journal article·2025-10Open access

A‐Site Cation Deficiency in Antiperovskites for Precisely Accelerating the Volmer Step of Alkaline Hydrogen Evolution

Yan Chen, Zuoqing Liu, Bin Chen, Wei‐Hsiang Huang, Zheng Tang, Mingkai Xu, Min‐Hsin Yeh, Chih‐Wen Pao, Mingjie Pu, Guangming Yang, Yufeng Guo, Zhiwei Hu, Yinlong Zhu

Advanced Energy Materials· Volume 15· Issue 37

Abstract

Abstract The slow kinetics of alkaline hydrogen evolution reaction (HER) leads to large activity gap between acidic and alkaline electrolytes mainly owing to the extra sluggish Volmer step involving water dissociation and OH − desorption. Herein, a facile and effective strategy is reported to regulate the electronic structures and interfacial water behavior through introducing A‐site cation deficiency in antiperovskites for jointly accelerating the Volmer reaction and thereby improving the alkaline HER performance. As a proof‐of‐concept, the In‐deficient In 0.9 NNi 3 antiperovskite shows significantly enhanced HER activity than stoichiometric counterpart and outperforms various state‐of‐the‐art non‐noble metal electrocatalysts ever reported. More importantly, when applied in a practical anion exchange membrane water electrolyzer (AEMWE) device, the In 0.9 NNi 3 ‐based cathode attains an industrial current density of 1 A cm −2 at a low voltage of 1.92 V and steadily operates up to 100 h, superior to the commercial Raney Ni catalyst. By combined theoretical studies and comprehensive experiments, the enhanced HER performance of In 0.9 NNi 3 is mainly originated from the Ni site‐expedited Volmer step, which includes boosted water dissociation by promoting the free water adsorption and spontaneous OH − desorption due to elongated Ni─N bonds. This work provides a significant inspiration to design high‐performance alkaline HER electrocatalysts via defect chemistry.
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Research context

OpenAlex topics: Electrocatalysts for Energy Conversion · Advanced battery technologies research · Fuel Cells and Related Materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Institute for Frontier Science Nanjing University of Aeronautics and Astronautics Nanjing 210016 China

State Key Laboratory of Materials‐Oriented Chemical Engineering College of Chemical Engineering Nanjing Tech University Nanjing 211816 China

State Key Laboratory of Intelligent Construction and Healthy Operation and Maintenance of Deep Underground Engineering Guangdong Provincial Key Laboratory of Deep Earth Sciences and Geothermal Energy Exploitation and Utilization Shenzhen Key Laboratory of Deep Underground Engineering Sciences and Green Energy College of Civil and Transportation Engineering Shenzhen University Shenzhen 518060 China

National Synchrotron Radiation Research Center (NSRRC) Hsinchu 300092 Taiwan

Sustainable Electrochemical Energy Development (SEED) Center National Taiwan University of Science and Technology Taipei 106 Taiwan

Department of Chemical Engineering National Taiwan University of Science and Technology Taipei 10607 Taiwan

School of Mechanical Engineering and Rail Transit Changzhou University Changzhou 213164 China

State Key Laboratory of Mechanics and Control for Aerospace Structures MOE Key Laboratory for Intelligent Nano Materials and Devices College of Aerospace Engineering Nanjing University of Aeronautics and Astronautics Nanjing 210016 China

Max Planck Institute for Chemical Physics of Solids Nothnitzer Strasse 40 01187 Dresden Germany

Funding

National Natural Science Foundation of China

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