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

Abstract

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.

Authors:
 [1];  [2];  [3];  [1];  [1];  [2];  [4];  [5];  [6];  [2]
  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
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Molecularly Engineered Energy Materials (MEEM)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1386639
DOE Contract Number:  
SC0001342
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 116; Journal Issue: 45; Related Information: MEEM partners with University of California, Los Angeles (lead); University of California, Berkeley; Eastern Washington University; University of Kansas; National Renewable Energy Laboratory; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; solar (photovoltaic), energy storage (including batteries and capacitors), charge transport, membrane, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Morris, William, He, Ning, Ray, Keith G., Klonowski, Peter, Furukawa, Hiroyasu, Daniels, Isaak N., Houndonougbo, Yao A., Asta, Mark, Yaghi, Omar M., and Laird, Brian B. A Combined Experimental-Computational Study on the Effect of Topology on Carbon Dioxide Adsorption in Zeolitic Imidazolate Frameworks. United States: N. p., 2012. Web. doi:10.1021/jp307170a.
Morris, William, He, Ning, Ray, Keith G., Klonowski, Peter, Furukawa, Hiroyasu, Daniels, Isaak N., Houndonougbo, Yao A., Asta, Mark, Yaghi, Omar M., & Laird, Brian B. A Combined Experimental-Computational Study on the Effect of Topology on Carbon Dioxide Adsorption in Zeolitic Imidazolate Frameworks. United States. doi:10.1021/jp307170a.
Morris, William, He, Ning, Ray, Keith G., Klonowski, Peter, Furukawa, Hiroyasu, Daniels, Isaak N., Houndonougbo, Yao A., Asta, Mark, Yaghi, Omar M., and Laird, Brian B. Thu . "A Combined Experimental-Computational Study on the Effect of Topology on Carbon Dioxide Adsorption in Zeolitic Imidazolate Frameworks". United States. doi:10.1021/jp307170a.
@article{osti_1386639,
title = {A Combined Experimental-Computational Study on the Effect of Topology on Carbon Dioxide Adsorption in Zeolitic Imidazolate Frameworks},
author = {Morris, William and He, Ning and Ray, Keith G. and Klonowski, Peter and Furukawa, Hiroyasu and Daniels, Isaak N. and Houndonougbo, Yao A. and Asta, Mark and Yaghi, Omar M. and Laird, Brian B.},
abstractNote = {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.},
doi = {10.1021/jp307170a},
journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 45,
volume = 116,
place = {United States},
year = {2012},
month = {11}
}