Engineering the regulation strategy of active sites to explore the intrinsic mechanism over single‑atom catalysts in electrocatalysis

The development of efficient and sustainable energy sources is a crucial strategy for addressing energy and environmental crises, with a particular focus on high-performance catalysts. Single-atom catalysts (SACs) have attracted significant attention because of their exceptionally high atom utilization efficiency and outstanding selectivity, offering broad application prospects in energy development and chemical production. This review systematically summarizes the latest research progress on SACs in five key electrochemical reactions: hydrogen evolution reaction, oxygen reduction reaction, carbon dioxide reduction reaction, nitrogen reduction reaction, and oxygen evolution reaction. Initially, a brief overview of the current understanding of electrocatalytic active sites in SACs is provided. Subsequently, the electrocatalytic mechanisms of these reactions are discussed. Emphasis is placed on various modification strategies for SAC surface-active sites, including coordination environment regulation, electronic structure modulation, support structure regulation, the introduction of structural defects, and multifunctional site design, all aimed at enhancing electrocatalytic performance. This review comprehensively examines SAC deactivation and poisoning mechanisms, highlighting the importance of stability enhancement for practical applications. It also explores the integration of density functional theory calculations and machine learning to elucidate the fundamental principles of catalyst design and performance optimization. Furthermore, various synthesis strategies for industrial-scale production are summarized, providing insights into commercialization. Finally, perspectives on future research directions for SACs are highlighted, including synthesis strategies, deeper insights into active sites, the application of artificial intelligence tools, and standardized testing and performance requirements.