skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Near-Perfect CO 2 /CH 4 Selectivity Achieved through Reversible Guest Templating in the Flexible Metal–Organic Framework Co(bdp)

Abstract

Metal-organic frameworks are among the most promising materials for industrial gas separations, including the removal of carbon dioxide from natural gas, although substantial improvements in adsorption selectivity are still sought. Herein, we use equilibrium adsorption experiments to demonstrate that the flexible metal-organic framework Co(bdp) (bdp2- = 1,4-benzenedipyrazolate) exhibits a large CO2 adsorption capacity and approaches complete exclusion of CH4 under 50:50 mixtures of the two gases, leading to outstanding CO2/CH4 selectivity under these conditions. In situ powder X-ray diffraction data indicate that this selectivity arises from reversible guest templating, in which the framework expands to form a CO2 clathrate and then collapses to the nontemplated phase upon desorption. Under an atmosphere dominated by CH4, Co(bdp) adsorbs minor amounts of CH4 along with CO2, highlighting the importance of studying all relevant pressure and composition ranges via multicomponent measurements when examining mixed-gas selectivity in structurally flexible materials. Altogether, these results show that Co(bdp) may be a promising CO2/CH4 separation material and provide insights for the further study of flexible adsorbents for gas separations.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [3];  [1];  [2];  [2];  [4]; ORCiD logo [5]
  1. Department of Chemistry, University of California, Berkeley, California 94720, United States; Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
  2. Department of Chemistry, University of California, Berkeley, California 94720, United States
  3. Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, United States
  4. NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, United States; National Renewable Energy Laboratory, Golden, Colorado 80401, United States
  5. Department of Chemistry, University of California, Berkeley, California 94720, United States; Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States; Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1466189
Report Number(s):
NREL/JA-5900-72238
Journal ID: ISSN 0002-7863
DOE Contract Number:  
AC36-08GO28308
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 32; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; metal-organic framework; gas separation; adsorption

Citation Formats

Taylor, Mercedes K., Runčevski, Tomče, Oktawiec, Julia, Bachman, Jonathan E., Siegelman, Rebecca L., Jiang, Henry, Mason, Jarad A., Tarver, Jacob D., and Long, Jeffrey R. Near-Perfect CO 2 /CH 4 Selectivity Achieved through Reversible Guest Templating in the Flexible Metal–Organic Framework Co(bdp). United States: N. p., 2018. Web. doi:10.1021/jacs.8b06062.
Taylor, Mercedes K., Runčevski, Tomče, Oktawiec, Julia, Bachman, Jonathan E., Siegelman, Rebecca L., Jiang, Henry, Mason, Jarad A., Tarver, Jacob D., & Long, Jeffrey R. Near-Perfect CO 2 /CH 4 Selectivity Achieved through Reversible Guest Templating in the Flexible Metal–Organic Framework Co(bdp). United States. doi:10.1021/jacs.8b06062.
Taylor, Mercedes K., Runčevski, Tomče, Oktawiec, Julia, Bachman, Jonathan E., Siegelman, Rebecca L., Jiang, Henry, Mason, Jarad A., Tarver, Jacob D., and Long, Jeffrey R. Sat . "Near-Perfect CO 2 /CH 4 Selectivity Achieved through Reversible Guest Templating in the Flexible Metal–Organic Framework Co(bdp)". United States. doi:10.1021/jacs.8b06062.
@article{osti_1466189,
title = {Near-Perfect CO 2 /CH 4 Selectivity Achieved through Reversible Guest Templating in the Flexible Metal–Organic Framework Co(bdp)},
author = {Taylor, Mercedes K. and Runčevski, Tomče and Oktawiec, Julia and Bachman, Jonathan E. and Siegelman, Rebecca L. and Jiang, Henry and Mason, Jarad A. and Tarver, Jacob D. and Long, Jeffrey R.},
abstractNote = {Metal-organic frameworks are among the most promising materials for industrial gas separations, including the removal of carbon dioxide from natural gas, although substantial improvements in adsorption selectivity are still sought. Herein, we use equilibrium adsorption experiments to demonstrate that the flexible metal-organic framework Co(bdp) (bdp2- = 1,4-benzenedipyrazolate) exhibits a large CO2 adsorption capacity and approaches complete exclusion of CH4 under 50:50 mixtures of the two gases, leading to outstanding CO2/CH4 selectivity under these conditions. In situ powder X-ray diffraction data indicate that this selectivity arises from reversible guest templating, in which the framework expands to form a CO2 clathrate and then collapses to the nontemplated phase upon desorption. Under an atmosphere dominated by CH4, Co(bdp) adsorbs minor amounts of CH4 along with CO2, highlighting the importance of studying all relevant pressure and composition ranges via multicomponent measurements when examining mixed-gas selectivity in structurally flexible materials. Altogether, these results show that Co(bdp) may be a promising CO2/CH4 separation material and provide insights for the further study of flexible adsorbents for gas separations.},
doi = {10.1021/jacs.8b06062},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 32,
volume = 140,
place = {United States},
year = {2018},
month = {7}
}