Study of the underlying electrochemistry of polycrystalline gold electrodes in aqueous solution and electrocatalysis by large amplitude Fourier transformed alternating current voltammetry

Polycrystalline gold electrodes of the kind that are routinely used in analysis and catalysis in aqueous media are often regarded as exhibiting relatively simple double-layer charging/discharging and monolayer oxide formation/ removal in the positive potential region. Application of the large amplitude Fourier transformed alternating current (FT-ac) voltammetric technique that allows the faradaic current contribution of fast electron-transfer processes to be emphasized in the higher harmonic components has revealed the presence of well-defined faradaic (premonolayer oxidation) processes at positive potentials in the double-layer region in acidic and basic media which are enhanced by electrochemical activation. These underlying quasi-reversible interfacial electron-transfer processes may mediate the course of electrocatalytic oxidation reactions of hydrazine, ethylene glycol, and glucose on gold electrodes in aqueous media. The observed responses support key assumptions associated with the incipient hydrous oxide adatom mediator (IHOAM) model of electrocatalysis.

The effect of light intensity and temperature on photocatalytic water splitting

Photocatalytic water splitting is a process which could potentially lead to commercially viable solar hydrogen production. This thesis uses an engineering perspective to investigate the technology. The effect of light intensity and temperature on photocatalytic water splitting was examined to evaluate the prospect of using solar concentration to increase the feasibility of the process. P25 TiO2 films deposited on conducting glass were used as photocatalyst electrodes and coupled with platinum electrodes which were also deposited on conducting glass. These films were used to form a photocatalysis cell and illuminated with a Xenon arc lamp to simulate solar light at intensities up to 50 suns. They were also tested at temperatures between 20°C and 100°C. The reaction demonstrated a sub-linear relationship with intensity. Photocurrent was proportional to intensity with an exponential value of 0.627. Increasing temperature resulted in an exponential relationship. This proved to follow an Arrhenius relationship with an activation energy of 10.3 kJ mol-1 and a pre-exponential factor of approximately 8.7×103. These results then formed the basis of a mathematical model which extrapolated beyond the range of the experimental tests. This model shows that the loss of efficiency from performing the reaction under high light intensity is offset by the increased reaction rate and efficiency from the associated temperature increase. This is an important finding for photocatalytic water splitting. It will direct future research in system design and materials research and may provide an avenue for the commercialisation of this technology.

Effect of the mediator in feedback mode-based SECM interrogation of indium tin-oxide and boron-doped diamond electrodes

Indium tin-oxide (ITO) and polycrystalline boron-doped diamond (BDD) have been examined in detail using the scanning electrochemical microscopy technique in feedback mode. For the interrogation of electrodes made from these materials, the choice of mediator has been varied. Using Ru(CN) 4− 6 (aq), ferrocene methanol (FcMeOH), Fe(CN) 3− 6 (aq) and Ru(NH 3) 3+ 6 (aq), approach curve experiments have been performed, and for purposes of comparison, calculations of the apparent heterogeneous electron transfer rates (k app) have been made using these data. In general, it would appear that values of k app are affected mainly by the position of the mediator reversible potential relative to the relevant semiconductor band edge (associated with majority carriers). For both the ITO (n type) and BDD (p type) electrodes, charge transfer is impeded and values are very low when using FcMeOH and Fe(CN) 3− 6 (aq) as mediators, and the use of Ru(NH 3) 3+ 6(aq) results in the largest value of k app. With ITO, the surface is chemically homogeneous and no variation is observed for any given mediator. Data is also presented where the potential of the ITO electrode is fixed using a ratio of the mediators Fe(CN) 3− 6(aq) and Fe(CN) 4− 6(aq). In stark contrast, the BDD electrode is quite the opposite and a range of k app values are observed for all mediators depending on the position on the surface. Both electrode surfaces are very flat and very smooth, and hence, for BDD, variations in feedback current imply a variation in the electrochemical activity. A comparison of the feedback current where the substrate is biased and unbiased shows a surprising degree of proportionality.

Reduction of Au3+ ions by activated surface atoms of platinum

In this work it is demonstrated that Pt electrodes can be activated by cathodic polarisation in the hydrogen evolution region which makes it prone to oxidation at potentials below that of bulk oxide formation. When an activated Pt electrode is placed in an aqueous HAuCl4 solution the electroless deposition of Au onto the surface of the electrode is observed and confirmed by cyclic voltammetry and XPS measurements. It is demonstrated that the oxidation of active Pt surface atoms provides the driving force for the spontaneous reduction of Au3+ ions into metallic Au to generate a Pt/Au surface which is highly active for the electro-oxidation of ethanol.

