Metal-Oxygen Hybridization Determined Activity in Spinel-Based Oxygen Evolution Catalysts: A Case Study of ZnFe2- xCrxO4

Haiyan Li; Shengnan Sun; Shibo Xi; Yubo Chen; Ting Wang; Yonghua Du; Matthew Sherburne; Joel W. Ager; Adrian C. Fisher; Zhichuan J. Xu

doi:10.1021/acs.chemmater.8b02871

Metal-Oxygen Hybridization Determined Activity in Spinel-Based Oxygen Evolution Catalysts: A Case Study of ZnFe_{2- x}Cr_xO₄

Haiyan Li, Shengnan Sun, Shibo Xi^*, Yubo Chen, Ting Wang, Yonghua Du, Matthew Sherburne, Joel W. Ager, Adrian C. Fisher, Zhichuan J. Xu

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

80 Citations (Scopus)

Abstract

A good understanding of the correlation between electronic properties and catalytic performance is vital to the rational design of active oxygen evolution reaction (OER) catalysts. Here, a volcano-shaped correlation between the OER activity and the Cr substitution amount was found for spinel oxides ZnFe_2-xCr_xO₄ (x = 0-2), in which Zn²⁺ resides in tetrahedral (Td) sites while Fe³⁺ and Cr³⁺ occupy octahedral (Oh) sites. Such a relationship probably is because Cr substitution tunes the e_g occupancy of Oh-site transition metals (TM_Oh) via the Oh-Oh superexchange effect. Density functional calculations further revealed the hybridization degree between the TM_Oh 3d and the O 2p states, and a volcano-shaped trend was also found in the variation of TM_Oh 3d-O 2p hybridization with the amount of Cr substitution. The good correlation between the OER activity and the hybridization highlights the important role of metal-oxygen hybridization in determining the OER activity of these spinel oxides.

Original language	English
Pages (from-to)	6839-6848
Number of pages	10
Journal	Chemistry of Materials
Volume	30
Issue number	19
DOIs	https://doi.org/10.1021/acs.chemmater.8b02871
Publication status	Published - Oct 9 2018
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2018 American Chemical Society.

ASJC Scopus Subject Areas

General Chemistry
General Chemical Engineering
Materials Chemistry

Access to Document

10.1021/acs.chemmater.8b02871

Cite this

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title = "Metal-Oxygen Hybridization Determined Activity in Spinel-Based Oxygen Evolution Catalysts: A Case Study of ZnFe2- xCrxO4",

abstract = "A good understanding of the correlation between electronic properties and catalytic performance is vital to the rational design of active oxygen evolution reaction (OER) catalysts. Here, a volcano-shaped correlation between the OER activity and the Cr substitution amount was found for spinel oxides ZnFe2-xCrxO4 (x = 0-2), in which Zn2+ resides in tetrahedral (Td) sites while Fe3+ and Cr3+ occupy octahedral (Oh) sites. Such a relationship probably is because Cr substitution tunes the eg occupancy of Oh-site transition metals (TMOh) via the Oh-Oh superexchange effect. Density functional calculations further revealed the hybridization degree between the TMOh 3d and the O 2p states, and a volcano-shaped trend was also found in the variation of TMOh 3d-O 2p hybridization with the amount of Cr substitution. The good correlation between the OER activity and the hybridization highlights the important role of metal-oxygen hybridization in determining the OER activity of these spinel oxides.",

author = "Haiyan Li and Shengnan Sun and Shibo Xi and Yubo Chen and Ting Wang and Yonghua Du and Matthew Sherburne and Ager, {Joel W.} and Fisher, {Adrian C.} and Xu, {Zhichuan J.}",

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AU - Li, Haiyan

AU - Sun, Shengnan

AU - Xi, Shibo

AU - Chen, Yubo

AU - Wang, Ting

AU - Du, Yonghua

AU - Sherburne, Matthew

AU - Ager, Joel W.

AU - Fisher, Adrian C.

AU - Xu, Zhichuan J.

PY - 2018/10/9

Y1 - 2018/10/9

N2 - A good understanding of the correlation between electronic properties and catalytic performance is vital to the rational design of active oxygen evolution reaction (OER) catalysts. Here, a volcano-shaped correlation between the OER activity and the Cr substitution amount was found for spinel oxides ZnFe2-xCrxO4 (x = 0-2), in which Zn2+ resides in tetrahedral (Td) sites while Fe3+ and Cr3+ occupy octahedral (Oh) sites. Such a relationship probably is because Cr substitution tunes the eg occupancy of Oh-site transition metals (TMOh) via the Oh-Oh superexchange effect. Density functional calculations further revealed the hybridization degree between the TMOh 3d and the O 2p states, and a volcano-shaped trend was also found in the variation of TMOh 3d-O 2p hybridization with the amount of Cr substitution. The good correlation between the OER activity and the hybridization highlights the important role of metal-oxygen hybridization in determining the OER activity of these spinel oxides.

AB - A good understanding of the correlation between electronic properties and catalytic performance is vital to the rational design of active oxygen evolution reaction (OER) catalysts. Here, a volcano-shaped correlation between the OER activity and the Cr substitution amount was found for spinel oxides ZnFe2-xCrxO4 (x = 0-2), in which Zn2+ resides in tetrahedral (Td) sites while Fe3+ and Cr3+ occupy octahedral (Oh) sites. Such a relationship probably is because Cr substitution tunes the eg occupancy of Oh-site transition metals (TMOh) via the Oh-Oh superexchange effect. Density functional calculations further revealed the hybridization degree between the TMOh 3d and the O 2p states, and a volcano-shaped trend was also found in the variation of TMOh 3d-O 2p hybridization with the amount of Cr substitution. The good correlation between the OER activity and the hybridization highlights the important role of metal-oxygen hybridization in determining the OER activity of these spinel oxides.

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