Monodispersed core/shell nanospheres of ZnS/NiO with enhanced H₂ generation and quantum efficiency at versatile photocatalytic conditions

This investigation is first to elucidate the synthesis of mono-dispersed ZnS/NiO-core/shell nanostructures with a uniform thin layer of NiO-shell on the ZnS-nanospheres as a core under controlled thermal treatments. NiO-shell thickness varied to 8.2, 12.4, 18.2, and 24.2 nm, while the ZnS-core diameter remained stable about 96 ± 6 nm. The crystalline phase and core/shell structure of the materials were confirmed using XRD and HRTEM techniques, respectively. Optical properties through UV–vis spectroscopy analysis revealed the manifestation of red-shift in the absorption spectrum of core/shell materials, while the XPS analysis of elements elucidated their stable oxidation states in ZnS/NiO core/shell structure. The optimized ZnS/NiO-core/shell showed 1.42 times higher H₂ generation (162.1 mmol h⁻¹ g⁻¹_cat) than the pristine ZnS-core (113.2 mmol h⁻¹ g⁻¹_cat), and 64.5 times higher than the pristine NiO-shell (2.5 mmol h⁻¹ g⁻¹_cat). The quantum efficiency at wavelengths of 420, 365 nm, and 1.5 G air mass filters was found to be 13.5%, 25.0%, and 45.3%, respectively. Water splitting experiments was also performed without addition of any additives, which showed enhanced H₂ gas evolution of 1.6 mmol h⁻¹ g⁻¹_cat under the sunlight illumination. Photoelectrochemical measurements revealed the stable photocurrent density and minimized charge recombination in the system. The performed recyclability and reusability tests for five recycles demonstrated the excellent stability of the developed photocatalysts.