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Title: A Universal Descriptor for the Entropy of Adsorbed Molecules in Confined Spaces

Abstract

Confinement of hydrocarbons in nanoscale pockets and pores provides tunable capability for controlling molecules in catalysts, sorbents, and membranes for reaction and separation applications. While computation of the enthalpic interactions of hydrocarbons in confined spaces has improved, understanding and predicting the entropy of confined molecules remains a challenge. Here we show, using a set of nine aluminosilicate zeolite frameworks with broad variation in pore and cavity structure, that the entropy of adsorption can be predicted as a linear combination of rotational and translational entropy. The extent of entropy lost upon adsorption is predicted using only a single material descriptor, the occupiable volume (V occ). Predictive capability of confined molecular entropy permits an understanding of the relation with adsorption enthalpy, the ability to computationally screen microporous materials, and an understanding of the role of confinement on the kinetics of molecules in confined spaces.

Authors:
ORCiD logo [1];  [2]
  1. Univ. of Minnesota, Minneapolis, MN (United States); Catalysis Center for Energy Innovation, Colburn Laboratory, Newark, DE (United States)
  2. Catalysis Center for Energy Innovation, Colburn Laboratory, Newark, DE (United States); Univ. of Massachusetts, Amherst, MA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI); Univ. of Delaware, Newark, DE (United States); Univ. of Minnesota, Twin Cities, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1469048
Alternate Identifier(s):
OSTI ID: 1498686; OSTI ID: 1508624
Grant/Contract Number:  
SC0001004
Resource Type:
Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Volume: 4; Journal Issue: 9; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Dauenhauer, Paul J., and Abdelrahman, Omar A. A Universal Descriptor for the Entropy of Adsorbed Molecules in Confined Spaces. United States: N. p., 2018. Web. doi:10.1021/acscentsci.8b00419.
Dauenhauer, Paul J., & Abdelrahman, Omar A. A Universal Descriptor for the Entropy of Adsorbed Molecules in Confined Spaces. United States. doi:10.1021/acscentsci.8b00419.
Dauenhauer, Paul J., and Abdelrahman, Omar A. Fri . "A Universal Descriptor for the Entropy of Adsorbed Molecules in Confined Spaces". United States. doi:10.1021/acscentsci.8b00419.
@article{osti_1469048,
title = {A Universal Descriptor for the Entropy of Adsorbed Molecules in Confined Spaces},
author = {Dauenhauer, Paul J. and Abdelrahman, Omar A.},
abstractNote = {Confinement of hydrocarbons in nanoscale pockets and pores provides tunable capability for controlling molecules in catalysts, sorbents, and membranes for reaction and separation applications. While computation of the enthalpic interactions of hydrocarbons in confined spaces has improved, understanding and predicting the entropy of confined molecules remains a challenge. Here we show, using a set of nine aluminosilicate zeolite frameworks with broad variation in pore and cavity structure, that the entropy of adsorption can be predicted as a linear combination of rotational and translational entropy. The extent of entropy lost upon adsorption is predicted using only a single material descriptor, the occupiable volume (Vocc). Predictive capability of confined molecular entropy permits an understanding of the relation with adsorption enthalpy, the ability to computationally screen microporous materials, and an understanding of the role of confinement on the kinetics of molecules in confined spaces.},
doi = {10.1021/acscentsci.8b00419},
journal = {ACS Central Science},
number = 9,
volume = 4,
place = {United States},
year = {2018},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acscentsci.8b00419

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Entropy loss upon adsorption on surfaces and confined spaces.

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.