
Rint
Final R1 values (I > 2σ(I))
Final wR(F2) values (I > 2σ(I))
Final R1 values (all data)
Final wR(F2) values (all data)
Banasorb22
C52H48F12N4O21Zn4
1554.42
Cubic
25.765(5)
25.765(5)
25.765(5)
90.00
90.00
90.00
17104(6)
297(2)
Fm-3m
8
34035
844
0.0689
0.1068
0.3247
0.1390
0.3438
Figure 4 Comparison of single crystal XRD calculated and PXRD of microwave
synthesized Banasorb-22
Supplementary Material (ESI) for Chemical Communications
This journal is (c) The Royal Society of Chemistry 2010
Table 2 Elemental Analyses of IRMOF-1 and Banasorb-22 before and after water vapour
exposure.
IRMOF-1
Element
Zn
Calculated
33.97%
Found before (±0.4%)
31.12%
Found after (±0.4%)
30.07%
C
37.44%
33.38%
33.30%
H
1.57%
1.57%
1.75%
N
0.00%
0.23%
0.19%
Element
Zn
C
Calculated
25.60%
31.73%
Found before (±0.4%)
21.46%
32.80%
Found after (±0.4%)
21.94%
32.84%
H
0.89%
1.47%
1.53%
N
0.00%
0.80%
1.05%
F
16.73%
10.82%
11.11%
Banasorb-22