Pyrrolic N‐Stabilized Monovalent Ni Single‐Atom Electrocatalyst for Efficient CO 2 Reduction: Identifying the Role of Pyrrolic–N and Synergistic Electrocatalysis

Engineering the electronic structure of metal, N‐doped carbon catalysts is a potential strategy for increasing the activity and selectivity of CO 2 electroreduction reaction (CO 2 RR). However, establishing a definitive link between structure and performance is extremely difficult due to constrained synthesis approaches that lack the ability to precisely control the specific local environment of MNC catalysts. Herein, a soft‐template aided technique is developed for the first time to synthesize pyrrolic N 4 Ni sites coupled with varying N‐type defects to synergistically enhance the CO 2 RR performance. The optimal catalyst helps attain a CO Faradaic efficiency of 94% at a low potential of −0.6 V and CO partial current density of 59.6 mA cm −2 at −1 V. Results of controlled experimental investigations indicate that the synergy between NiN 4 and metal free defect sites can effectively promote the CO 2 RR activity. Theoretical calculations revealed that the pyrrolic N coordinated NiN 4 sites and C atoms next to pyrrolic N (pyrrolic NC) have a lower energy barrier for the formation of COOH* intermediate and optimum CO* binding energy. The pyrrolic N regulate the electronic structure of the catalyst, resulting in lower CO 2 adsorption energy and higher intrinsic catalytic activity.