Light-driven ammonia synthesis under mild conditions using lithium hydride

Photon-driven chemical processes are usually mediated by oxides, nitrides and sulfides whose photo-conversion efficiency is limited by charge carrier recombination. Here we show that lithium hydride undergoes photolysis upon ultraviolet illumination to yield long-lived photon-generated electrons residing in hydrogen vacancies, known as F centres. We demonstrate that photon-driven dehydrogenation and dark rehydrogenation over lithium hydride can be fulfilled reversibly at room temperature, which is about 600 K lower than the corresponding thermal process. As light-driven F centre generation could provide an alternative approach to charge carrier separation to favour chemical transformations that are kinetically or thermodynamically challenging, we show that light-activated lithium hydride cleaves the N≡N triple bond to form a N-H bond under mild conditions. Co-feeding a N₂/H₂ mixture with low H₂ partial pressure leads to photocatalytic ammonia formation at near ambient conditions. This work provides insights into the development of advanced materials and processes for light harvesting and conversion.