Ramchandra Tiruvalam

Solvent-Free Oxidation of Primary Carbon-Hydrogen Bonds in Toluene Using Au-Pd Alloy Nanoparticles

A gold- and palladium-based catalyst can be used to oxidize toluene and form a commercially useful ester. Selective oxidation of primary carbon-hydrogen bonds with oxygen is of crucial importance for the sustainable exploitation of available feedstocks. To date, heterogeneous catalysts have either shown low activity and/or selectivity or have required activated oxygen donors. We report here that supported gold-palladium (Au-Pd) nanoparticles on carbon or TiO2 are active for the oxidation of the primary carbon-hydrogen bonds in toluene and related molecules, giving high selectivities to benzyl benzoate under mild solvent-free conditions. Differences between the catalytic activity of the Au-Pd nanoparticles on carbon and TiO2 supports are rationalized in terms of the particle/support wetting behavior and the availability of exposed corner/edge sites.

Facile removal of stabilizer-ligands from supported gold nanoparticles

Metal nanoparticles that comprise a few hundred to several thousand atoms have many applications in areas such as photonics, sensing, medicine and catalysis. Colloidal methods have proven particularly suitable for producing small nanoparticles with controlled morphologies and excellent catalytic properties. Ligands are necessary to stabilize nanoparticles during synthesis, but once the particles have been deposited on a substrate the presence of the ligands is detrimental for catalytic activity. Previous methods for ligand removal have typically involved thermal and oxidative treatments, which can affect the size or morphology of the particles, in turn altering their catalytic activity. Here, we report a procedure to effectively remove the ligands without affecting particle morphology, which enhances the surface exposure of the nanoparticles and their catalytic activity over a range of reactions. This may lead to developments of nanoparticles prepared by colloidal methods for applications in fields such as environmental protection and energy production.

Promotion of phenol photodecomposition over TiO2 using Au, Pd, and Au-Pd nanoparticles

Noble metal nanoparticles (Au, Pd, Au-Pd alloys) with a narrow size distribution supported on nanocrystalline TiO(2) (M/TiO(2)) have been synthesized via a sol-immobilization route. The effect of metal identity and size on the photocatalytic performance of M/TiO(2) has been systematically investigated using phenol as a probe molecule. A different phenol degradation pathway was observed when using M/TiO(2) catalysts as compared to pristine TiO(2). We propose a mechanism to illustrate how the noble metal nanoparticles enhance the efficiency of phenol decomposition based on photoreduction of p-benzoquinone under anaerobic conditions. Our results suggest that the metal nanoparticles not only play a role in capturing photogenerated electrons, but are strongly involved in the photocatalytic reaction mechanism. The analysis of the reaction intermediates allows us to conclude that on M/TiO(2) undesired redox reactions that consume photogenerated radicals are effectively suppressed. The analysis of the final products shows that the reusability performance of the catalyst is largely dependent on the pretreatment of the catalyst and the identity of the metal nanoparticle. Interestingly, the as-prepared Pd and Au-Pd decorated TiO(2) materials exhibit excellent long-term photoactivity, in which ~90% of the phenol can be fully decomposed to CO(2) in each cycle.

Designer titania-supported Au-Pd nanoparticles for efficient photocatalytic hydrogen production

Photocatalytic hydrogen evolution may provide one of the solutions to the shift to a sustainable energy society, but the quantum efficiency of the process still needs to be improved. Precise control of the composition and structure of the metal nanoparticle cocatalysts is essential, and we show that fine-tuning the Au-Pd nanoparticle structure modifies the electronic properties of the cocatalyst significantly. Specifically, Pd(shell)-Au(core) nanoparticles immobilized on TiO2 exhibit extremely high quantum efficiencies for H2 production using a wide range of alcohols, implying that chemical byproducts from the biorefinery industry can be used as feedstocks. In addition, the excellent recyclability of our photocatalyst material indicates a high potential in industrial applications. We demonstrate that this particular elemental segregation provides optimal positioning of the unoccupied d-orbital states, which results in an enhanced utilization of the photoexcited electrons in redox reactions. We consider that the enhanced activity observed on TiO2 is generic in nature and can be transferred to other narrow band gap semiconductor supports for visible light photocatalysis.

