School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070, China
Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430074, China
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A novel strategy of constructing oxygen-contained amorphous MoSx cocatalyst by electron density manipulation and amorphization is proposed to simultaneously enhance H-adsorption affinity of saturated S and increase unsaturated S number for efficient H2-production performance of CdS photocatalyst. The amorphous MoOSx cocatalyst is modified on the surface of CdS photocatalyst by a one-step photodeposition using (NH4)2[MoO(S4)2] as the precursor and the MoOSx/CdS achieves higher H2-production rate than the CdS, MoSx/CdS, and annealed MoOSx/CdS.
Abstract
Traditional bulk MoS2 as an effective H2-evolution cocatalyst is mainly subjected to the weak hydrogen-adsorption ability of high-porpotion saturated S, resulting in a slow interfacial H2-evolution reaction. In this paper, an efficient strategy for enhancing hydrogen adsorption of saturated S by manipulating electron density through O atoms is proposed to boost photocatalytic performance of CdS. Simultaneously, amorphization of MoS2 can further increase the unsaturated active S sites. Herein, oxygen-contained amorphous MoSx (a-MoOSx) nanoparticles (10–30 nm) were tightly loaded on the CdS surface through a mild photoinduced deposition method by using (NH4)2[MoO(S4)2] solution as the precursor at room temperature. The photocatalytic H2-evolution result showed that the a-MoOSx/CdS performed the superior H2-production activity (382 μmol·h−1, apparent quantum efficiencies (AQE) = 11.83%) with a lot of visual H2 bubbles, which was 54.6, 2.5, and 5.1 times as high as that of CdS, MoSx/CdS, and annealed a-MoOSx/CdS, respectively. Characterizations and density functional theory (DFT) calculations revealed the mechanism of improved H2-evolution activity is that the O heteroatom in amorphous MoOSx can enhance the atomic H-adsorption ability by manipulating the electron density to form electron-deficient S(2−δ)− sites. This study provides a new idea to improve the efficiency and number of H2-evolution active sites for developing efficient cocatalysts in the field of photocatalytic hydrogen evolution.
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