Molecular Design Strategies toward Binary (Ge, Mo, Sn, Ti, V)S ₂ High-Entropy Sulfide

Metal dichalcogenides (MDCs) of the type MS 2 have emerged as promising electrocatalysts for the hydrogen evolution reaction (HER) due to their earth abundance, tunable electronic properties, and distinctive layered structures, which provide a high density of active edge sites and enable efficient interlayer charge transport. However, the controlled incorporation of multiple metal species into a single-phase MS 2 framework remains challenging, particularly in the context of high-entropy design principles. In this study, we present a molecular precursor strategy for the controlled synthesis of tetravalent high-entropy sulfides using metal tert -butyl thiolates of the general formula [M(S t Bu) 4 ] with M = Mo, Sn, Ti, V, and the germanium alkoxide [Ge(OEt) 4 ]. Through partial thiolysis of an equimolar mixture of five precursors resulting in gel formation, a homogeneous network and preorganization of high-entropy elements is formed at the molecular level, allowing precise composition control. Subsequent thermal treatment yielded crystalline MS 2 -type high-entropy sulfides with a uniform elemental distribution. These materials exhibit significantly enhanced electrocatalytic activity toward HER when compared with their lower-entropy analogues. Overall, this study highlights thiolate-based sol–gel chemistry as a versatile and scalable route for synthesizing compositionally complex sulfide electrocatalysts.