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

Dauenhauer, Paul J.; Abdelrahman, Omar A.

doi:10.1021/acscentsci.8b00419

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 (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.

Authors:

^[1]; Abdelrahman, Omar A. ^[2]

University of Minnesota, 484 Amundson Hall, 421 Washington Avenue SE, Minneapolis, Minnesota 55455, United States, Catalysis Center for Energy Innovation, 150 Academy Street, Colburn Laboratory, Newark, Delaware 19716, United States
Catalysis Center for Energy Innovation, 150 Academy Street, Colburn Laboratory, Newark, Delaware 19716, United States, University of Massachusetts Amherst, 686 North Pleasant Street, 112F Goessmann Laboratory, Amherst, Massachusetts 01003, United States

Publication Date:: Fri Sep 07 00:00:00 EDT 2018

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)

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 Name: ACS Central Science Journal Volume: 4 Journal Issue: 9; Journal ID: ISSN 2374-7943

Publisher:: American Chemical Society

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.

Copy to clipboard


                    Dauenhauer, Paul J., & Abdelrahman, Omar A. A Universal Descriptor for the Entropy of Adsorbed Molecules in Confined Spaces.  United States.  https://doi.org/10.1021/acscentsci.8b00419

Copy to clipboard


                    Dauenhauer, Paul J., and Abdelrahman, Omar A. Fri .  
"A Universal Descriptor for the Entropy of Adsorbed Molecules in Confined Spaces".  United States.  https://doi.org/10.1021/acscentsci.8b00419.

Copy to clipboard


                    
@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         = {Fri Sep 07 00:00:00 EDT 2018},

  month        = {Fri Sep 07 00:00:00 EDT 2018}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Publisher's Version of Record
https://doi.org/10.1021/acscentsci.8b00419

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 45 works

Citation information provided by
Web of Science

Figures / Tables:

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

All figures and tables (7 total)

Save / Share:

Export Metadata

Save to My Library

Figures / Tables found in this record:

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

Similar Records in DOE PAGES and OSTI.GOV collections:

Mixed Enthalpy–Entropy Descriptor for the Rational Design of Synthesizable High-Entropy Materials Over Vast Chemical Spaces

Journal Article Dey, Dibyendu ; Liang, Liangbo ; Yu, Liping - Journal of the American Chemical Society

The practically unlimited high-dimensional composition space of high-entropy materials (HEMs) has emerged as an exciting platform for functional material design and discovery. However, the identification of stable and synthesizable HEMs and robust design rules remains a daunting challenge. Here, we propose a mixed enthalpy–entropy descriptor (MEED) that enables highly efficient, robust, high-throughput prediction of synthesizable HEMs across vast chemical spaces from first-principles. The MEED is based on two parameters: the relative formation enthalpy with respect to the most stable competing compound and the spread of the point-defect formation energy spectrum. The former measures the relative synthesizability of an HEM tomore »« less
https://doi.org/10.1021/jacs.4c00209
Adsorption and Transport Properties of Zeolite SAPO-34 for Krypton/Xenon Separations

Journal Article Kwon, Yeon Hye ; Benjamin, Emily ; Pisharodi, Vivek ; ... - Transactions of the American Nuclear Society

Nuclear power is an economical means of providing carbon-free energy, but requires effective ways to deal with the radioactive waste products. As part of the overall process for recycling used nuclear fuel (UNF), it is necessary to develop technologies to separate the off-gases formed during the fission of uranium and plutonium in nuclear power reactors. The off-gas contains {sup 129}I (radioisotope), NO, NO{sub 2}, CO{sub 2} containing {sup 14}C (radioisotope), {sup 3}H{sub 2}O (radioactive tritium oxide), {sup 85}Kr (radioisotope), and {sup 136}Xe. Separating and capturing each gas is essential to reduce the volume of radioactive waste for storage. Currently theremore »« less
Adsorption of furan, hexanoic acid, and alkanes in a hierarchical zeolite at reaction conditions: Insights from molecular simulations

Journal Article Josephson, Tyler R. ; Dauenhauer, Paul J. ; Tsapatsis, Michael ; ... - Journal of Computational Science

Hierarchical zeolites containing both micropores and mesopores are valuable catalysts for facilitating reactions of large molecules. Furan acylation by fatty acids is a promising reaction for valorizing biomass, and the self-pillared pentasil (SPP) zeolite was found to perform particularly well for this reaction. To better understand the distribution of molecules in hierarchical zeolites at the elevated temperature (T = 523 K) and the elevated pressure (p >1 bar) associated with typical reaction conditions, unary and binary adsorption were predicted using Monte Carlo simulations in the isothermal–isobaric Gibbs ensemble. Adsorption of six species (furan, hexanoic acid, -hexane, -decane, -tetradecane, and 3,6-diethyloctane)more »« less
https://doi.org/10.1016/j.jocs.2020.101267

Full Text Available
Tailoring nanoscopic confines to maximize catalytic activity of hydronium ions

Journal Article Shi, Hui ; Eckstein, Sebastian ; Vjunov, Aleksei ; ... - Nature Communications

Acid catalysis by hydronium ions is ubiquitous in aqueous-phase organic reactions. Here we show that hydronium ion catalysis, exemplified by intramolecular dehydration of cyclohexanol, is markedly influenced by steric constraints, yielding turnover rates that increase by up to two orders of magnitude in tight confines relative to an aqueous solution of a Brønsted acid. The higher activities in zeolites BEA and FAU than in water are caused by more positive activation entropies that more than offset higher activation enthalpies. The higher activity in zeolite MFI with pores smaller than BEA and FAU is caused by a lower activation enthalpy inmore »« less
https://doi.org/10.1038/ncomms15442
An experimental approach for controlling confinement effects at catalyst interfaces

Journal Article Slot, Thierry K. ; Riley, Nathan ; Shiju, N. Raveendran ; ... - Chemical Science

Catalysts are conventionally designed with a focus on enthalpic effects, manipulating the Arrhenius activation energy. This approach ignores the possibility of designing materials to control the entropic factors that determine the pre-exponential factor. Here we investigate a new method of designing supported Pt catalysts with varying degrees of molecular confinement at the active site. Combining these with fast and precise online measurements, we analyse the kinetics of a model reaction, the platinum-catalysed hydrolysis of ammonia borane. We control the environment around the Pt particles by erecting organophosphonic acid barriers of different heights and at different distances. This is done bymore »« less
https://doi.org/10.1039/D0SC04118A

Similar Records