Tuning CatalyticSelectivity at the Metal–SupportInterface: Review and Outlook on Copper-Based Systems for SustainableCO2 Electroreduction

Abstract Copper-based supported catalysts have emerged as highly promising catalysts for electrochemical CO2 reduction (CO2RR) due to their improved stability, enhanced electron transfer, and superior catalytic performance. This Review provides a comprehensive overview of recent developments in copper-supported electrocatalysts, focusing on various metal oxide supports, which contribute to better CO2 adsorption, stabilization of reaction intermediates, and enhanced product selectivity. Key catalyst design strategies, including alloying, defect engineering, atomically dispersed catalyst, and single-atom alloy approaches on advanced supports like graphitic carbon nitride, are discussed for their role in improving catalytic efficiency and reducing energy barriers. The importance of metal–support interface in tuning catalytic activity and selectivity is also emphasized. Additionally, interfacial engineering of Cu-based catalysts with roles of reducible and nonreducible oxides, oxygen vacancies, charge transfer direction, and interfacial electronic structure has been discussed in detail. This Review also examines advances in electrochemical reactor configurations, such as H-cells, flow cells with gas diffusion electrodes, and membrane electrode assemblies, that address challenges related to mass transport and system scalability. This work aims to offer a comprehensive perspective on the design of copper-based supported catalysts and reactor systems, providing guidance for the development of efficient, selective, and industrially viable CO2-electroreduction technologies.