Cu-Based Versatile p-d Bimetallic Catalysts for Efficient CO2 Reduction Reaction via Orbital Matching Mechanism

Abstract Electrocatalytic carbon dioxide reduction reaction to high-value multicarbon products represents a highly promising strategy for achieving carbon neutrality goals. Among various electrocatalysts, copper-based materials occupy a central position due to their unique capability for *CO adsorption and dimerization; however, they still face severe challenges, including high overpotentials and limited product selectivity. Orbital engineering, particularly the construction of p-d bimetallic systems through the introduction of p-block metals, has emerged as a pivotal approach to surmounting the performance bottlenecks of Cu-based catalysts. This review systematically summarizes the recent research progress in copper-based p-d bimetallic catalysts designed via orbital engineering for efficient CO2 reduction reaction. We provide an in-depth discussion on the modulation mechanisms of p-block metals on the performance of Cu active centers from three key dimensions: electronic effects, geometric effects, and microenvironment regulation. Furthermore, we summarize the primary challenges currently facing the field of p-d orbital matching and offer perspectives on the rational design of future CO2 reduction catalytic systems that possess high activity, stability, and energy efficiency, aiming to provide theoretical guidance and practical insights for the large-scale application of green energy conversion technologies.