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ABSTRACT Hydrogen evolution reaction (HER) is a crucial process for sustainable hydrogen production, yet the development of efficient, stable, and cost‐effective electrocatalysts remains a major challenge. Cu‐based materials have emerged as promising candidates owing to their earth abundance and high electrical conductivity, but their weak hydrogen binding energy (HBE) results in their inherently poor reactivity. This review systematically summarizes the most recent progress in Cu‐based HER catalysts, with a particular focus on the modification strategies, including point defect engineering, multifunctional site construction, strain engineering, and heterointerface engineering. The structure‐activity relationships and catalytic mechanisms underlying these strategies are comprehensively analyzed, highlighting how local electronic modulation, synergistic active sites, and interfacial charge transfer collectively govern the HER kinetics for Cu‐based electrocatalysts. Moreover, emerging phenomena such as dynamic surface reconstruction and gradient compositional design are discussed, revealing their critical roles in generating adaptive active structures and directional charge transport pathways during electrochemical operation. Furthermore, future perspectives are proposed, emphasizing the combination of atomic‐level fabrication, in situ/operando characterization, and data‐driven models, to enable rational and predictive design of high‐performance Cu‐based HER catalysts.
Qian et al. (Mon,) studied this question.