Efficient and Stable Hydrogen Evolution from HI Splitting Using a Robust 2D Tin-Iodide Perovskite

Abstract

Photocatalytic hydrogen (H2) production with 2D Ruddlesden–Popper tin-iodide perovskites has recently emerged as a promising route toward sustainable solar-to-fuel conversion. However, a major limitation of these systems lies in their rapid degradation caused by tin and iodide oxidation. In the present study, we report the synthesis of 4-fluorophenethylammonium tin-iodide (4FPSI) perovskite microcrystals in a mixture of hydroiodic acid (HI) and H2O, which exhibit remarkable long-term photostability and sustained photocatalytic H2 production via HI splitting. Intermittent light irradiation was shown to further boost H2 production by promoting efficient charge separation and suppressing the accumulation of trapped charge carriers that drive recombination. Notably, reused and aged materials showed enhanced photocatalytic performance, which theoretical simulations attributed to surface reconstruction that exposes additional tin catalytic active sites. The samples that underwent degradation after multiple photocatalytic tests could be recovered through a simple chemical treatment and restore the H2 production capability. Together, these findings highlight tin-iodide perovskites as highly promising photocatalysts for solar H2 production, combining durability, recyclability, and facile recovery strategies to simultaneously advance all key performance metrics.