Rational Design of Copper Catalysts for Carbon Dioxide Electroreduction Reaction: Toward Efficient C–C Coupling and C 2+ Generation

ABSTRACT With the growing global demand for carbon neutrality and renewable energy technologies, the electrochemical reduction of carbon dioxide (CO 2 RR) 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 CO 2 toward multicarbon (C 2+ ) products. Hence, copper (Cu)‐based materials have attracted extensive research interest in this field. This Review summarizes recent advances in Cu‐based catalysts for CO 2 electroreduction toward C 2+ 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 CO 2 RR catalysts.