Abstract
Lithium hydride (LiH), a saline hydride with a hydrogen density of 12.6 wt %, is highly thermostable, which hinders its extensive application in hydrogen storage. In this study, we demonstrate a distinct photodecomposition of LiH under ambient conditions. Ultraviolet–visible (UV–vis) illumination induces hydrogen release and creates surface hydrogen vacancies on LiH. The subsequent H– migration enables hydrogen desorption and the accumulation of vacancies at the subsurface, resulting in the generation of metallic Li clusters. Rehydrogenation, on the contrary, can be charged under UV–vis illumination in 1 bar H2. Such phenomena show that the thermodynamic and kinetic limits in the re/dehydrogenation of LiH can be broken under illumination, which allows hydrogen storage over the LiH surface at temperatures ∼600 K lower than those of the corresponding thermal process. This work provides new insights into the interaction of semiconducting hydrides and photons and opens an avenue for the development and optimization of materials for hydrogen storage and related photodriven reactions.