Balancing Activity and Stability in Spinel Cobalt Oxides through Geometrical Sites Occupation towards Efficient Electrocatalytic Oxygen Evolution

Li An; Hong Zhang; Jiamin Zhu; Shibo Xi; Bolong Huang; Mingzi Sun; Yong Peng; Pinxian Xi; Chun-Hua Yan

doi:10.1002/anie.202214600

Balancing Activity and Stability in Spinel Cobalt Oxides through Geometrical Sites Occupation towards Efficient Electrocatalytic Oxygen Evolution

Angew Chem Int Ed Engl. 2023 Jan 16;62(3):e202214600. doi: 10.1002/anie.202214600. Epub 2022 Dec 8.

Authors

Li An¹, Hong Zhang², Jiamin Zhu¹, Shibo Xi³, Bolong Huang⁴, Mingzi Sun⁴, Yong Peng², Pinxian Xi¹, Chun-Hua Yan^{1

5}

Affiliations

¹ State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Frontiers Science Center for Rare Isotopes, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, P. R. China.
² Electron Microscopy Centre of Lanzhou University, School of Materials and Energy, Key Laboratory of Magnetism and Magnetic Materials of Ministry of Education, School of Physical Science and Technology, Lanzhou University, Lanzhou, 730000, China.
³ Institute of Chemical and Engineering Sciences, Agency for Science, Technology and Research (A*STAR), 1 Pesek Road, Singapore, 627833, Singapore.
⁴ Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kow-loon, Hong Kong SAR, China.
⁵ Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.

PMID: 36367220
DOI: 10.1002/anie.202214600

Abstract

Designing active and stable oxygen evolution reaction (OER) catalysts are vitally important to various energy conversion devices. Herein, we introduce elements Ni and Mn into (Co)_tet (Co₂ )_oct O₄ nanosheets (NSs) at fixed geometrical sites, including Mn_oct , Ni_oct , and Ni_tet , to optimize the initial geometrical structure and modulate the CoCo₂ O₄ surface from oxygen-excess to oxygen-deficiency. The pristine (Ni,Mn)-(Co)_tet (Co₂ )_oct O₄ NSs shows excellent OER activity with an overpotential of 281.6 mV at a current density of 10 mA cm^-2 . Moreover, without damaging their initial activity, the activated (Act)-(Ni,Mn)-(Co)_tet (Co₂ )_oct O₄ NSs after surface reconstruction exhibit long-term stability of 100 h under 10 mA cm^-2 , 50 mA cm^-2 , or even 100 mA cm^-2 . The optimal balance between electroactivity and stability leads to remarkable OER performances, providing a pivotal guideline for designing ideal electrocatalysts and inspiring more works to focus on the dynamic change of each occupation site component.

Keywords: OER; decoupled proton-electron transfer; geometrical site occupation; surface reconstruction; well-balanced performance.

Abstract

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