Advances in In Situ Investigations of Heterogeneous Catalytic Ammonia Synthesis

Ammonia is a key “platform” raw chemical for fertilizers and nitrogen-containing chemicals, with a global annual production of ~180 million tons. Recently, ammonia has also come to be seen as an excellent hydrogen-containing liquid promising for long-term, large-scale hydrogen storage and transport. Therefore, artificial N2 fixation, an ammonia synthesis reaction, will play a pivotal role influencing food and energy for human society. Till now, industrial ammonia synthesis has relied on high temperature and high pressure (420~500 °C, 10~15 MPa). Researchers are devoted to developing new catalysts as well as optimizing the traditional Fe-based catalysts continuously. However, the relation between the catalysts’ detailed structure and ammonia production efficiency are not yet fully understood, which is crucial to provide guidance on further improving the efficacy of this importance reaction. Recently, in situ characterization techniques have achieved significant improvements and new understandings have been achieved on the central topic of catalysis. In this review, recent advances in in situ investigations of heterogeneous catalytic ammonia synthesis are summarized and the key results are discussed. In the end, a concluding remark and perspective are proposed, with the hope of inspiring future investigations dedicated to unveiling the principles of designing catalysts for ammonia synthesis.