Effect of functionalized groups on gas-adsorption properties: syntheses of functionalized microporous metal-organic frameworks and their high gas-storage capacity.
The microporous metal-organic framework (MMOF) Zn4O(L1)2⋅9 DMF⋅9 H2O (1-H) and its functionalized derivatives Zn4O(L1-CH3)2⋅9 DMF⋅9 H2O (2-CH3) and Zn4O(L1-Cl)2⋅9 DMF⋅9 H2O (3-Cl) have been synthesized and characterized (H3L1=4-[N,N-bis(4-methylbenzoic acid)amino]benzoic acid, H3L1-CH3=4-[N,N-bis(4-methylbenzoic acid)amino]-2-methylbenzoic acid, H3L1-Cl=4-[N,N-bis(4-methylbenzoic acid)amino]-2-chlorobenzoic acid). Single-crystal X-ray diffraction analyses confirmed that the two functionalized MMOFs are isostructural to their parent MMOF, and are twofold interpenetrated three-dimensional (3D) microporous frameworks. All of the samples possess enduring porosity with Langmuir surface areas over 1950 cm(2) g(-1). Their pore volumes and surface areas decrease in the order 1-H>2-CH3 >3-Cl. Gas-adsorption studies show that the H2 uptakes of these samples are among the highest of the MMOFs (2.37 wt% for 3-Cl at 77 K and 1 bar), although their structures are interpenetrating. Furthermore, this work reveals that the adsorbate-adsorbent interaction plays a more important role in the gas-adsorption properties of these samples at low pressure, whereas the effects of the pore volumes and surface areas dominate the gas-adsorption properties at high pressure.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou 350002 (P.R. China), Fax: (+86) 591-8371-4946; Graduate School of the Chinese Academy of Sciences, Beijing 100039 (P.R. China).
Yanlong
Y
Wang
Chunhong
C
Tan
Zhihao
Z
Sun
Zhenzhen
Z
Xue
Qilong
Q
Zhu
Chaojun
C
Shen
Yuehong
Y
Wen
Shengmin
S
Hu
Yong
Y
Wang
Tianlu
T
Sheng
Xintao
X
Wu
adsorption; functionalization; gas storage; metal-organic frameworks; porous materials