期刊
JOURNAL OF PHYSICAL CHEMISTRY C
卷 116, 期 45, 页码 24084-24090出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp307170a
关键词
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资金
- Molecularly Engineered Energy Materials, an Energy Frontier Research Center
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0001342]
- Office of Science of the U.S. Department of Energy [DE-AC02-05CH11231]
We report CO2 adsorption data for four zeolitic imidazolate frameworks (ZIFs) to 55 bar, namely ZIF-7, ZIF-11, ZIF-93, and ZIF-94. Modification of synthetic conditions allows access to different topologies with the same metal ion and organic link: ZIF-7 (ZIF-94) having sod topology and ZIF-11 (ZIF-93) having the rho topology. The varying topology, with fixed metal ion and imidazolate functionality, makes these systems ideal for studying the effect of topology on gas adsorption in ZIFs. The experiments show that the topologies with the smaller pores (ZIF-7 and 94) have larger adsorptions than their counterparts (ZIF-11 and 93, respectively) at low pressures (<1 bar); however, the reverse is true at higher pressures where the larger-pore structures have significantly higher adsorption. Molecular modeling and heat of adsorption measurements indicate that while the binding potential wells for the smaller pore structures are deeper than those of the larger pore structures, they are relatively narrow and cannot accommodate multiple CO2 occupancy, in contrast to the much broader potential wells seen in the larger pore structures.
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