Formation of polyaniline/Pt nanoparticle composite films and their electrocatalytic properties

Polyaniline (PANI) thin films modified with platinum nanoparticles have been prepared by several methods, characterised and assessed in terms of electrocatalytic properties. These composite materials have been prepared by the in situ reduction of a platinum salt (K2PtCl4) by PANI, in a variety of solvents, resulting in the formation of platinum nanoparticles and clusters of different sizes. The further deposition of platinum clusters at spin cast thin films of PANI/Pt composites from a neutral aqueous solution of K2PtCl4 has also been demonstrated. Thin-film electrodes prepared from these materials have been investigated for their electrocatalytic activity by studying hydrazine oxidation and dichromate reduction. The properties of the composite materials have been determined using UV–visible spectroscopy, atomic force microscopy and transmission electron microscopy. The nature of the material formed is strongly dependent on the solvent used to dissolve PANI, the method of preparation of the PANI/Pt solution and the composition of the spin cast thin film before subsequent deposition of platinum from the aqueous solution of K2PtCl4.

Small gold nanoparticles as crystallization "catalysts": Effect of seed size and concentration on Au-ZnO hetero nanoparticles

This work reports the effect of seed nanoparticle size and concentration effects on heterogeneous crystal nucleation and growth in colloidal suspensions. We examined these effects in the Au nanoparticle-seeded growth of Au-ZnO hetero-nanocrystals under synthesis conditions that generate hexagonal, cone-shaped ZnO nanocrystals. It was observed that small (~ 4 nm) Au seed nanoparticles form one-to-one Au-ZnO hetero dimers and that Au nanoparticle seeds of this size can also act as crystallization ‘catalysts’ that readily promote the nucleation and growth of ZnO nanocrystals. Larger seed nanoparticles (~9 nm, ~ 11 nm) provided multiple, stable ZnO-nucleation sites, generating multi-crystalline hetero trimers, tetramers and oligomers.

Self-organized Au nanoarrays on vertical graphenes : an advanced three-dimensional sensing platform

A three-dimensional surface enhanced Raman scattering (SERS)/plasmonic sensing platform based on plasma-enabled, catalyst-free, few-layer vertical graphenes decorated with self-organized Au nanoparticle arrays is demonstrated. This platform is viable for multiple species detection and overcomes several limitations of two-dimensional sensors.

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 materials 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. By introducing 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.

Understanding the enhancement in photoelectrochemical properties of photocatalytically prepared TiO2-reduced graphene oxide composite

Solution-phase photocatalytic reduction of graphene oxide to reduced graphene oxide (RGO) by titanium dioxide (TiO2) nanoparticles produces an RGO-TiO2 composite that possesses enhanced charge transport properties beyond those of pure TiO2 nanoparticle films. These composite films exhibit electron lifetimes up to four times longer than that of intrinsic TiO2 films due to RGO acting as a highly conducting intraparticle charge transport network within the film. The intrinsic UV-active charge generation (photocurrent) of pure TiO2 was enhanced by a factor of 10 by incorporating RGO; we attribute this to both the highly conductive nature of the RGO and to improved charge collection facilitated by the intimate contact between RGO and the TiO2, uniquely afforded by the solution-phase photocatalytic reduction method. Integrating RGO into nanoparticle films using this technique should improve the performance of photovoltaic devices that utilize nanoparticle films, such as dye-sensitized and quantum-dot-sensitized solar cells.

Fabrication of metal-nanoparticle-modified semiconducting copper--and silver--TCNQ materials as substrates for the reduction of chromium (VI) using thiosulfate ions at ambient temperature

The formation of readily recoverable and reusable organic semiconducting Cu- and AgTCNQ (TCNQ=7,7,8,8-tetracyanoquinodimethane) microstructures decorated with Pt and Pd metallic nanoparticles is described for the effective reduction of CrVI ions in aqueous solution at room temperature using both formic acid and an environmentally friendly thiosulfate reductant. The M-TCNQ (M=metal) materials were formed by electrocrystallisation onto a glassy carbon surface followed by galvanic replacement in the presence of H2PtCl6 or PdCl2 to form the composite material. It was found that loading of the surface with nanoparticles could easily be controlled by changing the metal salt concentration. Significantly, the M-TCNQ substrates facilitated the formation of well-isolated metal nanoparticles on their surfaces under appropriate galvanic replacement conditions. The semiconductor–metal nanoparticle combination was also found to be critical to the catalyst performance, wherein the best-performing material was CuTCNQ modified by well-isolated Pt nanoparticles with both formic acid and thiosulfate ions as the reductant.

Visible light enhanced oxidant free dehydrogenation of aromatic alcohols using Au-Pd alloy nanoparticle catalysts

We find that visible light irradiation of gold–palladium alloy nanoparticles supported on photocatalytically inert ZrO2 significantly enhances their catalytic activity for oxidant-free dehydrogenation of aromatic alcohols to the corresponding aldehydes at ambient temperatures. Dehydrogenation is also the dominant process in the selective oxidation of the alcohols to the corresponding aldehydes with molecular oxygen. The alloy nanoparticles strongly absorb light and exhibit superior catalytic and photocatalytic activity when compared to either pure palladium or gold nanoparticles. Analysis with a free electron gas model for the bulk alloy structure reveals that the alloying increases the surface charge heterogeneity on the alloy particle surface, which enhances the interaction between the alcohol molecules and the metal NPs. The increased surface charge heterogeneity of the alloy particles is confirmed with density function theory applied to small alloy clusters. Optimal catalytic activity was observed with a Au : Pd molar ratio of 1 : 186, which is in good agreement with the theoretical analysis. The rate-determining step of the dehydrogenation is hydrogen abstraction. The conduction electrons of the nanoparticles are photo-excited by the incident light giving them the necessary energy to be injected into the adsorbed alcohol molecules, promoting the hydrogen abstraction. The strong chemical adsorption of alcohol molecules facilitates this electron transfer. The results show that the alloy nanoparticles efficiently couple thermal and photonic energy sources to drive the dehydrogenation. These findings provide useful insight into the design of catalysts that utilize light for various organic syntheses at ambient temperatures.

Au-Pd alloy nanoparticle catalyzed selective oxidation of benzyl alcohol and tandem synthesis of imines at ambient conditions

Alloy nanoparticles (NPs) of gold and palladium on ZrO2 support (Au–Pd@ZrO2) were found to be highly active in oxidation of benzyl alcohols and can be used for the tandem synthesis of imines from benzyl alcohols and amines via a one-pot, two-step process at mild reaction conditions. The first step of the process is oxidation of benzyl alcohol to benzaldehyde, excellent yields were achieved after 7 h reaction at 40 °C without addition of any base. In the second step, aniline was introduced into the reaction system to produced N-benzylideneaniline. The benzaldehyde obtained in the first step was completely consumed within 1 h. A range of benzyl alcohols and amines were investigated for the general applicability of the Au–Pd alloy catalysts. It is found that the performance of the catalysts depends on the Au–Pd metal contents and composition. The optimal catalyst is 3.0 wt% Au–Pd@ZrO2 with a Au:Pd molar ratio 1:1. The alloy NP catalyst exhibited superior catalytic properties to pure AuNP or PdNP because the surface of alloy NPs has higher charge heterogeneity than that of pure metal NPs according to simulation of density function theory (DFT)