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Title: Brønsted–Evans–Polanyi relation for CO oxidation on metal oxides following the Mars–van Krevelen mechanism

Abstract

Scaling relations are widely used to model catalytic reactions on metal surfaces, but they are less commonly applied to metal oxides. Oxygen vacancy formation energies have been suggested as a descriptor for the activity toward oxidation reactions via the Mars-van Krevelen mechanism. However, there is currently no function that maps oxygen vacancy formation energies to CO oxidation barriers. We have compiled a data set for CO oxidation on doped and pristine metal oxide surfaces as well as metal/metal oxide interface sites using density functional theory. Based on this data, we can predict CO oxidation barriers from oxygen vacancy formation energies using a Brønsted–Evans–Polanyi relation with a mean absolute error of 14 kJ/mol. Contrary to what is known for reactions on metal surfaces, we find that the scaling parameter α that describes the lateness of the transition state for CO oxidation on metal oxides is not constant.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1569466
Alternate Identifier(s):
OSTI ID: 1558674
Grant/Contract Number:  
FG02-05ER15731; AC02-05CH11231; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 377; Journal Issue: C; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kropp, Thomas, and Mavrikakis, Manos. Brønsted–Evans–Polanyi relation for CO oxidation on metal oxides following the Mars–van Krevelen mechanism. United States: N. p., 2019. Web. doi:10.1016/j.jcat.2019.08.002.
Kropp, Thomas, & Mavrikakis, Manos. Brønsted–Evans–Polanyi relation for CO oxidation on metal oxides following the Mars–van Krevelen mechanism. United States. doi:10.1016/j.jcat.2019.08.002.
Kropp, Thomas, and Mavrikakis, Manos. Sun . "Brønsted–Evans–Polanyi relation for CO oxidation on metal oxides following the Mars–van Krevelen mechanism". United States. doi:10.1016/j.jcat.2019.08.002. https://www.osti.gov/servlets/purl/1569466.
@article{osti_1569466,
title = {Brønsted–Evans–Polanyi relation for CO oxidation on metal oxides following the Mars–van Krevelen mechanism},
author = {Kropp, Thomas and Mavrikakis, Manos},
abstractNote = {Scaling relations are widely used to model catalytic reactions on metal surfaces, but they are less commonly applied to metal oxides. Oxygen vacancy formation energies have been suggested as a descriptor for the activity toward oxidation reactions via the Mars-van Krevelen mechanism. However, there is currently no function that maps oxygen vacancy formation energies to CO oxidation barriers. We have compiled a data set for CO oxidation on doped and pristine metal oxide surfaces as well as metal/metal oxide interface sites using density functional theory. Based on this data, we can predict CO oxidation barriers from oxygen vacancy formation energies using a Brønsted–Evans–Polanyi relation with a mean absolute error of 14 kJ/mol. Contrary to what is known for reactions on metal surfaces, we find that the scaling parameter α that describes the lateness of the transition state for CO oxidation on metal oxides is not constant.},
doi = {10.1016/j.jcat.2019.08.002},
journal = {Journal of Catalysis},
number = C,
volume = 377,
place = {United States},
year = {2019},
month = {9}
}

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