title: Controlling Au Photodeposition on Large ZnO Nanoparticles.
abstract: This study investigated how to control the rate of photoreduction of metastable AuCl2(-) at the solid-solution interface of large ZnO nanoparticles (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 ZnO-solution interface were adjusted by changing the solvent, and these rates were observed to strongly depend on the solvent's permittivity (ε) 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 ε solvent mixtures (ε ≈ 9.5) possessed markedly higher rates of photocatalytic interfacial electron transfer (∼3.2 × 10(4) electrons·particle(-1)·s(-1)) compared to solvent mixtures with high ε (ε = 29.9, ∼1.9 × 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 ZnO-Au NP hybrid. Under conditions where electron discharge was rapid (such as in low ε solvents), AuCl2(-) precursor ions photoreduced at ZnO surfaces in less than 5 s, leading to deposition of several small, isolated ∼6 nm Au NP on the ZnO host instead.
authors.affiliation: School of Chemistry, Physics and Mechanical Engineering, Science and Engineering Faculty, Queensland University of Technology , Brisbane, Queensland 4000, Australia.
authors.forename: Joseph F S
authors.initials: JF
authors.lastname: Fernando
authors.affiliation: School of Chemistry, Physics and Mechanical Engineering, Science and Engineering Faculty, Queensland University of Technology , Brisbane, Queensland 4000, Australia.
authors.forename: Matthew P
authors.initials: MP
authors.lastname: Shortell
authors.affiliation: Centre for Advanced Imaging, University of Queensland , Brisbane, Queensland 4072, Australia.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Noble
authors.affiliation: Centre for Advanced Imaging, University of Queensland , Brisbane, Queensland 4072, Australia.
authors.forename: Jeffrey R
authors.initials: JR
authors.lastname: Harmer
authors.affiliation: School of Chemistry, Physics and Mechanical Engineering, Science and Engineering Faculty, Queensland University of Technology , Brisbane, Queensland 4000, Australia.
authors.forename: Esa A
authors.initials: EA
authors.lastname: Jaatinen
authors.affiliation: School of Chemistry, Physics and Mechanical Engineering, Science and Engineering Faculty, Queensland University of Technology , Brisbane, Queensland 4000, Australia.
authors.forename: Eric R
authors.initials: ER
authors.lastname: Waclawik
keywords: Au; Au−ZnO nanoparticle hybrids; ZnO; interfacial electron transfer; nanoparticle composites; photocatalysis; photochemical reduction; photodeposition