Defect Engineering in Bi‐based Photo/electrocatalysts for Nitrogen Reduction to Ammonia

Main group Bi‐based materials have gained popularity as N2 reduction reaction (NRR) photo/electrocatalysts due to their ability to inhibit competitive H2 evolution reactions (HER) and the unique N2 adsorption activities. The introduction of defects in Bi‐based catalysts represents a highly effective strategy for enhancing light absorption, promoting efficient separation of photogenerated carriers, optimizing the activity of free radicals, regulating electronic structure, and improving catalytic performance. In this review, we outline the various applications of state of the defect engineering in Bi‐based catalysts and elucidate the impact of vacancies on NRR performance. In particular, the types of defects, methods of defects tailoring, advanced characterization techniques, as well as the Bi‐based catalysts with abundant defects and their corresponding catalytic behavior in NRR were elucidated in detail. Finally, the main challenges and opportunities for future development of defective Bi‐based NRR catalysts are discussed, which provides a comprehensive theoretical guidance for this field.