Enabling Sustainable Ammonia Synthesis: From Nitrogen Activation Strategies to Emerging Materials.

Ammonia (NH) is one of the most important precursors of various chemicals and fertilizers. Given that ammonia synthesis via the traditional Haber-Bosch process requires high temperatures and pressures, it is critical to explore effective strategies and catalysts for ammonia synthesis under mild reaction conditions. Although electrocatalysis and photocatalysis can convert N to NH under mild conditions, their efficiencies and production scales are still far from the requirements for industrialization. Thermal catalysis has been proven to be the most direct and effective approach for ammonia synthesis. Over the past few decades, significant efforts have been made to develop novel catalysts capable of nitrogen fixation and ammonia generation via thermal catalytic processes. In parallel with catalyst exploration, new strategies such as self-electron donation, hydride fixation, hydridic hydrogen reduction, and anionic vacancy promotion have also been explored to moderate the operating conditions and improve the catalytic efficiency of ammonia synthesis. In this review, the emergence of new materials and strategies for promoting N activation and NH formation during thermal catalysis is briefly summarized. Moreover, challenges and prospects are proposed for the future development of thermal catalytic ammonia synthesis.