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Research Article

Activating copper oxide for stable electrocatalytic ammonia oxidation reaction via in-situ introducing oxygen vacancies

Jingjing Huang1,2,3,§, Zhe Chen1,4,§, Jinmeng Cai5, Yongzhen Jin1,2,3, Tao Wang4,6( ), Jianhui Wang1,2,3( )
Department of Chemistry, Zhejiang University, Hangzhou 310027, China
Key Laboratory of 3D Micro/Nano Fabrication and Characterization of Zhejiang Province, School of Engineering, Westlake University, Hangzhou 310024, China
Institute of Advanced Technology, Westlake Institute for Advanced Study, Hangzhou 310024, China
Center of Artificial Photosynthesis for Solar Fuels, School of Science, Westlake University, Hangzhou 310024, China
Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou 450001, China
School of Science, Westlake Institute for Advanced Study, Hangzhou 310024, China

§ Jingjing Huang and Zhe Chen contributed equally to this work.

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Graphical Abstract

In-situ electrochemically introducing oxygen vacancies (Vo) not only turns the inactive CuO into efficient electrocatalytic ammonia oxidation reaction (EAOR) catalyst but also achieves a high stability of over 400 h at a high current density of ~ 200 mA·cm−2. The presence of Vo on the CuO surface induces a remarkable upshift of the d-band center of active Cu site closer to the Fermi level, which significantly stabilizes the reaction intermediates (*NHx) and efficiently oxidizes NH3 into N2.

Abstract

Electrocatalytic ammonia oxidation reaction (EAOR) provides an ideal solution for on-board hydrogen supply for fuel cells, while the lack of efficient and durable EAOR catalysts has been a long-standing obstacle for its practical application. Herein, we reported that the defect engineering via in-situ electrochemically introducing oxygen vacancies (Vo) not only turns the inactive CuO into efficient EAOR catalyst but also achieves a high stability of over 400 h at a high current density of ~ 200 mA·cm−2. Theoretical simulation reveals that the presence of Vo on the CuO surface induces a remarkable upshift of the d-band center of active Cu site closer to the Fermi level, which significantly stabilizes the reaction intermediates (*NHx) and efficiently oxidizes NH3 into N2. This Vo-modulated CuO shows a different catalytic mechanism from that on the conventional Pt-based catalysts, paving a new avenue to develop inexpensive, efficient, and robust catalysts, not limited to EAOR.

Keywords

electrocatalysisammonia oxidation reactionoxygen vacancyCuOstability

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Nano Research
Volume 15 Issue 7,
July 2022
Pages 5987-5994
DOI: 10.1007/s12274-022-4279-5
Cite this article:
Huang J, Chen Z, Cai J, et al. Activating copper oxide for stable electrocatalytic ammonia oxidation reaction via in-situ introducing oxygen vacancies. Nano Research, 2022, 15(7): 5987-5994. https://doi.org/10.1007/s12274-022-4279-5
Topics:
Electrocatalysts

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Received: 01 January 2022
Revised: 26 February 2022
Accepted: 27 February 2022
Published: 30 April 2022
© Tsinghua University Press 2022
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