Recent Advances in Electrocatalytic Hydrogenation Reactions on Copper‐Based Catalysts

Abstract Hydrogenation reactions play a critical role in the synthesis of value‐added products within the chemical industry. Electrocatalytic hydrogenation (ECH) using water as the hydrogen source has emerged as an alternative to conventional thermocatalytic processes for sustainable and decentralized chemical synthesis under mild conditions. Among the various ECH catalysts, copper‐based (Cu‐based) nanomaterials are promising candidates due to their earth‐abundance, unique electronic structure, versatility, and high activity/selectivity. Herein, recent advances in the application of Cu‐based catalysts in ECH reactions for the upgrading of valuable chemicals are systematically analyzed. The unique properties of Cu‐based catalysts in ECH are initially introduced, followed by design strategies to enhance their activity and selectivity. Then, typical ECH reactions on Cu‐based catalysts are presented in detail, including carbon dioxide reduction for multicarbon generation, alkyne‐to‐alkene conversion, selective aldehyde conversion, ammonia production from nitrogen‐containing substances, and amine production from organic nitrogen compounds. In these catalysts, the role of catalyst composition and nanostructures toward different products is focused. The co‐hydrogenation of two substrates (e.g., CO₂ and NO_xⁿ, SO₃^2–, etc.) via C─N, C─S, and C─C cross‐coupling reactions are also highlighted. Finally, the critical issues and future perspectives of Cu‐catalyzed ECH are proposed to accelerate the rational development of next‐generation catalysts.