Abstract Realizing large-scale electrochemical hydrogen evolution in alkaline and neutral media by robust and non-noble-metal heterogeneous catalysts is highly ambitious due to the sluggish reaction kinetics at low H+ conditions. Herein, highly efficient hydrogen evolution reaction (HER) catalysts, comprising Ni, NiO clusters, and defective carbon, are successfully constructed via a facile and large-scale route. Multiple synchrotron radiation-based X-ray spectroscopic characterizations, combining high-resolution transmission electron microscopy measurements, indicate the formation of ternary interfacial superstructure with intimate interfacial coupling through abundant Ni O C bonds. Impressively, the optimized catalyst loaded onto the usual glass carbon electrode exhibits exceptional catalytic activities with overpotentials of 64 and 76 mV to reach 10 mA cm−2 in 1 M KOH and 1 M phosphate buffer solution (PBS), respectively, representing one of the best non-noble-metal HER electrocatalysts to date. Insights into the metal/oxide interfacial effects through density functional theory calculations reveal that the interface sites could efficiently lower the energy barrier of the rate-determining step (RDS), contributing to the fast reaction kinetics. This work not only provides comprehensive insights into interfacial feature of highly active HER catalysts but also broadens the fundamental understanding of interfacial effects toward HER catalysis.

中文翻译：

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三元界面超结构实现非凡的析氢电催化

摘要 由于在低 H+ 条件下反应动力学缓慢，因此通过稳健的非贵金属多相催化剂在碱性和中性介质中实现大规模电化学析氢具有很高的挑战性。在此，通过简便且大规模的路线成功构建了包含 Ni、NiO 簇和缺陷碳的高效析氢反应 (HER) 催化剂。基于多同步辐射的 X 射线光谱表征，结合高分辨率透射电子显微镜测量，表明通过丰富的 Ni OC 键形成具有紧密界面耦合的三元界面超结构。令人印象深刻的是，负载在普通玻璃碳电极上的优化催化剂表现出卓越的催化活性，在 1 M KOH 和 1 M 磷酸盐缓冲溶液 (PBS) 中的过电位分别为 64 和 76 mV，达到 10 mA cm-2，是最好的非-迄今为止的贵金属 HER 电催化剂。通过密度泛函理论计算对金属/氧化物界面效应的洞察表明，界面位点可以有效地降低限速步骤 (RDS) 的能垒，有助于快速反应动力学。这项工作不仅提供了对高活性 HER 催化剂界面特征的全面见解，而且拓宽了对界面效应对 HER 催化的基本理解。代表迄今为止最好的非贵金属 HER 电催化剂之一。通过密度泛函理论计算对金属/氧化物界面效应的洞察表明，界面位点可以有效地降低限速步骤 (RDS) 的能垒，有助于快速反应动力学。这项工作不仅提供了对高活性 HER 催化剂界面特征的全面见解，而且拓宽了对界面效应对 HER 催化的基本理解。代表迄今为止最好的非贵金属 HER 电催化剂之一。通过密度泛函理论计算对金属/氧化物界面效应的洞察表明，界面位点可以有效地降低限速步骤 (RDS) 的能垒，有助于快速反应动力学。这项工作不仅提供了对高活性 HER 催化剂界面特征的全面见解，而且拓宽了对界面效应对 HER 催化的基本理解。