Triggering the Channel‐Sulfur Sites in 1T′‐ReS2 Cocatalyst toward Splendid Photocatalytic Hydrogen Generation

Abstract

AbstractElectron density manipulation of active sites in cocatalysts is of great essential to realize the optimal hydrogen adsorption/desorption behavior for constructing high‐efficient H2‐evolution photocatalyst. Herein, a strategy about weakening metal–metal bond strength to directionally optimize the electron density of channel‐sulfur(S) sites in 1T′ Re1−xMoxS2 cocatalyst is clarified to improve their hydrogen adsorption strength (S─H bond) for rapid H2‐production reaction. In this case, the ultrathin Re1−xMoxS2 nanosheet is in situ anchored on the TiO2 surface to form Re1−xMoxS2/TiO2 photocatalyst by a facial molten salt method. Remarkably, numerous visual H2 bubbles are constantly generated on the optimal Re0.92Mo0.08S2/TiO2 sample with a 10.56 mmol g−1 h−1 rate (apparent quantum efficiency is about 50.6%), which is 2.6 times higher than that of traditional ReS2/TiO2 sample. Density functional theory and in situ/ex situ X‐ray photoelectron spectroscopy results collectively demonstrate that the weakened Re─Re bond strength via Mo introduction can induce the formation of unique electron‐deficient channel‐S sites with suitable electron density, which yield thermoneutral S─H bonds to realize superior interfacial H2‐generation performance. This work provides fundamental guidance on purposely optimizing the electronic state of active sites by manipulating the intrinsic bonding structure, which opens an avenue for designing efficacious photocatalytic materials.