Coordination Confined Thermolysis Synthesis of the Ni Single Atom Catalyst on the N‑Doped Commercial Carbon for the Production of Syngas

The electrochemical conversion of CO2 into controllable syngas (CO/H2) over a wide potential range is challenging. The main electrocatalysts are based on the noble metals Au (Ag) or heavy metal Pb. The development of alternative nonprecious catalysts is of paramount importance for practice. In this work, a simple coordination confined thermal pyrolysis method has been developed for the synthesis of Ni single-atom catalyst loaded onto nitrogen-doped commercial carbon. The catalyst is in the form of NiN3–C, which exhibits a high-performance electrocatalytic reduction of CO2 toward producing syngas with Faraday efficiencies of 62.28% of CO and 36.7% of H2. The Gibbs free energies of COOH* and H* on the NiN3–C structure were estimated by using density functional theory (DFT). The formation of COOH* intermediate is the speed-limiting step in the process, with ΔG COOH* being 0.7 eV, while H* is the speed-limiting step in the hydrogen evolution, respectively. This work provides a feasible method for the achievement of nonprecious catalysts for the resourceful use of CO2.