Light-driven hydrogen evolution reactivity of molecular thio-oxomolybdate catalysts
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Heterogeneous molybdenum sulfides are widely used noble metal-free hydrogen evolution reaction (HER) catalysts. Thiomolybdates, their molecular analogues have been developed as viable minimal models to study reactivity at the molecular level. Here, we explore the light-driven HER reactivity and stability of the mixed thio-oxo-molybdate prototype [Mo2O2S6]2− in homogeneous solution. In combination with the photosensitizer [Ru(bpy)3]2+, [Mo2O2S6]2− shows promising HER performance (turnover number TON > 500), as well as strong reactivity dependence on the reaction conditions. Mechanistic experimental studies combined with density functional theory computations reveal complex speciation of the catalyst in solution, as well as light-induced and light-independent reaction pathways for catalyst and photosensitizer which are in line with disulfide-for-solvent ligand exchange reactions. These structure–reactivity insights outline design rules for more robust, solvent-tolerant thiomolybdate HER catalysts.
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Sustainable energy & fuels : interdisciplinary research for the development of sustainable energy technologies, 10, 9, RSC, Cambridge, 2026, https://doi.org/10.1039/D6SE00061D