An electrochromic ionic liquid: design, characterisation and performance in a solid state platform

This work describes the synthesis and characteristics of a novel electrochromic ionic liquid (IL) based on a phosphonium core tethered to a viologen moiety. When integrated into a solid-state electrochromic platform, the viologen modified IL behaved as both the electrolyte and the electrochromic material. Platform fabrication was achieved through in situ photo-polymerisation and encapsulation of this novel IL within a hybrid sol-gel. Important parameters of the platform performance, including its coloration efficiency, switching kinetics and optical properties were characterised using UV/Vis spectroscopy and cyclic voltammetry in tandem. The electrochromic platform exhibits a coloration efficiency of 10.72 cm2C-1, and a varied optical output as a function of the incident current. Despite the rather viscous nature of the material, the platform exhibited approximately two orders of magnitude faster switching kinetics (221 seconds to reach 95 % absorbance) when compared to previously reported electrochromic ILs (18,000 seconds)

Tunable Nanostructures and Crystal Structures in Titanium Oxide Films

Controllable nanostructures in spin coated titanium oxide (TiO2) films have been achieved by a very simple means, through change of post deposition annealing temperature. Electron beam imaging and reciprocal space analysis revealed as-deposited TiO2films to be characterized by a dominant anatase phase which converts to the rutile form at 600 °C and reverts to the anatase modification at 1,200 °C. The phase changes are also accompanied by changes in the film microstructure: from regular nanoparticles (as-deposited) to nanowires (600 °C) and finally to dendrite like shapes at 1,200 °C. Photoluminescence studies, Raman spectral results, and X-ray diffraction data also furnish evidence in support of the observed solid state phase transformations in TiO2

In-situ laser Raman scattering and far infrared spectroscopy studies of corrosion-passivation phenomena in metals.

Vibrational spectroscopic and electrochemical techniques are among the most useful tools for the elucidation of corrosion-passivation phenomena in metals. The former can provide information on the structure and composition of corrosion films ''in situ'' in aqueous solution environments, while thermodynamic and kinetic information may be obtained using electrochemical techniques. In this paper, we demonstrate the application of Laser Raman Scattering (LRS) and Synchrotrons Far Infrared Reflectance Spectroscopy (SFIRS), coupled with electrochemical methods, for the determination of the structure and composition of surface films on nickel and copper in aqueous solution environment. The corrosion film on nickel has been found to consist of NiO and Ni(OH){sub 2} in the passive region of potential and NiOOH in the transpassive region. The film on copper consists of Cu{sub 2}O, CUO and Cu(OH){sub 2}. We also show for the first time that SFIRS can be used to obtain information on the adsorption of ions on a metal surface with sub-monolayer sensitivity. Adsorption of Cl{sup {minus}}, Br{sup {minus}}, SO{sup {minus}2}, and PO{sub 4}{sup {minus}3} was found to occur at gold electrodes in perchloric acid solution. We also observed that when two different ions are present in solution, the more strongly adsorbed ion determined the corrosion behavior of the metal

``In-situ'' spectro-electrochemical studies of radionuclide-contaminated surface films on metals

The incorporation of heavy metal ions and radioactive contaminants into hydrous oxide films has been investigated in order to provide fundamental knowledge that could lead to the technological development of cost-effective processes and techniques for the decontamination of storage tanks, piping systems, surfaces, etc., in DOE nuclear facilities. The formation of oxide/hydroxide films was simulated by electrodeposition onto a graphite substrate from solutions of the appropriate metal salt. Synchrotron X-ray Absorption Spectroscopy (XAS), supplemented by Laser Raman Spectroscopy (LRS), was used to determine the structure and composition of the host oxide film, as well as the impurity ion. Results have been obtained for the incorporation of Ce, Sr, Cr, Fe, and U into hydrous nickel oxide films. Ce and Sr oxides/hydroxides are co-precipitated with the nickel oxides in separate phase domains. Cr and Fe, on the other hand, are able to substitute into Ni lattice sites or intercalate in the interlamellar positions of the brucite structure of Ni(OH){sub 2}. U was found to co-deposit as a U(VI) hydroxide. The mode of incorporation of metal ions depends both on the size and charge of the metal ion. The structure of iron oxide (hydroxide) films prepared by both anodic and cathodic deposition has also been extensively studied. The structure of Fe(OH){sub 2} was determined to be similar to that of {alpha}-Ni(OH){sub 2}. Anodic deposition from solutions containing Fe{sup 2+} results in a film with a structure similar to {gamma}-FeOOH. From the knowledge gained from the present studies, principles and methods for decontamination have become apparent. Contaminants sorbed on oxide surfaces or co-precipitated may be removed by acid wash and selective dissolution or complexation. Ions incorporated into lattice sites and interlamellar layers will require more drastic cleaning procedures. Electropolishing and the use of an electrochemical brush are among concepts that should be considered seriously for the latter cases. The incorporation of radionuclides into the structure of highly defective, insoluble oxides and clays should be considered for long-term storage and disposal. The establishment of a truly long-term (10 to 20 years) basic program on environmental science by DOE is strongly recommended. Avenues for future work are suggested