Superior visible-light absorbing Ag@ZnO nanorods hybrid photocatalyst for efficient decomposition of commercial pharmaceuticals tetracycline and amoxicillin

Abstract

This work assesses the role of the noble metal silver in the visible-light sensitization of UV-active ZnO by introducing a localized plasmonic resonance effect and enhancing the spatial charge carrier separation. We herein synthesize ZnO nanorods via a solvothermal approach, yielding nanorods of length and diameter 1.356 ± 0.619 μm and 120.56 ± 25.09 nm, respectively. Silver nanoparticles are reduced on the surface of ZnO nanorods via the photodeposition route. XRD spectra reveal a high crystallinity and wurtzite-type structure for ZnO with new peaks for cubic phase Ag upon Ag-loading. The diffraction peaks shift upon Ag modification, indicating partial incorporation of Ag into the ZnO lattice. Further, upon Ag-decoration, a slight increase in dislocation density and micro strain is obtained, which could suppress the recombination rate of charge carriers. The DRS spectra reveal a band gap contraction of materials from 3.19 to 2.98 eV with increasing Ag density. The PL spectra confirmed that the optimum Ag concentration of 3 wt% is proficient in harvesting visible light towards high photocatalytic degradation efficiencies of tetracycline (92.1 %) and amoxicillin (76.4 %) in 90 min as compared to 49.4 % and 38 % over pristine ZnO nanorods. TOC studies reveal only partial mineralization of ∼42.7 % (tetracycline) and ∼31.3 % (amoxicillin) due to the formation of reaction intermediates identified by HR-MS chromatograms. In addition, degradation pathways are proposed through the fragments at different m/z ratios.