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Title: Understanding solvent effects on adsorption and protonation in porous catalysts

Abstract

Abstract Solvent selection is a pressing challenge in developing efficient and selective liquid phase catalytic processes, as predictive understanding of the solvent effect remains lacking. In this work, an attenuated total reflection infrared spectroscopy technique is developed to quantitatively measure adsorption isotherms on porous materials in solvent and decouple the thermodynamic contributions of van der Waals interactions within zeolite pore walls from those of pore-phase proton transfer. While both the pore diameter and the solvent identity dramatically impact the confinement (adsorption) step, the solvent identity plays a dominant role in proton-transfer. Combined computational and experimental investigations show increasingly favorable pore-phase proton transfer to pyridine in the order: water < acetonitrile < 1,4 – dioxane. Equilibrium methods unaffected by mass transfer limitations are outlined for quantitatively estimating fundamental thermodynamic values using statistical thermodynamics.

Authors:
; ; ; ; ; ORCiD logo; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Univ. of Delaware, Newark, DE (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1619537
Alternate Identifier(s):
OSTI ID: 1629984
Grant/Contract Number:  
SC0001004
Resource Type:
Published Article
Journal Name:
Nature Communications
Additional Journal Information:
Journal Name: Nature Communications Journal Volume: 11 Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gould, Nicholas S., Li, Sha, Cho, Hong Je, Landfield, Harrison, Caratzoulas, Stavros, Vlachos, Dionisios, Bai, Peng, and Xu, Bingjun. Understanding solvent effects on adsorption and protonation in porous catalysts. United Kingdom: N. p., 2020. Web. https://doi.org/10.1038/s41467-020-14860-6.
Gould, Nicholas S., Li, Sha, Cho, Hong Je, Landfield, Harrison, Caratzoulas, Stavros, Vlachos, Dionisios, Bai, Peng, & Xu, Bingjun. Understanding solvent effects on adsorption and protonation in porous catalysts. United Kingdom. https://doi.org/10.1038/s41467-020-14860-6
Gould, Nicholas S., Li, Sha, Cho, Hong Je, Landfield, Harrison, Caratzoulas, Stavros, Vlachos, Dionisios, Bai, Peng, and Xu, Bingjun. Wed . "Understanding solvent effects on adsorption and protonation in porous catalysts". United Kingdom. https://doi.org/10.1038/s41467-020-14860-6.
@article{osti_1619537,
title = {Understanding solvent effects on adsorption and protonation in porous catalysts},
author = {Gould, Nicholas S. and Li, Sha and Cho, Hong Je and Landfield, Harrison and Caratzoulas, Stavros and Vlachos, Dionisios and Bai, Peng and Xu, Bingjun},
abstractNote = {Abstract Solvent selection is a pressing challenge in developing efficient and selective liquid phase catalytic processes, as predictive understanding of the solvent effect remains lacking. In this work, an attenuated total reflection infrared spectroscopy technique is developed to quantitatively measure adsorption isotherms on porous materials in solvent and decouple the thermodynamic contributions of van der Waals interactions within zeolite pore walls from those of pore-phase proton transfer. While both the pore diameter and the solvent identity dramatically impact the confinement (adsorption) step, the solvent identity plays a dominant role in proton-transfer. Combined computational and experimental investigations show increasingly favorable pore-phase proton transfer to pyridine in the order: water < acetonitrile < 1,4 – dioxane. Equilibrium methods unaffected by mass transfer limitations are outlined for quantitatively estimating fundamental thermodynamic values using statistical thermodynamics.},
doi = {10.1038/s41467-020-14860-6},
journal = {Nature Communications},
number = 1,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
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https://doi.org/10.1038/s41467-020-14860-6

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