Effect of Zr doping and aging on optical and photocatalytic properties of ZnS nanopowder

A facile single step chemical method is reported for the synthesis of Zr doped ZnS nanopowder and its photocatalytic performance has been studied. The average crystallite size of the synthesized powder estimated from X-ray diffraction (XRD) is nearly 1.1 nm. Transmission electron microscopy (TEM) study shows that nanoparticles are agglomerated having a particle size of nearly 10 nm. The optical band gap of ZnS and Zr-doped ZnS, estimated with the help of UV-visible spectroscopy, is 3.7 and 2.9 eV, respectively. Photoluminescence (PL) spectroscopy indicated the role of lattice defects (vacancy, interstitial defects) on optical emission characteristics of doped ZnS samples. The photocatalytic activity of synthesized samples has also been investigated by degrading methylene blue (MB) dye under UV-visible illumination. The degradation quenching has been observed beyond 0.4 mol% doping of Zr in ZnS with maximum efficiency i.e. 80% in 4 h. Thereafter, the effect of aging is monitored for 1.5 months in which the modified emission properties of defect sites modulated the photocatalytic performance of Zr-doped ZnS sample. Further, with the help of various spectroscopic techniques (absorbance, PL and XPS), a mechanism for the photodegradation of MB dye by using Zr-doped ZnS nanopowder has been proposed.