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Electrochemical nitrogen reduction reaction (NRR) to ammonia (NH3) is considered as a promising alternative for the traditional Haber-Bosch process due to its lower energy consumption under ambient conditions. However, major obstacles still remain in improving the NRR activity and selectivity, mainly arising from the chemical inertness of N2 molecule, the sluggish reaction kinetics, and the competition between hydrogen evolution reaction (HER) and NRR. The defect engineering can regulate and modify the local coordination environment of electrocatalysts, which could be considered as effective strategies to promote the intrinsic activity. In this review, recent advances on defect engineering of nanostructured electrocatalysts for NRR, including vacancy, doping, single atom, amorphization and high-index facet, are summarized. Particularly, the strategies of defect engineering, the reaction mechanisms, and the reliable NH3 detection methods, are systematically discussed. Finally, the opportunities and challenges towards the rational design and synthesis of advanced electrocatalysts with controlled defects for NRR are proposed.
Recent advances on defect engineering for nitrogen reduction reaction (NRR), including vacancy, doping, single atom, amorphization and high-index facet, are summarized. [Display omitted]
•The recent achievements of NRR electrocatalysts with various defect structure have been summarized.•The principles of each defect engineering strategy and the existing problems have been analyzed in detail.•The reaction mechanisms for the reduction of N2 to NH3 on the heterogeneous surfaces have been systematically disscussed.•The methods of ammonia detection and the ways to improve the reliability of nitrogen reduction research have been disscussed.