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Title: Exploring perovskites for methane activation from first principles

The diversity of perovskites offers many opportunities for catalysis, but an overall trend has been elusive. In this paper, using density functional theory, we studied a large set of perovskites in the ABO 3 formula via descriptors of oxygen reactivity such as vacancy formation energy, hydrogen adsorption energy, and the first C–H activation energy of methane. It was found that changing the identity of B within a period increases the oxygen reactivity from the early to late transition metals, while changing A within a group has a much smaller effect on oxygen reactivity. Within the same group, B in the 3d period has the most reactive lattice oxygen compared to the 4d or 5d period. Some perovskites display large differences in reactivity for different terminations. Further examination of the second C–H bond breaking on these perovskites revealed that larger A cations and non-transition metal B cations have higher activation energies, which is conducive to the formation of coupling products instead of oxidation to CO or CO 2. Balance between the first C–H bond breaking and methyl desorption suggests a just right oxygen reactivity as described by the hydrogen adsorption energy. Finally, these insights may help in designing better perovskite catalystsmore » for methane activation.« less
Authors:
 [1] ;  [2] ;  [2] ; ORCiD logo [1]
  1. Univ. of California, Riverside, CA (United States). Dept. of Chemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division. Center for Nanophase Materials Sciences
Publication Date:
Grant/Contract Number:
AC05-00OR22725; AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 8; Journal Issue: 3; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of California, Riverside, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1468195

Fung, Victor, Polo-Garzon, Felipe, Wu, Zili, and Jiang, De-en. Exploring perovskites for methane activation from first principles. United States: N. p., Web. doi:10.1039/C7CY01791J.
Fung, Victor, Polo-Garzon, Felipe, Wu, Zili, & Jiang, De-en. Exploring perovskites for methane activation from first principles. United States. doi:10.1039/C7CY01791J.
Fung, Victor, Polo-Garzon, Felipe, Wu, Zili, and Jiang, De-en. 2017. "Exploring perovskites for methane activation from first principles". United States. doi:10.1039/C7CY01791J. https://www.osti.gov/servlets/purl/1468195.
@article{osti_1468195,
title = {Exploring perovskites for methane activation from first principles},
author = {Fung, Victor and Polo-Garzon, Felipe and Wu, Zili and Jiang, De-en},
abstractNote = {The diversity of perovskites offers many opportunities for catalysis, but an overall trend has been elusive. In this paper, using density functional theory, we studied a large set of perovskites in the ABO3 formula via descriptors of oxygen reactivity such as vacancy formation energy, hydrogen adsorption energy, and the first C–H activation energy of methane. It was found that changing the identity of B within a period increases the oxygen reactivity from the early to late transition metals, while changing A within a group has a much smaller effect on oxygen reactivity. Within the same group, B in the 3d period has the most reactive lattice oxygen compared to the 4d or 5d period. Some perovskites display large differences in reactivity for different terminations. Further examination of the second C–H bond breaking on these perovskites revealed that larger A cations and non-transition metal B cations have higher activation energies, which is conducive to the formation of coupling products instead of oxidation to CO or CO2. Balance between the first C–H bond breaking and methyl desorption suggests a just right oxygen reactivity as described by the hydrogen adsorption energy. Finally, these insights may help in designing better perovskite catalysts for methane activation.},
doi = {10.1039/C7CY01791J},
journal = {Catalysis Science and Technology},
number = 3,
volume = 8,
place = {United States},
year = {2017},
month = {11}
}

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