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research article

Statistical mechanical model of gas adsorption in porous crystals with dynamic moieties

Simon, Cory M.
•
Braun, Efrem
•
Carraro, Carlo
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2017
Proceedings Of The National Academy Of Sciences Of The United States Of America (PNAS)

Some nanoporous, crystalline materials possess dynamic constituents, for example, rotatable moieties. These moieties can undergo a conformation change in response to the adsorption of guest molecules, which qualitatively impacts adsorption behavior. We pose and solve a statistical mechanical model of gas adsorption in a porous crystal whose cages share a common ligand that can adopt two distinct rotational conformations. Guest molecules incentivize the ligands to adopt a different rotational configuration than maintained in the empty host. Our model captures inflections, steps, and hysteresis that can arise in the adsorption isotherm as a signature of the rotating ligands. The insights disclosed by our simple model contribute a more intimate understanding of the response and consequence of rotating ligands integrated into porous materials to harness them for gas storage and separations, chemical sensing, drug delivery, catalysis, and nanoscale devices. Particularly, our model reveals design strategies to exploit these moving constituents and engineer improved adsorbents with intrinsic thermal management for pressure-swing adsorption processes.

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Type
research article
DOI
10.1073/pnas.1613874114
Web of Science ID

WOS:000392095800005

Author(s)
Simon, Cory M.
Braun, Efrem
Carraro, Carlo
Smit, Berend  
Date Issued

2017

Publisher

National Academy of Sciences

Published in
Proceedings Of The National Academy Of Sciences Of The United States Of America (PNAS)
Volume

114

Issue

3

Start page

E287

End page

E296

Subjects

metal-organic frameworks

•

flexible metal-organic frameworks

•

statistical mechanics

•

porous materials

•

gas storage

URL

URL

http://www.pnas.org/content/114/3/E287.full.pdf
Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
CEN  
Available on Infoscience
February 17, 2017
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/134521
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