Abstract
The renewable-energy-powered electrocatalytic CO(2) reduction reaction (CO(2)RR) efficiently converts CO(2) into high-value chemicals and fuels, offering a promising approach to addressing environmental and energy sustainability challenges. This process is of immense significance for constructing a sustainable artificial carbon cycle. Cu-based catalysts exhibit remarkable catalytic activity and broad product selectivity in CO(2)RR, which can be attributed to their excellent electrical conductivity, moderate adsorption energy, and unique electronic structure. This review comprehensively summarizes the advantages, practical applications, and mechanistic insights of Cu-based catalysts in CO(2)RR, with a systematic based on recent advances in tuning strategies via electronic effects and structural design. Specifically, it emphasizes the influence of electronic structure tuning (electron-donating/-withdrawing effects and steric hindrance effects), active center tuning (single-atom catalysts, heterogeneous synergetic effects, and polymer modification), and surface structure (morphology effect, valence-state effect, and crystalline-facet effect) influences on catalytic performance. By rationally designing the catalyst structure, the adsorption behavior of reaction intermediates can be effectively regulated, thereby enabling the highly selective generation of target products. The objective of this paper is to provide a theoretical framework and actionable strategies for the structural design and catalytic performance optimization of Cu-based catalysts, with the ultimate goal of promoting the development and practical application of efficient CO(2)RR catalytic systems.