High‐Throughput Screening of Bicationic Redox Materials for Chemical Looping Ammonia Synthesis

Ammonia recently has gained increasing attention as a carrier for the efficient and safe usage of hydrogen to further advance the hydrogen economy. However, there is a pressing need to develop new ammonia synthesis techniques to overcome the problem of intense energy consumption associated with the widely used Haber–Bosch process. Chemical looping ammonia synthesis (CLAS) is a promising approach to tackle this problem, but the ideal redox materials to drive these chemical looping processes are yet to be discovered. Here, by mining the well‐established MP database, the reaction free energies for CLAS involving 1699 bicationic inorganic redox pairs are screened to comprehensively investigate their potentials as efficient redox materials in four different CLAS schemes. A state‐of‐the‐art machine learning strategy is further deployed to significantly widen the chemical space for discovering the promising redox materials from more than half a million candidates. Most importantly, using the three‐step H(2)O‐CL as an example, a new metric is introduced to determine bicationic redox pairs that are “cooperatively enhanced” compared to their corresponding monocationic counterparts. It is found that bicationic compounds containing a combination of alkali/alkaline‐earth metals and transition metal (TM)/post‐TM/metalloid elements are compounds that are particularly promising in this respect.