High-Throughput Discovery of Cu0/Cuδ+ Interfacial Catalysts for CO2 Electroreduction toward C2+ Products

Abstract Electrocatalytic CO2 reduction reaction (CO2RR) toward C2+ products offers a sustainable route for producing high-value chemicals, but is limited by the sluggish C–C coupling step. Copper (Cu)-based catalysts are uniquely effective for C2+ products, and their performance is strongly governed by the interplay between Cu0 and Cuδ+ species. Here, we developed a workflow to evaluate Cu compounds by high-throughput density functional theory (DFT) calculations and proposed potential Cu0/Cuδ+ interfacial catalysts for CO2RR to C2+ products. By applying a set of predetermined criteria, we screened 7 promising candidates from 860 Cu compounds, which could be potentially effective in stabilizing Cuδ+ and constructing a Cu0/Cuδ+ interface to facilitate C–C coupling. Notably, we found that the electrochemical stability of Cuδ+ species is governed by the Cu–X bond strength, and Cuδ+ sites coordinated with S, Se, Te, N, and As could exhibit enhanced stability. The difference between *CO adsorption energy on the Cu0 site and *CHO adsorption energy on the Cuδ+ site is expected to be a key descriptor governing C–C coupling at the Cu0/Cuδ+ interface, and ΔG(*CHO@Cuδ+) – ΔG(*CO@Cu0) should be controlled at ∼–0.5 eV. These findings offer fundamental guidance for the design of Cu0/Cuδ+ interfacial catalysts for CO2RR. This work gives a direction for developing promising Cu0/Cuδ+ interfacial catalysts for CO2RR and provides a framework for high-throughput screening of potential interfacial catalysts for other reactions.