Advancement of Bismuth‐Based Materials for Electrocatalytic and Photo(electro)catalytic Ammonia Synthesis

Ammonia (NH3) plays a vital role in the fertilizer industry, nitrogen‐containing chemical production, and hydrogen storage. The development of electrocatalytic and photo(electro)catalytic nitrogen reduction reaction (NRR) to synthesize NH3 are desirable, which are more environmentally friendly than the conventional Haber–Bosch process. Due to the strong nonpolar bonding of the NN bond, the discovery of efficient catalysts is essential to overcome the high kinetic barrier. Here, bismuth‐based materials that show proven activities for NRR are highlighted. The fundamental knowledge, including thermodynamics, mechanisms, reaction systems, evaluation aspects of NRR, and product quantification, is introduced. Together with scientific reasoning and exhibited activities, the strategies for improving the performance are discussed in detail. Perspective and outlook, as well as the opportunities to further develop bismuth‐based materials for NH3 synthesis, are provided. This review aims to provide a comprehensive understanding of the advancement in this field and serves as a guide for the future design of highly efficient NRR catalysts. This review presents an insightful and comprehensive discussion on the advancement in bismuth‐based materials for photocatalytic, electrocatalytic, and photoelectrocatalytic nitrogen reduction reaction (NRR) to ammonia. The fundamental knowledge, including thermodynamics, mechanisms, reaction systems, evaluation aspects of NRR, and product quantification is introduced. The strategies for improving the performance, together with scientific reasoning and exhibited activities, are discussed in detail.