Solid-state synthesis of ZnS/ZnO nanocomposites and their decoration with NiS cocatalyst for photocatalytic hydrogen production

Abstract

Herein was demonstrated the facile solid-state synthesis of ZnS/ZnO nanocomposites using planetary ball milling followed by subsequent thermal treatment. X-ray diffraction analysis has shown that the ZnS/ZnO products are nanocrystalline with an estimated crystallite size of less than 60 nm. A transmission electron microscope has demonstrated the presence of spherical heterostructures and core-shell structured ZnS/ZnO nanocomposites with the size being 40–80 nm in diameter. Fourier transform infrared spectroscopy analysis confirmed the presence of Zn–O and Zn–S bonds. The formation of a thin boundary between the ZnS and ZnO phases, where the sulfur oxidation state varies from −2 to +6, was determined by X-ray photoelectron spectroscopy. Degradation of methylene blue and Orange II organic dyes was used to assess the photocatalytic activity of ZnS/ZnO nanocomposites, and the nanocomposites of ZnS/ZnO, with a mass ratio of ∼1:1, demonstrated the highest visible light photocatalytic activity. For photocatalytic hydrogen production experiments, the surface of ZnS/ZnO nanocomposites was in situ decorated with NiS nanoparticles, where the mass content of NiS was 1.5%. The presence of NiS cocatalyst promotes the separation and transfer of photogenerated charges, thereby increasing the photocatalytic activity of ZnS/ZnO nanocomposites during hydrogen generation. The apparent quantum efficiency of photocatalytic hydrogen generation using ZnS/ZnO-3h-NiS photocatalyst was equal to 1.13%. This contribution shows the possibility to prepare nano-structured photocatalysts via mechanochemistry.