Controlling Au Photodeposition on Large ZnO Nanoparticles

This study investigated how to control the rate of photoreduction of metastable AuC1(2)(-) at the solid-solution interface of large ZnO nanoparticle's (NPs) (50-100 nm size). Band-gap photoexcitation of electronic charge in ZnO by 370 nm UV light yielded Au NP deposition and the formation of ZnO-Au NP hybrids. Au NP growth was observed to be nonepitaXial, and the patterns of Au photodeposition onto ZnO NPs observed by high-resolution transmission electron microscopy were consistent with reduction of AuCl2- at ZnO facet edges and corner sites. Au NP photodeposition was effective in the presence of labile oleylamine ligands attached to the ZnO surface; however, when a strong-binding dodecanethiol ligand coated the surface, photodeposition was quenched. Rates of interfacial electron transfer at the ZnQsolutioo' interface were adjusted by changing the solvent, and these rates were observed to, strongly depend on the solvent's permittivity,(epsilon) and viscosity. From measurements of electron transfer from ZnO to the organic dye toluidine blue at the ZnO-solution interface, it was confirmed that low e solvent mixtures (epsilon approximate to 9.5) possessed markedly higher rates of photocatalytic interfacial electron transfer (similar to 3.2 X 10(4) electrons particle(-1) s(-1)) compared to solvent mixtures with high a.(e = 29.9, similar to 1.9 X 10(4) electrons-particle(-1)s(-1)). Dissolved oxygen content in the solvent and the exposure time Of ZnO to band-gap, near-UV photoexcitation were also identified as factors that strongly affected Au photodeposition behavior. Production of Au clusters was favored under conditions that caused electron accumulation in the ZnQ-Au NP hybrid: Under conditions where electron discharge was rapid (such as' in low e solvents), AuCl2- precursor -ions photoreduced at ZnO surfaces in less than 5 s, leading to deposition of several small, isolated similar to 6 nm Au NP on the ZnO host instead.