Switch of the Rate-Determining Step of Water Oxidation by Spin-Selected Electron Transfer in Spinel Oxides

Shengnan Sun, Yuanmiao Sun, Ye Zhou, Jingjing Shen, Daniel Mandler, Ronny Neumann, Zhichuan J. Xu*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

72 Scopus citations


The 3d transition-metal oxides are a class of promising catalysts for the oxygen evolution reaction (OER) in alkaline media. Manganese-based spinel oxides usually do not show impressive OER performance, and their activity is generally lower than the counterparts containing cobalt. The OER activity and the electronic structure of spinel oxides ZnMn2O4, ZnCo2O4, and the cobalt-substituted ZnMn2O4 were investigated. It has been found that compared to ZnCo2O4, the lower activity of ZnMn2O4 arises from the limitation of spin-selective electron transfer and orbital symmetry restrictions between adsorption of the oxygen species onto the conduction band and the electron transfer from the conduction band to the valence band. The substitution of cobalt into ZnMn2O4 alleviates the spin incompatibility and enables the increase in OER activity.

Original languageAmerican English
Pages (from-to)8106-8111
Number of pages6
JournalChemistry of Materials
Issue number19
StatePublished - 8 Oct 2019

Bibliographical note

Funding Information:
S.S. and Y.S. contributed equally to this work. This work was supported by the Singapore Ministry of Education Tier 1 grant (RG3/18 (S)), Tier 2 grant (MOE2018-T2-2-027), the Singapore National Research Foundation under its Campus for Research Excellence and Technological Enterprise (CREATE) programme, and a PBC Fellowship for Outstanding Post-Doctoral Fellows from China and India 2018/19, Israel’s Council for Higher Education Planning and Budgeting Committee.

Publisher Copyright:
Copyright © 2019 American Chemical Society.


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