Revealing the Kinetic Balance between Proton-Feeding and Hydrogenation in CO₂ Electroreduction

Electrocatalytic reduction of CO₂ to high-value-added chemicals provides a feasible path for global carbon balance. Herein, the fabrication of Ni_{NP x} @Ni_{SA y} -NG (x,y = 1, 2, 3; NG = nitrogen-doped graphite) is reported, in which Ni single atom sites (Ni_SA ) and Ni nanoparticles (Ni_NP ) coexist. These Ni_{NP x} @Ni_{SA y} -NG presented a volcano-like trend for maximum CO Faradaic efficiency (FE_CO ) with the highest point at Ni_NP2 @Ni_SA2 -NG in CO₂ RR. Ni_NP2 @Ni_SA2 -NG exhibited ≈98% of maximum FE_CO and a large current density of -264 mA cm^-2 at -0.98 V (vs. RHE) in the flow cell. In situ experiment and density functional theory (DFT) calculations confirmed that the proper content of Ni_SA and Ni_NP balanced kinetic between proton-feeding and CO₂ hydrogenation. The Ni_NP in Ni_NP2 @Ni_SA2 -NG promoted the formation of H* and reduced the energy barrier of *CO₂ hydrogenation to *COOH, and CO desorption can be efficiently facilitated by Ni_SA sites, thereby resulting in enhanced CO₂ RR performance.