Defect engineering for enhanced optical and photocatalytic properties of ZnS nanoparticles synthesized by hydrothermal method

Defect engineering is a promising method for improving light harvesting in photocatalytic materials like Zinc sulphide (ZnS). By altering the S/Zn molar ratio during hydrothermal processes, Zn and S defects are successfully introduced into the ZnS crystal. The band structures can be modified by adding defects to the crystal structure of ZnS samples. During the treatment process, defects are formed on the surface. XRD and Raman studies are used for the confirmation of the crystallinity and phase formation of the samples. Using an X-ray peak pattern assessment based on the Debye Scherer model, the Williamson-Hall model, and the size strain plot, it was possible to study the influence of crystal defect on the structural characteristics of ZnS nanoparticles. The band gap (Eg) values were estimated using UV-Vis diffuse spectroscopy (UV-Vis DRS) and found that the Eg is reduced from 3.28 to 3.49 eV by altering the S/Zn molar ratio. Photoluminescence study (PL) shows these ZnS nanoparticles emit violet and blue radiations. In keeping with the results of XRD, TEM demonstrated the nanoscale of the prepared samples and exhibited a small agglomeration of homogenous nanoparticles. Scanning electron microscopy (SEM) was used to examine the surface morphology of the ZnS particles. Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) and X-ray photoelectron spectroscopy (XPS) were used to evaluate and validate the elemental composition. XPS results indicate the presence of defects on the prepared ZnS nanoparticles. For the investigation of vacancy-dependent catalytic activity under exposure to visible light, defective ZnS with different quantities of Zn and S voids are used as catalysts. The lowest S/Zn sample, ZnS0.67 and the highest S/Zn sample, ZnS3, show superior photocatalytic activity.