Oxygen‐regulated Ni‐based single‐atom catalysts (SACs) show great potential in accelerating the kinetics of electrocatalytic CO2 reduction reaction (CO2RR). However, it remains a challenge to precisely control the coordination environment of NiO moieties and achieve high activity at high overpotentials. Herein, a facile carbonization coupled oxidation strategy is developed to mass produce NiO clusters‐decorated NiNC SACs that exhibit a high Faradaic efficiency of CO (maximum of 96.5%) over a wide potential range (−0.9 to −1.3 V versus reversible hydrogen electrode) and a high turnover frequency for CO production of 10 120 h−1 even at the high overpotential of 1.19 V. Density functional theory calculations reveal that the highly dispersed NiO clusters induce electron delocalization of active sites and reduce the energy barriers for *COOH intermediates formation from CO2, leading to an enhanced reaction kinetics for CO production. This study opens a new universal pathway for the construction of oxygen‐regulated metal‐based SACs for various catalytic applications.

Electrocatalytic CO2 reduction is a promising strategy for converting the greenhouse gas CO2 into high value-added products and achieving carbon neutrality. The rational design of electrocatalysts for CO2 reduction is of great significance. Defect chemistry is an important category for enhancing the intrinsic catalytic performance of electrocatalysts. Defect engineering breaks the catalytic inertia inherent in perfect structures by imparting unique electronic structures and physicochemical properties to electrocatalysts, thereby improving catalytic activity. Recently, various defective nanomaterials have been studied and show great potential in electrocatalytic CO2 reduction. There is an urgent need to gain insight into the effect of defects on catalytic performance. Here, we summarized the recent research advances on the design of various types of defects, including carbon-based materials (intrinsic defects, heteroatom doping and single-metal-atom sites) and metal compounds (vacancies, grain boundaries, and lattice defects). The major challenges and prospects of defect chemistry in electrocatalytic CO2 reduction are also proposed. This review is expected to be instructive in the development of defect engineering for CO2 reduction catalysts.

The conversion of CO2 to syngas (H2 and CO) via electrochemical reduction has been considered a promising strategy to mitigate the greenhouse effect. However, it is a great challenge to...