Heterogeneous Single‐Atom Catalysts for Electrochemical CO₂ Reduction Reaction

The electrochemical CO₂ reduction reaction (CO₂ RR) is of great importance to tackle the rising CO₂ concentration in the atmosphere. The CO₂ RR can be driven by renewable energy sources, producing precious chemicals and fuels, with the implementation of this process largely relying on the development of low-cost and efficient electrocatalysts. Recently, a range of heterogeneous and potentially low-cost single-atom catalysts (SACs) containing non-precious metals coordinated to earth-abundant elements have emerged as promising candidates for the CO₂ RR. Unfortunately, the real catalytically active centers and the key factors that govern the catalytic performance of these SACs remain ambiguous. Here, this ambiguity is addressed by developing a fundamental understanding of the CO₂ RR-to-CO process on SACs, as CO accounts for the major product from CO₂ RR on SACs. The reaction mechanism, the rate-determining steps, and the key factors that control the activity and selectivity are analyzed from both experimental and theoretical studies. Then, the synthesis, characterization, and the CO₂ RR performance of SACs are discussed. Finally, the challenges and future pathways are highlighted in the hope of guiding the design of the SACs to promote and understand the CO₂ RR on SACs.