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Title: Crossing the great divide between single-crystal reactivity and actual catalyst selectivity with pressure transients

Abstract

The quantitative prediction of catalyst selectivity is essential to the design of efficient catalytic processes and requires a detailed knowledge of the reaction mechanism and rate constants. Here we present a study that accurately predicts, using the kinetics and a mechanism derived from fundamental studies on single-crystal gold, the product distribution resulting from the complex reaction network that governs the oxidative coupling of methanol, catalysed by nanoporous gold between 360 and 425 K and for a vast range of pressures. Analysis of the transient product responses to micropulses of methanol over nanoporous gold yields a precise understanding of the marked dependence of selectivity on pressure, surface oxygen coverage and temperature. The key to a high selectivity for methyl formate is the surface lifetime and abundance of the methoxy. In conclusion, this successful microkinetic modelling of catalytic reactions across a wide set of reaction conditions is broadly applicable to predicting catalytic selectivity and provides a pathway to designing more efficient catalytic processes.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [1];  [1]
  1. Harvard Univ., Cambridge, MA (United States)
  2. Univ. of Oslo (Norway)
  3. Univ. of South Carolina, Columbia, SC (United States)
Publication Date:
Research Org.:
Harvard Univ., Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1595977
Grant/Contract Number:  
SC0012573
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Catalysis
Additional Journal Information:
Journal Volume: 1; Journal Issue: 11; Journal ID: ISSN 2520-1158
Publisher:
Springer Nature
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Reece, Christian, Redekop, Evgeniy A., Karakalos, Stavros, Friend, Cynthia M., and Madix, Robert. J. Crossing the great divide between single-crystal reactivity and actual catalyst selectivity with pressure transients. United States: N. p., 2018. Web. doi:10.1038/s41929-018-0167-5.
Reece, Christian, Redekop, Evgeniy A., Karakalos, Stavros, Friend, Cynthia M., & Madix, Robert. J. Crossing the great divide between single-crystal reactivity and actual catalyst selectivity with pressure transients. United States. doi:10.1038/s41929-018-0167-5.
Reece, Christian, Redekop, Evgeniy A., Karakalos, Stavros, Friend, Cynthia M., and Madix, Robert. J. Mon . "Crossing the great divide between single-crystal reactivity and actual catalyst selectivity with pressure transients". United States. doi:10.1038/s41929-018-0167-5. https://www.osti.gov/servlets/purl/1595977.
@article{osti_1595977,
title = {Crossing the great divide between single-crystal reactivity and actual catalyst selectivity with pressure transients},
author = {Reece, Christian and Redekop, Evgeniy A. and Karakalos, Stavros and Friend, Cynthia M. and Madix, Robert. J.},
abstractNote = {The quantitative prediction of catalyst selectivity is essential to the design of efficient catalytic processes and requires a detailed knowledge of the reaction mechanism and rate constants. Here we present a study that accurately predicts, using the kinetics and a mechanism derived from fundamental studies on single-crystal gold, the product distribution resulting from the complex reaction network that governs the oxidative coupling of methanol, catalysed by nanoporous gold between 360 and 425 K and for a vast range of pressures. Analysis of the transient product responses to micropulses of methanol over nanoporous gold yields a precise understanding of the marked dependence of selectivity on pressure, surface oxygen coverage and temperature. The key to a high selectivity for methyl formate is the surface lifetime and abundance of the methoxy. In conclusion, this successful microkinetic modelling of catalytic reactions across a wide set of reaction conditions is broadly applicable to predicting catalytic selectivity and provides a pathway to designing more efficient catalytic processes.},
doi = {10.1038/s41929-018-0167-5},
journal = {Nature Catalysis},
issn = {2520-1158},
number = 11,
volume = 1,
place = {United States},
year = {2018},
month = {11}
}

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Cited by: 11 works
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