Optimizing Atomic Hydrogen Desorption of Sulfur-Rich NiS_{1+ x} Cocatalyst for Boosting Photocatalytic H₂ Evolution

Low-cost transition-metal chalcogenides (MS_x ) are demonstrated to be potential candidate cocatalyst for photocatalytic H₂ generation. However, their H₂ -generation performance is limited by insufficient quantities of exposed sulfur (S) sites and their strong bonding with adsorbed hydrogen atoms (SH_ads ). To address these issues, an efficient coupling strategy of active-site-enriched regulation and electronic structure modification of active S sites is developed by rational design of core-shell Au@NiS_{1+ x} nanostructured cocatalyst. In this case, the Au@NiS_{1+ x} cocatalyst can be skillfully fabricated to synthesize the Au@NiS_{1+ x} modified TiO₂ (denoted as TiO₂ /Au@NiS_{1+ x} ) by a two-step route. Photocatalytic experiments exhibit that the resulting TiO₂ /Au@NiS_{1+ x} (1.7:1.3) displays a boosted H₂ -generation rate of 9616 µmol h^-1 g^-1 with an apparent quantum efficiency of 46.0%  at 365 nm, which is 2.9 and 1.7 times the rate over TiO₂ /NiS_{1+ x} and TiO₂ /Au, respectively. In situ/ex situ XPS characterization and density functional theory calculations reveal that the free-electrons of Au can transfer to sulfur-enriched NiS_{1+ x} to induce the generation of electron-enriched S^{δ -} active centers, which boosts the desorption of H_ads for rapid hydrogen formation via weakening the strong SH_ads bonds. Hence, an electron-enriched S^{δ -} -mediated mechanism is proposed. This work delivers a universal strategy for simultaneously increasing the active site number and optimizing the binding strength between the active sites and hydrogen adsorbates.