The Development, Essence and Perspective of Nitrogen Reduction to Ammonia

Abstract Ammonia plays a pivotal role in agriculture and meanwhile holds promising potential as an energy vector for the hydrogen economy, where the nitrogen reduction to ammonia is a critical pathway for achieving sustainable development. Over the past hundred years, ammonia synthesis has undergone several breakthrough developments from Haber‐Bosch process to photo/electro‐catalysis and Li‐mediated strategy, but still faces the challenges of low yield rate, selectivity and efficiency. Therefore, there is a pressing demand to develop efficient and green ammonia synthesis from nitrogen. This review summarizes the development of the nitrogen reduction to ammonia, highlighting six milestones during the whole journey. From the development direction, this work finds and extracts the essence of ammonia synthesis, that is the reaction pathways are affected by the energy barrier of reaction intermediates, which can be altered by proton sources, auxiliaries and catalysts. Then this work discusses the detailed overview of the significant development of proton source, auxiliaries and catalysts. Finally, based on the essence, the possible opportunities of ammonia synthesis from nitrogen reduction are presented, including the design of new ammonia synthesis pathways and efficient catalysts. The deep insight of nitrogen reduction to ammonia will provide a design guidance for efficient ammonia synthesis.