Shifting Oxygen Charge Towards Octahedral Metal: A Way to Promote Water Oxidation on Cobalt Spinel Oxides

Cobalt spinel oxides are a class of promising transition metal (TM) oxides for catalyzing oxygen evolution reaction (OER). Their catalytic activity depends on the electronic structure. In a spinel oxide lattice, each oxygen anion is shared amongst its four nearest transition metal cations, of which...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-04, Vol.58 (18), p.6042-6047
Main Authors: Sun, Shengnan, Sun, Yuanmiao, Zhou, Ye, Xi, Shibo, Ren, Xiao, Huang, Bicheng, Liao, Hanbin, Wang, Luyuan Paul, Du, Yonghua, Xu, Zhichuan J.
Format: Article
Language:English
Subjects:
Anions
Catalysis
Catalytic activity
Cations
Charge distribution
Cobalt
Electronic structure
geometry effects
Interstices
Metal ions
metal-oxygen covalency
Metals
Oxidation
Oxides
Oxygen
oxygen charge
Oxygen evolution reactions
Spinel
spinel oxides
Transition metals
water oxidation
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Summary:Cobalt spinel oxides are a class of promising transition metal (TM) oxides for catalyzing oxygen evolution reaction (OER). Their catalytic activity depends on the electronic structure. In a spinel oxide lattice, each oxygen anion is shared amongst its four nearest transition metal cations, of which one is located within the tetrahedral interstices and the remaining three cations are in the octahedral interstices. This work uncovered the influence of oxygen anion charge distribution on the electronic structure of the redox‐active building block Co−O. The charge of oxygen anion tends to shift toward the octahedral‐occupied Co instead of tetrahedral‐occupied Co, which hence produces strong orbital interaction between octahedral Co and O. Thus, the OER activity can be promoted by pushing more Co into the octahedral site or shifting the oxygen charge towards the redox‐active metal center in CoO6 octahedra. The oxygen evolution activity of Co‐based spinel oxides is dominated by the catalytically critical TMO6 octahedra. Pushing more active Co into octahedral sites and shifting the oxygen charge to octahedral Co significantly enhance the activity.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201902114