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Title: New Bonding Model of Radical Adsorbate on Lattice Oxygen of Perovskites

Abstract

In this paper, a new model of bonding between radical adsorbates and lattice oxygens is proposed that considers both the adsorbate–oxygen bonding and the weakening of the metal–oxygen bonds. Density functional calculations of SrMO 3 perovskites for M being 3d, 4d, and 5d transition metals are used to correlate the bulk electronic structure with the surface-oxygen reactivity. Occupation of the metal–oxygen antibonding states, examined via the crystal orbital Hamilton population (COHP), is found to be a useful bulk descriptor that correlates with the vacancy formation energy of the lattice oxygen and its hydrogen adsorption energy. Analysis of density-of-states and COHP indicates that H adsorption energy is a combined result of formation of the O–H bond and the weakening of the surface metal–oxygen bond due to occupation of the metal–oxygen antibonding states by the electron from H. Lastly, this insight will be useful in understanding the trends in surface reactivity of perovskites and transition-metal oxides in general.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of California, Riverside, CA (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1502543
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 9; Journal Issue: 21; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Fung, Victor N., Wu, Zili, and Jiang, De-en. New Bonding Model of Radical Adsorbate on Lattice Oxygen of Perovskites. United States: N. p., 2018. Web. doi:10.1021/acs.jpclett.8b02749.
Fung, Victor N., Wu, Zili, & Jiang, De-en. New Bonding Model of Radical Adsorbate on Lattice Oxygen of Perovskites. United States. doi:10.1021/acs.jpclett.8b02749.
Fung, Victor N., Wu, Zili, and Jiang, De-en. Wed . "New Bonding Model of Radical Adsorbate on Lattice Oxygen of Perovskites". United States. doi:10.1021/acs.jpclett.8b02749.
@article{osti_1502543,
title = {New Bonding Model of Radical Adsorbate on Lattice Oxygen of Perovskites},
author = {Fung, Victor N. and Wu, Zili and Jiang, De-en},
abstractNote = {In this paper, a new model of bonding between radical adsorbates and lattice oxygens is proposed that considers both the adsorbate–oxygen bonding and the weakening of the metal–oxygen bonds. Density functional calculations of SrMO3 perovskites for M being 3d, 4d, and 5d transition metals are used to correlate the bulk electronic structure with the surface-oxygen reactivity. Occupation of the metal–oxygen antibonding states, examined via the crystal orbital Hamilton population (COHP), is found to be a useful bulk descriptor that correlates with the vacancy formation energy of the lattice oxygen and its hydrogen adsorption energy. Analysis of density-of-states and COHP indicates that H adsorption energy is a combined result of formation of the O–H bond and the weakening of the surface metal–oxygen bond due to occupation of the metal–oxygen antibonding states by the electron from H. Lastly, this insight will be useful in understanding the trends in surface reactivity of perovskites and transition-metal oxides in general.},
doi = {10.1021/acs.jpclett.8b02749},
journal = {Journal of Physical Chemistry Letters},
issn = {1948-7185},
number = 21,
volume = 9,
place = {United States},
year = {2018},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on October 17, 2019
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