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Title: Defect‐Mediated Ordering of Condensed Water Structures in Microporous Zeolites

Abstract

Abstract Ab‐initio molecular dynamics simulations and transmission infrared spectroscopy are employed to characterize the structure of water networks in defect‐functionalized microporous zeolites. Thermodynamically stable phases of clustered water molecules are localized at some of the defects in zeolite Beta, which include catalytic sites such as framework Lewis acidic Sn atoms in closed and hydrolyzed‐open forms, as well as silanol nests. These water clusters compete with ideal gas‐like structures at low water densities and pore‐filling phases at higher water densities, with the equilibrium phase determined by the water chemical potential. The physical characteristics of these phases are determined by the defect identity, with the local binding and orientation of hydroxyl moieties around the defects playing a central role. The results suggest general principles for how the structure of polar solvents in microporous solid acids is influenced by local defect functionalization, and the thermodynamic stability of the condensed phases surrounding such sites, in turn, implies that the catalysis of Lewis acids will be influenced by local water ordering.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Charles D. Davidson School of Chemical Engineering Purdue University 480 Stadium Mall Drive West Lafayette IN 47907 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1567908
Grant/Contract Number:  
SC0010379
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition) Journal Volume: 58 Journal Issue: 46; Journal ID: ISSN 1433-7851
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Bukowski, Brandon C., Bates, Jason S., Gounder, Rajamani, and Greeley, Jeffrey. Defect‐Mediated Ordering of Condensed Water Structures in Microporous Zeolites. Germany: N. p., 2019. Web. doi:10.1002/anie.201908151.
Bukowski, Brandon C., Bates, Jason S., Gounder, Rajamani, & Greeley, Jeffrey. Defect‐Mediated Ordering of Condensed Water Structures in Microporous Zeolites. Germany. https://doi.org/10.1002/anie.201908151
Bukowski, Brandon C., Bates, Jason S., Gounder, Rajamani, and Greeley, Jeffrey. Mon . "Defect‐Mediated Ordering of Condensed Water Structures in Microporous Zeolites". Germany. https://doi.org/10.1002/anie.201908151.
@article{osti_1567908,
title = {Defect‐Mediated Ordering of Condensed Water Structures in Microporous Zeolites},
author = {Bukowski, Brandon C. and Bates, Jason S. and Gounder, Rajamani and Greeley, Jeffrey},
abstractNote = {Abstract Ab‐initio molecular dynamics simulations and transmission infrared spectroscopy are employed to characterize the structure of water networks in defect‐functionalized microporous zeolites. Thermodynamically stable phases of clustered water molecules are localized at some of the defects in zeolite Beta, which include catalytic sites such as framework Lewis acidic Sn atoms in closed and hydrolyzed‐open forms, as well as silanol nests. These water clusters compete with ideal gas‐like structures at low water densities and pore‐filling phases at higher water densities, with the equilibrium phase determined by the water chemical potential. The physical characteristics of these phases are determined by the defect identity, with the local binding and orientation of hydroxyl moieties around the defects playing a central role. The results suggest general principles for how the structure of polar solvents in microporous solid acids is influenced by local defect functionalization, and the thermodynamic stability of the condensed phases surrounding such sites, in turn, implies that the catalysis of Lewis acids will be influenced by local water ordering.},
doi = {10.1002/anie.201908151},
journal = {Angewandte Chemie (International Edition)},
number = 46,
volume = 58,
place = {Germany},
year = {2019},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/anie.201908151

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Cited by: 30 works
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