Multicomponent electrocatalytic coupling of CO2 with small molecules: From active-site coordination to reactor-level integration

Multicomponent electrocatalytic coupling between small molecule conversion and CO 2 reduction has emerged as a promising route for the sustainable synthesis of value-added chemicals, offering improved atom economy, enhanced energy efficiency, and expanded product diversity beyond conventional electrochemical CO 2 reduction. Relative to single-reactant CO 2 reduction, multicomponent coupling imposes additional constraints associated with concurrent reactant activation and interfacial mass transport, rendering performance dependent on highly efficient catalyst development and reactor-level design. This mini-review comprehensively summarizes recent advances in this field, with particular emphasis on the design of catalytic active sites, the mechanistic investigation of C–C, C–N, and C–O bond formation, and the engineering of advanced electrolyzers. Finally, we present the current perspectives and future outlook in this area to guide the rational development of multiscale-integrated electrocatalytic systems, along with practical recommendations to accelerate the transition from laboratory research to scalable industrial implementation. • Multicomponent electrocatalytic coupling of ECO 2 RR with small molecules enhances carbon utilization and product complexity. • C–C, C–N, and C–O bond formation pathways are governed by active-site coordination and electronic structure modulation. • Key intermediates and coupling mechanisms are revealed by advanced DFT calculations and in situ techniques. • Improvement of catalytic activity and selectivity is achieved through regulating the mass transport and local microenvironment by electrolyzer engineering.