Atomically Structural Regulations of Carbon-Based Single-Atom Catalysts for Electrochemical CO₂ Reduction

The electrochemical carbon dioxide reduction reaction (CO₂ RR) converting CO₂ into value-added chemicals and fuels to realize carbon recycling is a solution to the problem of renewable energy shortage and environmental pollution. Among all the catalysts, the carbon-based single-atom catalysts (SACs) with isolated metal atoms immobilized on conductive carbon substrates have shown significant potential toward CO₂ RR, which intrigues researchers to explore high-performance SACs for fuel and chemical production by CO₂ RR. Especially, regulating the coordination structures of the metal centers and the microenvironments of the substrates in carbon-based SACs has emerged as an effective strategy for the tailoring of their CO₂ RR catalytic performance. In this review, the current in situ/operando study techniques and the fundamental parameters for CO₂ RR performance are first briefly presented. Furthermore, the recent advances in synthetic strategies which regulate the atomic structures of the carbon-based SACs, including heteroatom coordination, coordination numbers, diatomic metal centers, and the microenvironments of substrates are summarized. In particular, the structure-performance relationship of the SACs toward CO₂ RR is highlighted. Finally, the inevitable challenges for SACs are outlined and further research directions toward CO₂ RR are presented from the perspectives.