A replacement strategy for regulating local environment of single-atom Co-S_xN_4-x catalysts to facilitate CO₂...

The performances of single-atom catalysts are governed by their local coordination environments. Here, a thermal replacement strategy is developed for the synthesis of single-atom catalysts with precisely controlled and adjustable local coordination environments. A series of Co-S_xN_4-x (x = 0, 1, 2, 3) single-atom catalysts are successfully synthesized by thermally replacing coordinated N with S at elevated temperature, and a volcano relationship between coordinations and catalytic performances toward electrochemical CO₂ reduction is observed. The Co-S₁N₃ catalyst has the balanced COOH*and CO* bindings, and thus locates at the apex of the volcano with the highest performance toward electrochemical CO₂ reduction to CO, with the maximum CO Faradaic efficiency of 98 ± 1.8% and high turnover frequency of 4564 h^-1 at an overpotential of 410 mV tested in H-cell with CO₂-saturated 0.5 M KHCO₃, surpassing most of the reported single-atom catalysts. This work provides a rational approach to control the local coordination environment of the single-atom catalysts, which is important for further fine-tuning the catalytic performance.