N,S coordination in Ni single-atom catalyst promoting CO2RR towards HCOOH

Carbon-based single atom catalysts (SACs) are attracting extensive attention in the CO2 reduction reaction (CO2RR) due to their maximal atomic utilization, easily regulated active center and high catalytic activity, in which the coordination environment plays a crucial role in the intrinsic catalytic activity. Taking NiN4 as an example, this study reveals that the introduction of different numbers of S atoms into N coordination (Ni-NxS4-x (x = 1-4)) results in outstanding structural stability and catalytic activity. Owing to the additional orbitals around -1.60 eV and abundant Ni dxz, dyz, dx2, and dz2 orbital occupation after S substitution, N,S coordination can effectively facilitate the protonation of adsorbed intermediates and thus accelerate the overall CO2RR. The CO2RR mechanisms for CO and HCOOH generation via two-electron pathways are systematically elucidated on NiN4, NiN3S1 and NiN2S2. NiN2S2 yields HCOOH as the most favorable product with a limiting potential of -0.24 V, surpassing NiN4 (-1.14 V) and NiN3S1 (-0.50 V), which indicates that the different S-atom substitution of NiN4 has considerable influence on the CO2RR performance. This work highlights NiN2S2 as a high-performance CO2RR catalyst to produce HCOOH, and demonstrates that N,S coordination is an effective strategy to regulate the performance of atomically dispersed electrocatalysts.