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Title: Temperature-regulated guest admission and release in microporous materials

Abstract

While it has long been known that some highly adsorbing microporous materials suddenly become inaccessible to guest molecules below certain temperatures, previous attempts to explain this phenomenon have failed. Here we show that this anomalous sorption behaviour is a temperature-regulated guest admission process, where the pore-keeping group’s thermal fluctuations are influenced by interactions with guest molecules. A physical model is presented to explain the atomic-level chemistry and structure of these thermally regulated micropores, which is crucial to systematic engineering of new functional materials such as tunable molecular sieves, gated membranes and controlled-release nanocontainers. The model was validated experimentally with H 2, N 2, Ar and CH 4 on three classes of microporous materials: trapdoor zeolites, supramolecular host calixarenes and metal-organic frameworks. We also demonstrate how temperature can be exploited to achieve appreciable hydrogen and methane storage in such materials without sustained pressure. Our findings also open new avenues for gas sensing and isotope separation.

Authors:
 [1];  [2];  [3];  [4];  [1];  [1];  [5];  [4]; ORCiD logo [6];  [5]; ORCiD logo [1]
  1. Univ. of Western Australia, Crawley, WA (Australia). Centre for Energy
  2. City Univ. of Hong Kong (China). School of Energy and Environmental Catalysis; Univ. of Melbourne (Australia). Dept. of Chemical and Biomolecular Engineering
  3. Australian Nuclear Science and Technology Organisation (ANSTO), Clayton, VIC (Australia). Australian Synchrotron
  4. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical and Biomolecular Engineering
  5. Univ. of Melbourne (Australia). Dept. of Chemical and Biomolecular Engineering
  6. Monash Univ., Melbourne, VIC (Australia). Dept. of Mechanical and Aerospace Engineering
Publication Date:
Research Org.:
Georgia Tech Research Corporation, Atlanta, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1374884
Grant/Contract Number:
SC0012577; DE140101824; DP130103708; IC150100019
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; chemical engineering; hydrogen storage materials; metal-organic frameworks; porous materials

Citation Formats

Li, Gang, Shang, Jin, Gu, Qinfen, Awati, Rohan V., Jensen, Nathan, Grant, Andrew, Zhang, Xueying, Sholl, David S., Liu, Jefferson Z., Webley, Paul A., and May, Eric F.. Temperature-regulated guest admission and release in microporous materials. United States: N. p., 2017. Web. doi:10.1038/ncomms15777.
Li, Gang, Shang, Jin, Gu, Qinfen, Awati, Rohan V., Jensen, Nathan, Grant, Andrew, Zhang, Xueying, Sholl, David S., Liu, Jefferson Z., Webley, Paul A., & May, Eric F.. Temperature-regulated guest admission and release in microporous materials. United States. doi:10.1038/ncomms15777.
Li, Gang, Shang, Jin, Gu, Qinfen, Awati, Rohan V., Jensen, Nathan, Grant, Andrew, Zhang, Xueying, Sholl, David S., Liu, Jefferson Z., Webley, Paul A., and May, Eric F.. Fri . "Temperature-regulated guest admission and release in microporous materials". United States. doi:10.1038/ncomms15777. https://www.osti.gov/servlets/purl/1374884.
@article{osti_1374884,
title = {Temperature-regulated guest admission and release in microporous materials},
author = {Li, Gang and Shang, Jin and Gu, Qinfen and Awati, Rohan V. and Jensen, Nathan and Grant, Andrew and Zhang, Xueying and Sholl, David S. and Liu, Jefferson Z. and Webley, Paul A. and May, Eric F.},
abstractNote = {While it has long been known that some highly adsorbing microporous materials suddenly become inaccessible to guest molecules below certain temperatures, previous attempts to explain this phenomenon have failed. Here we show that this anomalous sorption behaviour is a temperature-regulated guest admission process, where the pore-keeping group’s thermal fluctuations are influenced by interactions with guest molecules. A physical model is presented to explain the atomic-level chemistry and structure of these thermally regulated micropores, which is crucial to systematic engineering of new functional materials such as tunable molecular sieves, gated membranes and controlled-release nanocontainers. The model was validated experimentally with H2, N2, Ar and CH4 on three classes of microporous materials: trapdoor zeolites, supramolecular host calixarenes and metal-organic frameworks. We also demonstrate how temperature can be exploited to achieve appreciable hydrogen and methane storage in such materials without sustained pressure. Our findings also open new avenues for gas sensing and isotope separation.},
doi = {10.1038/ncomms15777},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {Fri Jun 09 00:00:00 EDT 2017},
month = {Fri Jun 09 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
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