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Title: Supramolecular binding and separation of hydrocarbons within a functionalized porous metal–organic framework

Abstract

Supramolecular interactions are fundamental to host–guest binding in many chemical and biological processes. Direct visualization of such supramolecular interactions within host–guest systems is extremely challenging, but crucial to understanding their function. Within this paper, we report a comprehensive study that combines neutron scattering, synchrotron X-ray and neutron diffraction, and computational modelling to define the detailed binding at a molecular level of acetylene, ethylene and ethane within the porous host NOTT-300. This study reveals simultaneous and cooperative hydrogen-bonding, π···π stacking interactions and intermolecular dipole interactions in the binding of acetylene and ethylene to give up to 12 individual weak supramolecular interactions aligned within the host to form an optimal geometry for the selective binding of hydrocarbons. In addition, we also report the cooperative binding of a mixture of acetylene and ethylene within the porous host, together with the corresponding breakthrough experiments and analysis of adsorption isotherms of gas mixtures.

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Oak Ridge National Laboratory, Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1286811
Alternate Identifier(s):
OSTI ID: 1352748
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 7; Journal Issue: 2; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Metal–organic frameworks

Citation Formats

Yang, Sihai, Ramirez-Cuesta, Anibal J., Newby, Ruth, Garcia-Sakai, Victoria, Manuel, Pascal, Callear, Samantha K., Campbell, Stuart I., Tang, Chiu C., and Schröder, Martin. Supramolecular binding and separation of hydrocarbons within a functionalized porous metal–organic framework. United States: N. p., 2014. Web. doi:10.1038/nchem.2114.
Yang, Sihai, Ramirez-Cuesta, Anibal J., Newby, Ruth, Garcia-Sakai, Victoria, Manuel, Pascal, Callear, Samantha K., Campbell, Stuart I., Tang, Chiu C., & Schröder, Martin. Supramolecular binding and separation of hydrocarbons within a functionalized porous metal–organic framework. United States. doi:10.1038/nchem.2114.
Yang, Sihai, Ramirez-Cuesta, Anibal J., Newby, Ruth, Garcia-Sakai, Victoria, Manuel, Pascal, Callear, Samantha K., Campbell, Stuart I., Tang, Chiu C., and Schröder, Martin. Mon . "Supramolecular binding and separation of hydrocarbons within a functionalized porous metal–organic framework". United States. doi:10.1038/nchem.2114. https://www.osti.gov/servlets/purl/1286811.
@article{osti_1286811,
title = {Supramolecular binding and separation of hydrocarbons within a functionalized porous metal–organic framework},
author = {Yang, Sihai and Ramirez-Cuesta, Anibal J. and Newby, Ruth and Garcia-Sakai, Victoria and Manuel, Pascal and Callear, Samantha K. and Campbell, Stuart I. and Tang, Chiu C. and Schröder, Martin},
abstractNote = {Supramolecular interactions are fundamental to host–guest binding in many chemical and biological processes. Direct visualization of such supramolecular interactions within host–guest systems is extremely challenging, but crucial to understanding their function. Within this paper, we report a comprehensive study that combines neutron scattering, synchrotron X-ray and neutron diffraction, and computational modelling to define the detailed binding at a molecular level of acetylene, ethylene and ethane within the porous host NOTT-300. This study reveals simultaneous and cooperative hydrogen-bonding, π···π stacking interactions and intermolecular dipole interactions in the binding of acetylene and ethylene to give up to 12 individual weak supramolecular interactions aligned within the host to form an optimal geometry for the selective binding of hydrocarbons. In addition, we also report the cooperative binding of a mixture of acetylene and ethylene within the porous host, together with the corresponding breakthrough experiments and analysis of adsorption isotherms of gas mixtures.},
doi = {10.1038/nchem.2114},
journal = {Nature Chemistry},
number = 2,
volume = 7,
place = {United States},
year = {2014},
month = {12}
}

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