Nickel-decorated ZnO nanoparticles for effective solar reduction of hexavalent chromium and removal of selected pharmaceuticals

• The optimal metal for decorating surface of ZnO was shown to be nickel. • The optimal grafting concentration was 0.5 wt% • The clusters were below 2 nm in size and were identified as oxo-clusters. • The improved reduction activity was due to the co-catalyst nature of nickel clusters. • Such material was capable of being immobilized onto glass beads and used in flow through mode to purify water under visible light. The efficient visible light driven photocatalytic reduction of hexavalent chromium, Cr(VI) was demonstrated using ZnO nanoparticles (NPs) decorated with oxo-clusters of transition metals. The ZnO NPs were synthesized by a facile one-pot solvothermal synthesis followed by a fast microwave-assisted (MW) grafting of transition metals on the surface of NPs. Nickel was found to be the most active transition metal for photocatalytic activity as demonstrated by reduction of Cr(VI) to Cr(III). The optimally grafted samples contained 0.5 wt% Ni and increased photocatalytic activity by almost one-fold. The oxo-clusters did not enter the lattice of ZnO but rather resided on the surface and their efficient bonding to the ZnO surface was proved by Raman, TEM and X-Ray absorption techniques. Influence of MW power was studied and shown that excessive power load leads to formation of elongated structures of ZnO which decreases the photocatalytic activity. It was demonstrated by measuring fluorescent radical products that electrons, efficiently transferred via oxygen, were the main active species in combination with the unchanged oxidation power of holes and • OH in the grafted samples. The applicability of the materials was tested in immobilized plug flow photoreactor system degrading five pharmaceuticals simultaneously where their long-term use was shown.