Sulfur‐Decorated Ni−N−C Catalyst for Electrocatalytic CO(2) Reduction with Near 100 % CO Selectivity

Developing highly efficient electrocatalysts for electrochemical CO(2) reduction (ECR) to value‐added products is important for CO(2) conversion and utilization technologies. In this work, a sulfur‐doped Ni−N−C catalyst is fabricated through a facile ion‐adsorption and pyrolysis treatment. The resulting Ni−NS−C catalyst exhibits higher activity in ECR to CO than S‐free Ni−N−C, yielding a current density of 20.5 mA cm(−2) under −0.80 V versus a reversible hydrogen electrode (vs. RHE) and a maximum CO faradaic efficiency of nearly 100 %. It also displays excellent stability with negligible activity decay after electrocatalysis for 19 h. A combination of experimental investigations and DFT calculations demonstrates that the high activity and selectivity of ECR to CO is due to a synergistic effect of the S and Ni−N( X ) moieties. This work provides insights for the design and synthesis of nonmetal atom‐decorated M−N−C‐based ECR electrocatalysts.