JOURNAL ARTICLE

Effect of functionalized groups on gas-adsorption properties: syntheses of functionalized microporous metal-organic frameworks and their high gas-storage capacity

Yanlong Wang, Chunhong Tan, Zhihao Sun, Zhenzhen Xue, Qilong Zhu, Chaojun Shen, Yuehong Wen, Shengmin Hu, Yong Wang, Tianlu Sheng, Xintao Wu
Chemistry: a European Journal 2014 January 27, 20 (5): 1341-8
24458914
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.

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