Gordon Armstrong

Surface Immobilization of a Tetra-Ruthenium Substituted Polyoxometalate Water Oxidation Catalyst Through the Employment of Conducting Polypyrrole and the Layer-by-Layer (LBL) Technique

A tetra Ru-substituted polyoxometalate Na10[{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2] (Ru4POM) has been successfully immobilised onto glassy carbon electrodes and indium tin oxide (ITO) coated glass slides through the employment of a conducting polypyrrole matrix and the layer-by-layer (LBL) technique. The resulting Ru4POM doped polypyrrole films showed stable redox behavior associated with the Ru centres within the Ru4POM, whereas, the POMs tungsten-oxo redox centres were not accessible. The films showed pH dependent redox behavior within the pH range 2-5 whilst exhibiting excellent stability towards redox cycling. The layer-by-layer assembly was constructed onto poly(diallyldimethylammonium chloride) (PDDA) modified carbon electrodes by alternate depositions of Ru4POM and a Ru(II) metallodendrimer. The resulting Ru4POM assemblies showed stable redox behavior for the redox processes associated with Ru4POM in the pH range 2-5. The charge transfer resistance of the LBL films was calculated through AC-Impedance. Surface characterization of both the polymer and LBL Ru4POM films was carried out using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Initial investigations into the ability of the Ru4POM LBL films to electrocatalytically oxidise water at pH 7 have also been conducted.

Titania–silver and alumina–silver composite nanoparticles: Novel, versatile synthesis, reaction mechanism and potential antimicrobial application

Titania-silver (TiO(2)-Ag) and alumina-silver (Al(2)O(3)-Ag) composite nanoparticles were synthesised by a simple, reproducible, wet chemical method under ambient conditions. The surface of the oxides was modified with oleic acid, which acted as an intermediate between the oxide surface and the silver nanoparticles. The resulting composite nanoparticles were thoroughly characterised by XRD, TEM, XPS, FTIR and TGA to elucidate the mode of assembly of Ag nanoparticles on the oxide surfaces. Epoxy nanocomposites were formulated with TiO(2)-Ag and Al(2)O(3)-Ag to examine potential applications for the composite nanoparticles. Preliminary results from disc diffusion assays against Escherichia coli DH5α and Staphylococcus epidermidis NCIMB 12721 suggest that these TiO(2)-Ag and Al(2)O(3)-Ag composite nanoparticles have potential as antimicrobial materials.

An introduction to polymer nanocomposites

This review presents an overview of the formulation, characterization and range of applications for polymer nanocomposites. After explaining how material properties at the nanometre scale can vary compared to those observed at longer length scales, typical methods used to formulate and characterize nanocomposites at laboratory and industrial scale will be described. The range of mechanical, electrical and thermal properties obtainable from nanocomposite materials, with examples of current commercial applications, will be outlined. Formulation and characterization of nanoparticle, nanotube and graphene composites will be discussed by reference to nanoclay-based composites, as the latter are presently of most technological relevance. Three brief case studies are presented to demonstrate how structure/property relationships may be controlled in a variety of polymer nanocomposite systems to achieve required performance in a given application. The review will conclude by discussing potential obstacles to commercial uptake of polymer nanocomposites, such as inconsistent protocols to characterize nanocomposites, cost/performance balances, raw material availability, and emerging legislation, and will conclude by discussing the outlook for future development and commercial uptake of polymer nanocomposites.

Thermal stability of a ureidopyrimidinone model compound

Abstract A dimer of N-[(butylamino)carbonyl]-6-methylisocytosine was prepared as a model compound in order to study the thermal stability of ureidopyrimidinone supramolecular polymers during heat/cool cycles. The dimer did not self-heal (i.e. disintegrate and reform reversibly) as expected; it underwent thermal degradation in three stages once heated to its melting point of 225 °C. Infrared spectra and optical micrographs were taken before and after these cycles, and the gases evolved at each stage of the degradation process were identified by gas chromatography-mass spectroscopy. A degradation mechanism is proposed whereby the dimers butane-1-isocyanate ‘tail’ cleaves first, followed by the isocytosine ‘head’ breaking down above 244 °C. The kinetics of the degradation process were also determined, from which the activation energy was calculated to be 71.5 kJ/mol. In conclusion, the implications for processing related supramolecular polymers are discussed.

Investigations into the electrochemical, surface, and electrocatalytic properties of the surface-immobilized polyoxometalate, TBA3K[SiW10O36(PhPO)2].

Surface anchoring of an organic functionalized POM, TBA3K[SiW10O36(PhPO)2] was carried out by two methods, the layer-by-layer (LBL) assembly technique by employing a pentaerythritol-based ruthenium(II) metallodendrimer as a cationic moiety and also by entrapping the POM in a conducting polypyrrole film. The redox behavior of the constructed films was studied by using cyclic voltammetry and electrochemical impedance spectroscopy. The surface morphologies of the constructed multilayers were examined by scanning electron microscopy and atomic force microscopy. X-ray photoelectron spectroscopy was conducted to confirm the elements present within the fabricated films. The multilayer assembly was also investigated for its catalytic efficiency towards the reduction of nitrite.

Compositional characterisation of metallurgical grade silicon and porous silicon nanosponge particles

Porous silicon is generally achieved through electro-chemical etching or chemical etching of bulk silicon in hydrofluoric acid based solutions. The work presented here explores the effect of a chemical etching process on a metallurgical grade silicon powder. It is found that the metallurgical grade silicon particles contain surface bound impurities that induce a porous structure formation upon reaction with the chemical etchant applied. The correlation between the resultant porous structure formed due to the material composition is examined in detail. The elemental composition is determined using a combination of X-ray Photoelectron Spectroscopy and Time of Flight Secondary Ion Mass Spectroscopy. The porous structure is analysed using Transmission Electron Microscopy and Scanning Electron Microscopy. Three samples of the silicon particles analysed for this study include an un-etched bulk silicon powder sample and two samples of chemically etched powder. Pore formation within the particles is found to be dependent on the presence, dispersion, and local concentration of surface bound impurities within the starting powder.