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The fabricated VS 4 /Ni 3 S 2 /NF NBs was prepared by self-templated strategy, with exposed abundant hetero-interfaces and high active disulfide (S 2 2-) sites. The density functional theory revealed the reversible conversion catalysis mechanism of bridge S 2 2- during HER process, jointly promoting the HER performance. [Display omitted] • A novel VS 4 nanoparticle decorated Ni 3 S 2 nanobelt array was synthesized via one-step organic ligand-assisted solvothermal method. • The abundant disulfide (S 2 2-) moieties grafted on the hetero-interfaces of VS 4 /Ni 3 S 2 led to strong electronic interaction and promote the chemisorption of H-containing intermediates. • The density functional theory reveals the reversible conversion catalysis mechanism about disulfide (S 2 2-) sites during HER process. • The findings provide fresh insights for developing potential polysulfides as high-performance hydrogen-evolving electrocatalysts from water splitting. Elaborate and rational design of cost-effective and high-efficiency non-noble metal electrocatalysts for pushing forward the sustainable hydrogen fuel production is of great significance. Herein, a novel VS 4 nanoparticle decorated Ni 3 S 2 nanobelt array in-situ grown on nickel foam (VS 4 /Ni 3 S 2 /NF NBs) was prepared by a self-templated synthesis strategy. Benefitting from the unique nanobelt array structure, abundant highly active bridge S 2 2- sites and strong electronic interaction between VS 4 and Ni 3 S 2 on the heterointerface, the integrated VS 4 /Ni 3 S 2 /NF NBs exhibited excellent electrocatalytic hydrogen evolution activity and robust stability. The density functional theory (DFT) further revealed the reversible conversion catalysis mechanism of bridging S 2 2- sites in VS 4 /Ni 3 S 2 /NF NBs during HER process. Notably, bidentate bridging S S bonds as the predominant catalytically active centers can spontaneously open once H adsorbed its surface, leading to the aggregation of negative charges on S atoms and thus facilitating the generation of H* intermediates, and spontaneously close when H* desorption is going to form H 2. Our work provides fresh insights for developing potential polysulfides as high-performance hydrogen-evolving electrocatalysts for prospective clean energy production from water splitting. [ABSTRACT FROM AUTHOR]