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 POM's 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.
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 nanoclaybased 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.
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