Direct Synthesis of Hydrogen Peroxide and Benzyl Alcohol Oxidation Using Au—Pd Catalysts Prepared by Sol Immobilization

We report the preparation of Au-Pd nanocrystalline catalysts supported on activated carbon prepared via a sol-immobilization technique and explore their use for the direct synthesis of hydrogen peroxide and the oxidation of benzyl alcohol. In particular, we examine the synthesis of a systematic set of Au-Pd colloidal nanoparticles having a range of Au/Pd ratios. The catalysts have been structurally characterized using a combination of UV-visible spectroscopy, transmission electron microscopy, STEM HAADF/XEDS, and X-ray photoelectron spectroscopy. The Au-Pd nanoparticles are found in the majority of cases to be homogeneous alloys, although some variation is observed in the AuPd composition at high Pd/Au ratios. The optimum performance for the synthesis of hydrogen peroxide is observed for a catalyst having a Au/Pd 1:2 molar ratio. However, the competing hydrogenation reaction of hydrogen peroxide increases with increasing Pd content, although Pd alone is less effective than when Au is also present. Investigation of the oxidation of benzyl alcohol using these materials also shows that the optimum selective oxidation to the aldehyde occurs for the Au/Pd 1:2 molar ratio catalyst. These measured activity trends are discussed in terms of the structure and composition of the supported Au-Pd nanoparticles.

Au–Pd supported nanocrystals prepared by a sol immobilisation technique as catalysts for selective chemical synthesis

Catalysis by gold and gold-palladium nanoparticles has attracted significant research attention in recent years. These nanocrystalline materials have been found to be highly effective for selective and total oxidation, but in most cases the catalysts are prepared using precipitation or impregnation. We report the preparation of Au-Pd nanocrystalline catalysts supported on carbon prepared via a sol-immobilisation technique and these have been compared with Au-Pd catalysts prepared via impregnation. The catalysts have been evaluated for two selective chemical syntheses, namely, oxidation of benzyl alcohol and the direct synthesis of hydrogen peroxide. The catalysts have been structurally characterised using a combination of scanning transmission electron microscopy and X-ray photoelectron spectroscopy. The catalysts prepared using the sol immobilisation technique show higher activity when compared with catalysts prepared by impregnation as they are more active for both hydrogen peroxide synthesis and hydrogenation, and also for benzyl alcohol oxidation. The method facilitates the use of much lower metal concentrations which is a key feature in catalyst design, particularly for the synthesis of hydrogen peroxide.

Controlling the Duality of the Mechanism in Liquid‐Phase Oxidation of Benzyl Alcohol Catalysed by Supported Au–Pd Nanoparticles

In the solvent-free oxidation of benzyl alcohol to benzaldehyde using supported gold-palladium nanoparticles as catalysts, two pathways have been identified as the sources of the principal product, benzaldehyde. One is the direct catalytic oxidation of benzyl alcohol to benzaldehyde by O(2), whereas the second is the disproportionation of two molecules of benzyl alcohol to give equal amounts of benzaldehyde and toluene. Herein we report that by changing the metal oxide used to support the metal-nanoparticles catalyst from titania or niobium oxide to magnesium oxide or zinc oxide, it is possible to switch off the disproportionation reaction and thereby completely stop the toluene formation. It has been observed that the presence of O(2) increases the turnover number of this disproportionation reaction as compared to reactions in a helium atmosphere, implying that there are two catalytic pathways leading to toluene.

Oxidation of Glycerol to Glycolate by using Supported Gold and Palladium Nanoparticles

Glycolic acid is an important chemical that has uses as a cleaning agent as well as a chemical intermediate. At present glycolic acid is manufactured from either chloroacetic acid or from formaldehyde hydrocyanation, both routes being nongreen and using nonsustainable resources. We investigate the possibility of producing glycolate from the oxidation of glycerol, a sustainable raw material. We show that by using 1 % wt Au/carbon catalysts prepared using a sol-immobilization method glycolate yields of ca. 60 % can be achieved, using hydrogen peroxide as oxidant in an autoclave reactor. We describe and discuss the reaction mechanism and consider the reaction conditions that maximize the formation of glycolate.

Involvement of surface-bound radicals in the oxidation of toluene using supported Au-Pd nanoparticles.

Au-Pd nanoparticles having a mean particle size of 3–4 nm and supported on titania (see figure; scale bar 2 nm) exhibit high activity in the selective oxidation of aromatic hydrocarbons using tert-butyl hydroperoxide as an oxidant. The supported nanoparticles stabilize surface-bound radicals.

Influence of Methyl Halide Treatment on Gold Nanoparticles Supported on Activated Carbon

Catalyzing concept: Methyl halides have been used to disperse large (around 20 nm) gold nanoparticles supported on carbon into dispersed gold atoms/dimers at low temperature and atmospheric pressure (see picture). The process occurs through the progressive removal of gold–halogen entities from the metal nanoparticles and a gradual decrease in the size of the gold nanoparticles on the minute timescale.