New Bonding Model of Radical Adsorbate on Lattice Oxygen of Perovskites

被引：52

作者：

Fung, Victor ^{[1
]}

Wu, Zili ^{[2
,3
]}

Jiang, De-en ^{[1
]}

机构：

[1] Univ Calif Riverside, Dept Chem, Riverside, CA 92521 USA

[2] Oak Ridge Natl Lab, Chem Sci Div, POB 2009, Oak Ridge, TN 37831 USA

[3] Oak Ridge Natl Lab, Ctr Nanophase Mat Sci, POB 2009, Oak Ridge, TN 37831 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2018年 / 9卷 / 21期

关键词：

TRANSITION-METAL OXIDES; COORDINATION NUMBERS; METHANE ACTIVATION; VACANCY FORMATION; TRENDS; SURFACES; ENERGY; PRINCIPLES; REACTIVITY; CATALYSIS;

D O I：

10.1021/acs.jpclett.8b02749

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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 Sd 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. This insight will be useful in understanding the trends in surface reactivity of perovskites and transition-metal oxides in general.

引用

页码：6321 / 6325

页数：9

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