Selectively Electrochemical Reduction of CO2 Based on Metal Clusters Catalysts

The electrochemical CO2 reduction reaction (eCO2RR) has emerged as a pivotal technology for addressing global climate challenges by converting CO2 into value‐added chemicals, thereby contributing to carbon neutrality efforts. Metal nanoclusters, characterized by their atomically precise structures and unique electronic properties, have recently gained significant attention as highly tunable catalysts for Eco2RR due to their exceptional activity, selectivity, and structure‐property relationships. This review systematically summarizes recent advancements in metal nanoclusters for CO2 conversion. First, we elucidate the fundamental reaction mechanisms and pathways governing the formation of key products such as CO, format, and hydrocarbons. Next, we summarize the catalysts involved in eCO2RR, including noble metal (e.g., Au, Ag) and non‐noble metal (e.g., Cu, Ni) clusters, and present the latest technical strategies for enhancing CO2 reduction efficiency, such as alloying, ligand engineering, defect engineering and heteroatom doping. Finally, we summarize the challenges of metal nanoclusters in eCO2RR and look forward to their future research directions and development prospects. This review systematically puts forward the cutting‐edge design strategy of atomic‐level precise metal nanocluster catalysts in CO2 electroreduction, which not only deeps the understanding of the basic science of electrocatalysis, but also provides a feasible technical roadmap for realizing sustainable CO2 circular economy.