Mechanistic Insights into Electrocatalytic CO2 Reduction Catalyzed by Graphdiyne-Supported Heteronuclear Dual-Atoms

Electrochemical CO2 reduction not only reduces the greenhouse effect and environmental pollution caused by the large amount of CO2 emissions, but also alleviates the energy depletion problem faced by the shortage of fossil fuels. Dual-atom catalysts (DACs) may have great potential to enhance catalytic performance owing to their flexible active sites and distinct electronic structures compared to single-atom catalysts (SACs). Herein, a series of Fe-based dual-atoms catalysts (FeTM–GDY, TM = Cr, Mn, Co, and Ni) are explored with Fe and transition metals (Cr, Mn, Co, Ni, and Cu) anchored on graphdiyne (GDY) substrate for high-performance CO2 reduction by density functional theory (DFT) calculations. The computational results indicated that FeTM-GDY (TM = Cr, Mn, Co, and Ni) have excellent electrocatalytic performance and the main products for CO2 reduction reaction (CO2RR) are CH4 with the limiting potentials of -0.46, -0.67, -0.54, and -0.67 V, respectively. The catalytic active sites for CO2 reduction on FeTM-GDY (TM = Cr, Mn, Co, and Ni) are metals, while HER preferentially occurs on the carbon atoms.