Exclusive Ni–N<sub>4</sub> Sites Realize Near-Unity CO Selectivity for Electrochemical CO<sub>2</sub> Reduction

Electrochemical reduction of carbon dioxide (CO<sub>2</sub>) to value-added carbon products is a promising approach to reduce CO<sub>2</sub> levels and mitigate the energy crisis. However, poor product selectivity is still a major obstacle to the development of CO<sub>2</sub> reduction. Here we demonstrate exclusive Ni–N<sub>4</sub> sites through a topo-chemical transformation strategy, bringing unprecedentedly high activity and selectivity for CO<sub>2</sub> reduction. Topo-chemical transformation by carbon layer coating successfully ensures preservation of the Ni–N<sub>4</sub> structure to a maximum extent and avoids the agglomeration of Ni atoms to particles, providing abundant active sites for the catalytic reaction. The Ni–N<sub>4</sub> structure exhibits excellent activity for electrochemical reduction of CO<sub>2</sub> with particularly high selectivity, achieving high faradaic efficiency over 90% for CO in the potential range from −0.5 to −0.9 V and gives a maximum faradaic efficiency of 99% at −0.81 V with a current density of 28.6 mA cm<sup>–2</sup>. We anticipate exclusive catalytic sites will shed new light on the design of high-efficiency electrocatalysts for CO<sub>2</sub> reduction.