High-spin Co3+ in cobalt oxyhydroxide for efficient water oxidation

Xin Zhang; Haoyin Zhong; Qi Zhang; Qihan Zhang; Chao Wu; Junchen Yu; Yifan Ma; Hang An; Hao Wang; Yiming Zou; Caozheng Diao; Jingsheng Chen; Zhi Gen Yu; Shibo Xi; Xiaopeng Wang; Junmin Xue

doi:10.1038/s41467-024-45702-4

High-spin Co³⁺ in cobalt oxyhydroxide for efficient water oxidation

Nat Commun. 2024 Feb 15;15(1):1383. doi: 10.1038/s41467-024-45702-4.

Authors

Xin Zhang^#¹, Haoyin Zhong^#¹, Qi Zhang¹, Qihan Zhang¹, Chao Wu^{2

3}, Junchen Yu¹, Yifan Ma¹, Hang An¹, Hao Wang¹, Yiming Zou⁴, Caozheng Diao⁵, Jingsheng Chen¹, Zhi Gen Yu⁶, Shibo Xi⁷, Xiaopeng Wang^{8

9

10

11}, Junmin Xue¹²

Affiliations

¹ Department of Materials Science and Engineering, National University of Singapore, Singapore, 117575, Singapore.
² Institute of Sustainability for Chemical, Energy and Environment (ISCE), Agency for Science, Technology and Research (A*STAR), Singapore, 627833, Singapore.
³ College of Materials Science and Engineering, Sichuan University, Chengdu, 610065, China.
⁴ School of Materials Science and Engineering, Nanyang Technological University, Singapore, 639798, Singapore.
⁵ Singapore Synchrotron Light Sources (SSLS), National University of Singapore, Singapore, 117603, Singapore.
⁶ Institute of High Performance Computing (IHPC), Agency for Science, Technology and Research (A*STAR), Singapore, 138632, Singapore.
⁷ Institute of Sustainability for Chemical, Energy and Environment (ISCE), Agency for Science, Technology and Research (A*STAR), Singapore, 627833, Singapore. Xi_shibo@isce2.a-star.edu.sg.
⁸ Department of Materials Science and Engineering, National University of Singapore, Singapore, 117575, Singapore. msewxia@nus.edu.sg.
⁹ College of Materials Science and Engineering, Sichuan University, Chengdu, 610065, China. msewxia@nus.edu.sg.
¹⁰ State Key Laboratory of Intelligent Construction and Healthy Operation and Maintenance of Deep Underground Engineering, Sichuan University, Chengdu, 610065, China. msewxia@nus.edu.sg.
¹¹ Tefusen Semiconductor & Hydrogen Energy Technology (Yunnan) Co., Ltd, Wenshan Zhuang and Miao Autonomous Prefecture, 663200, China. msewxia@nus.edu.sg.
¹² Department of Materials Science and Engineering, National University of Singapore, Singapore, 117575, Singapore. msexuejm@nus.edu.sg.

^# Contributed equally.

Abstract

Cobalt oxyhydroxide (CoOOH) is a promising catalytic material for oxygen evolution reaction (OER). In the traditional CoOOH structure, Co³⁺ exhibits a low-spin state configuration ([Formula: see text]), with electron transfer occurring in face-to-face [Formula: see text] orbitals. In this work, we report the successful synthesis of high-spin state Co³⁺ CoOOH structure, by introducing coordinatively unsaturated Co atoms. As compared to the low-spin state CoOOH, electron transfer in the high-spin state CoOOH occurs in apex-to-apex [Formula: see text] orbitals, which exhibits faster electron transfer ability. As a result, the high-spin state CoOOH performs superior OER activity with an overpotential of 226 mV at 10 mA cm^-2, which is 148 mV lower than that of the low-spin state CoOOH. This work emphasizes the effect of the spin state of Co³⁺ on OER activity of CoOOH based electrocatalysts for water splitting, and thus provides a new strategy for designing highly efficient electrocatalysts.

Abstract

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