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

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
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Thermodynamics of mixed-gas adsorption
journal, January 1965


Exceptional Framework Flexibility and Sorption Behavior of a Multifunctional Porous Cuprous Triazolate Framework
journal, May 2008

  • Zhang, Jie-Peng; Chen, Xiao-Ming
  • Journal of the American Chemical Society, Vol. 130, Issue 18, p. 6010-6017
  • DOI: 10.1021/ja800550a

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Robust dynamics
journal, May 2010

  • Deng, Hexiang; Olson, Mark A.; Stoddart, J. Fraser
  • Nature Chemistry, Vol. 2, Issue 6, p. 439-443
  • DOI: 10.1038/nchem.654

Hydrogen storage in metal–organic frameworks
journal, January 2009

  • Murray, Leslie J.; Dincă, Mircea; Long, Jeffrey R.
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1294-1314
  • DOI: 10.1039/b802256a

Separation of Hexane Isomers in a Metal-Organic Framework with Triangular Channels
journal, May 2013


Selective gas adsorption and separation in metal–organic frameworks
journal, January 2009

  • Li, Jian-Rong; Kuppler, Ryan J.; Zhou, Hong-Cai
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1477-1504
  • DOI: 10.1039/b802426j

Site-Specific CO2 Adsorption and Zero Thermal Expansion in an Anisotropic Pore Network
journal, December 2011

  • Queen, Wendy L.; Brown, Craig M.; Britt, David K.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 50, p. 24915-24919
  • DOI: 10.1021/jp208529p

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation
journal, February 2013

  • Nugent, Patrick; Belmabkhout, Youssef; Burd, Stephen D.
  • Nature, Vol. 495, Issue 7439, p. 80-84
  • DOI: 10.1038/nature11893