Rational Design of Copper Catalysts for Carbon Dioxide Electroreduction Reaction: Toward Efficient C-C Coupling and C2+ Generation.

With the growing global demand for carbon neutrality and renewable energy technologies, the electrochemical reduction of carbon dioxide (CO2RR) into high-value fuels and chemicals is regarded as one of the key strategies for achieving carbon recycling. Owing to their distinctive catalytic properties, copper-based materials can effectively promote the selective reduction of CO2 toward multicarbon (C2+) products. Hence, copper (Cu)-based materials have attracted extensive research interest in this field. This Review summarizes recent advances in Cu-based catalysts for CO2 electroreduction toward C2+ products from a mechanism-guided perspective. First, the fundamental reaction pathways, C-C coupling mechanisms, thermodynamic and kinetic factors, and dynamic reconstruction of Cu-based catalysts are discussed. Second, the unique characteristics of Cu-based catalysts and representative design strategies for regulating active-site structure, intermediate adsorption, and C-C coupling are highlighted. Representative catalyst systems, including Cu and Cu alloys, Cu-based heterostructures, and compound-derived Cu catalysts, are then discussed with emphasis on their structural features, catalytic performance, and mechanistic insights. Finally, emerging data-driven approaches, practical considerations, current challenges, and future perspectives are discussed, aiming to provide a theoretical basis and technical guidance for the rational design of highly efficient and durable Cu-based CO2RR catalysts.