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Title: A systematic study on Pt based, subnanometer-sized alloy cluster catalysts for alkane dehydrogenation: effects of intermetallic interaction

Abstract

Platinum-based bimetallic nanoparticles are analyzed by the application of density functional theory to a series of tetrahedral Pt3X cluster models, with element X taken from the P-block, preferably group 14, or from the D-block around group 10. Almost identical cluster geometries allow a systematic investigation of electronic effects induced by different elements X. Choosing the propane-to-propene conversion as the desired dehydrogenation reaction, we provide estimates for the activity and selectivity of the various catalysts based on transition state theory. No significant Brønsted–Evans–Polanyi-relation could be found for the given reaction. A new descriptor, derived from an energy decomposition analysis, captures the effect of element X on the rate-determining step of the first hydrogen abstraction. Higher activities than obtained for pure Pt4 clusters are predicted for Pt alloys containing Ir, Sn, Ge and Si, with Pt3Ir showing particularly high selectivity.

Authors:
 [1];  [1];  [1];  [1]
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  1. Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1571063
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 18; Journal Issue: 16; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hauser, Andreas W., Horn, Paul R., Head-Gordon, Martin, and Bell, Alexis T. A systematic study on Pt based, subnanometer-sized alloy cluster catalysts for alkane dehydrogenation: effects of intermetallic interaction. United States: N. p., 2016. Web. doi:10.1039/c6cp00360e.
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Hauser, Andreas W., Horn, Paul R., Head-Gordon, Martin, & Bell, Alexis T. A systematic study on Pt based, subnanometer-sized alloy cluster catalysts for alkane dehydrogenation: effects of intermetallic interaction. United States. https://doi.org/10.1039/c6cp00360e
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Hauser, Andreas W., Horn, Paul R., Head-Gordon, Martin, and Bell, Alexis T. Fri . "A systematic study on Pt based, subnanometer-sized alloy cluster catalysts for alkane dehydrogenation: effects of intermetallic interaction". United States. https://doi.org/10.1039/c6cp00360e. https://www.osti.gov/servlets/purl/1571063.
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@article{osti_1571063,
title = {A systematic study on Pt based, subnanometer-sized alloy cluster catalysts for alkane dehydrogenation: effects of intermetallic interaction},
author = {Hauser, Andreas W. and Horn, Paul R. and Head-Gordon, Martin and Bell, Alexis T.},
abstractNote = {Platinum-based bimetallic nanoparticles are analyzed by the application of density functional theory to a series of tetrahedral Pt3X cluster models, with element X taken from the P-block, preferably group 14, or from the D-block around group 10. Almost identical cluster geometries allow a systematic investigation of electronic effects induced by different elements X. Choosing the propane-to-propene conversion as the desired dehydrogenation reaction, we provide estimates for the activity and selectivity of the various catalysts based on transition state theory. No significant Brønsted–Evans–Polanyi-relation could be found for the given reaction. A new descriptor, derived from an energy decomposition analysis, captures the effect of element X on the rate-determining step of the first hydrogen abstraction. Higher activities than obtained for pure Pt4 clusters are predicted for Pt alloys containing Ir, Sn, Ge and Si, with Pt3Ir showing particularly high selectivity.},
doi = {10.1039/c6cp00360e},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 16,
volume = 18,
place = {United States},
year = {Fri Jan 01 00:00:00 EST 2016},
month = {Fri Jan 01 00:00:00 EST 2016}
}
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https://doi.org/10.1039/c6cp00360e
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