Photocatalysis with Pt-Au-ZnO and Au-ZnO Hybrids: Effect of Charge Accumulation and Discharge Properties of Metal Nanoparticles.

Metal-semiconductor hybrid nanomaterials are becoming increasingly popular for photocatalytic degradation of organic pollutants. Herein, a seed-assisted photodeposition approach is put forward for the site-specific growth of Pt on Au-ZnO particles (Pt-Au-ZnO). A similar approach was also utilized to enlarge the Au nanoparticles at epitaxial Au-ZnO particles (Au@Au-ZnO). An epitaxial connection at the Au-ZnO interface was found to be critical for the site-specific deposition of Pt or Au. Light on-off photocatalysis tests, utilizing a thiazine dye (toluidine blue) as a model organic compound, were conducted and confirmed the superior photodegradation properties of Pt-Au-ZnO hybrids compared to Au-ZnO. In contrast, Au-ZnO type hybrids were more effective toward photoreduction of toluidine blue to leuco-toluidine blue. It was deemed that photoexcited electrons of Au-ZnO (Au, ∼5 nm) possessed high reducing power owing to electron accumulation and negative shift in Fermi level/redox potential; however, exciton recombination due to possible Fermi-level equilibration slowed down the complete degradation of toluidine blue. In the case of Au@Au-ZnO (Au, ∼15 nm), the photodegradation efficiency was enhanced and the photoreduction rate reduced compared to Au-ZnO. Pt-Au-ZnO hybrids showed better photodegradation and mineralization properties compared to both Au-ZnO and Au@Au-ZnO owing to a fast electron discharge (i.e. better electron-hole seperation). However, photoexcited electrons lacked the reducing power for the photoreduction of toluidine blue. The ultimate photodegradation efficiencies of Pt-Au-ZnO, Au@Au-ZnO, and Au-ZnO were 84, 66, and 39%, respectively. In the interest of effective metal-semiconductor type photocatalysts, the present study points out the importance of choosing the right metal, depending on whether a photoreduction and/or photodegradation process is desired.

Multi-angle fluorometer technique for the determination of absorption and scattering coefficients of subwavelength nanoparticles.

A thorough analysis of the resonance light scattering (RLS) technique for quantitative scattering measurements of subwavelength nanoparticles is reported. The systematic error associated with using a measurement at a single angle to represent all of the scattered light is investigated. In-depth analysis of the reference material was performed to identify and minimize the error associated with the reference material. Semiconductor ZnO nanobullets and spherical Au nanoparticles of various sizes were used to verify the approach. A simple and inexpensive modification to standard fluorometers is demonstrated using a glass prism allowing scattering measurements in the slightly forward and backwards directions. This allows quantification of the systematic error associated with RLS which is consistently overlooked.

Controlling Au Photodeposition on Large ZnO Nanoparticles.

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.

Using pulse transit delay in Z-scan to discriminate between excited-state absorption and other nonlinear processes in ZnO nanocones.

We report a new approach that uses the single beam Z-scan technique, to discriminate between excited state absorption (ESA) and two and three photon nonlinear absorption. By measuring the apparent delay or advance of the pulse in reaching the detector, the nonlinear absorption can be unambiguously identified as either instantaneous or transient. The simple method does not require a large range of input fluences or sophisticated pulse-probe experimental apparatus. The technique is easily extended to any absorption process dependent on pulse width and to nonlinear refraction measurements. We demonstrate in particular, that the large nonlinear absorption in ZnO nanocones when exposed to nanosecond 532 nm pulses, is due mostly to ESA, not pure two-photon absorption.

Accurate measurement of the molecular thickness of thin organic shells on small inorganic cores using dynamic light scattering.

Dynamic light scattering (DLS) has become a primary nanoparticle characterization technique with applications from material characterization to biological and environmental detection. With the expansion in DLS use from homogeneous spheres to more complicated nanostructures comes a decrease in accuracy. Much research has been performed to develop different diffusion models that account for the vastly different structures, but little attention has been given to the effect on the light scattering properties in relation to DLS. In this work, small (core size < 5 nm) core-shell nanoparticles were used as a case study to measure the capping thickness of a layer of dodecanethiol (DDT) on Au and ZnO nanoparticles by DLS. We find that the DDT shell has very little effect on the scattering properties of the inorganic core and, hence, can be ignored to a first approximation. However, this results in conventional DLS analysis overestimating the hydrodynamic size in the volume- and number-weighted distributions. With the introduction of a simple correction formula that more accurately yields hydrodynamic size distributions, a more precise determination of the molecular shell thickness is obtained. With this correction, the measured thickness of the DDT shell was found to be 7.3 ± 0.3 Å, much less than the extended chain length of 16 Å. This organic layer thickness suggests that, on small nanoparticles, the DDT monolayer adopts a compact disordered structure rather than an open ordered structure on both ZnO and Au nanoparticle surfaces. These observations are in agreement with published molecular dynamics results.

Formation of one-dimensional capped ZnO nanoparticle assemblies at the air/water interface.

The self-assembling behavior and microscopic structure of zinc oxide nanoparticle Langmuir-Blodgett monolayer films were investigated for the case of zinc oxide nanoparticles coated with a hydrophobic layer of dodecanethiol. Evolution of nanoparticle film structure as a function of surface pressure (π) at the air-water interface was monitored in situ using Brewster's angle microscopy, where it was determined that π = 16 mN/m produced near-defect-free monolayer films. Transmission electron micrographs of drop-cast and Langmuir-Schaefer deposited films of the dodecanethiol-coated zinc oxide nanoparticles revealed that the nanoparticle preparation method yielded a microscopic structure that consisted of one-dimensional rodlike assemblies of nanoparticles with typical dimensions of 25 × 400 nm, encased in the organic dodecanethiol layer. These nanoparticle-containing rodlike micelles were aligned into ordered arrangements of parallel rods using the Langmuir-Blodgett technique.