A Combined Experimental-Computational Study on the Effect of Topology on Carbon Dioxide Adsorption in Zeolitic Imidazolate Frameworks

Journal Article · Thu Nov 01 00:00:00 EDT 2012 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/jp307170a· OSTI ID:1386639

Morris, William ^[1]; He, Ning ^[2]; Ray, Keith G. ^[3]; Klonowski, Peter ^[1]; Furukawa, Hiroyasu ^[1]; Daniels, Isaak N. ^[2]; Houndonougbo, Yao A. ^[4]; Asta, Mark ^[5]; Yaghi, Omar M. ^[6]; Laird, Brian B. ^[2]

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1. Center for Reticular Chemistry, Department of Chemistry and Biochemistry, University of California-Los Angeles, Los Angeles, California, 90095, United States
2. Department of Chemistry, University of Kansas, Lawrence, Kansas 66045, United States
3. Department of Physics, University of California, Berkeley, California 94720, United States
4. Department of Chemistry and Biochemistry, Eastern Washington University, Cheney, Washington 99004, United States
5. Department of Materials Science and Engineering, University of California, Berkeley, California 94720, United States
6. Center for Reticular Chemistry, Department of Chemistry and Biochemistry, University of California-Los Angeles, Los Angeles, California, 90095, United States; Department of Chemistry, University of California, Berkeley, California 94720, United States; Molecular Foundry, Division of Materials Sciences, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States; NanoCentury KAIST Institute and Graduate School of EEWS (WCU), Daejeon 305-701, Korea

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.

• Research Organization: Energy Frontier Research Centers (EFRC) (United States). Molecularly Engineered Energy Materials (MEEM)
• Sponsoring Organization: USDOE SC Office of Basic Energy Sciences (SC-22)
• DOE Contract Number: SC0001342
• OSTI ID: 1386639
• Journal Information: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 45 Vol. 116; ISSN 1932-7447
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

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