Predicting active material utilisation in LiFePO4 electrodes using a multi-scale mathematical model

A mathematical model is developed to simulate the discharge of a LiFePO4 cathode. This model contains 3 size scales, which match with experimental observations present in the literature on the multi-scale nature of LiFePO4 material. A shrinking-core is used on the smallest scale to represent the phase-transition of LiFePO4 during discharge. The model is then validated against existing experimental data and this validated model is then used to investigate parameters that influence active material utilisation. Specifically the size and composition of agglomerates of LiFePO4 crystals is discussed, and we investigate and quantify the relative effects that the ionic and electronic conductivities within the oxide have on oxide utilisation. We find that agglomerates of crystals can be tolerated under low discharge rates. The role of the electrolyte in limiting (cathodic) discharge is also discussed, and we show that electrolyte transport does limit performance at high discharge rates, confirming the conclusions of recent literature.

Single crystal Raman spectroscopy of brandholzite Mg[Sb(OH)6]2•6H2O and bottinoite Ni[Sb(OH)6]2•6H2O and the polycrystalline Raman spectrum of mopungite Na[Sb(OH)6]

The single crystal Raman spectra of minerals brandholzite and bottinoite, formula M[Sb(OH)6]2•6H2O, where M is Mg+2 and Ni+2 respectively, and the non-aligned Raman spectrum of mopungite, formula Na[Sb(OH)6], are presented for the first time. The mixed metal minerals comprise of alternating layers of [Sb(OH)6]-1 octahedra and mixed [M(H2O)6]+2 / [Sb(OH)6]-1 octahedra. Mopungite comprises hydrogen bonded layers of [Sb(OH)6]-1 octahedra linked within the layer by Na+ ions. The spectra of the three minerals were dominated by the Sb-O symmetric stretch of the [Sb(OH)6]-1 octahedron, which occurs at approximately 620 cm-1. The Raman spectrum of mopungite showed many similarities to spectra of the di-octahedral minerals informing the view that the Sb octahedra gave rise to most of the Raman bands observed, particularly below 1200 cm-1. Assignments have been proposed based on the spectral comparison between the minerals, prior literature and density field theory calculations of the vibrational spectra of the free [Sb(OH)6]-1 and [M(H2O)6]+2 octahedra by a model chemistry of B3LYP/6-31G(d) and lanl2dz for the Sb atom. The single crystal data spectra showed good mode separation, allowing the majority of the bands to be assigned a symmetry species of A or E.

Platinum/graphene nanosheet/SiC contacts and their application for hydrogen gas sensing

Pt/graphene nanosheet/SiC based devices are fabricated and characterized and their performances toward hydrogen gas are investigated. The graphene nanosheets are synthesized via the reduction of spray-coated graphite oxide deposited onto SiC substrates. Raman and X-ray photoelectron spectroscopies indicate incomplete reduction of the graphite oxide, resulting in partially oxidized graphene nanosheet layers of less than 10 nm thickness. The effects of interfaces on the nonlinear behavior of the Pt/graphene and graphene/SiC junctions are investigated. Current-voltage measurements of the sensors toward 1% hydrogen in synthetic air gas mixture at various temperatures ranging up to 100. ° C are performed. From the dynamic response, a voltage shift of ∼100 mV is recorded for 1% hydrogen at a constant current bias of 1 mA at 100. °C. © 2010 American Chemical Society.

Size effects on tensile and fatigue behaviour of polycrystalline metal foils at the micrometer scale

Tensile and fatigue properties of as-rolled and annealed polycrystalline Cu foils with different thicknesses at the micrometer scale were investigated. Uniaxial tensile testing results showed that with decreasing foil thickness the uniform elongation decreases for both as-rolled and annealed foils, whereas the yield strength and ultimate tensile strength increase for as-rolled foils, but decrease for the annealed foils. For both the as-rolled or annealed foils, bending fatigue resistance decreases with decreasing the foil thickness. Deformation and fatigue damage behaviour of the free-standing foils were characterised as a function of foil thickness. In addition, the fatigue strength of various small-scale Cu foils was compared to understand they physical mechanisms of size effects on mechanical properties of the metallic material at micrometer scales.

Low temperature synthesis of carbon nanotubes on indium tin oxide electrodes for organic solar cells

The electrical performance of indium tin oxide (ITO) coated glass was improved by including a controlled layer of carbon nanotubes directly on top of the ITO film. Multi-wall carbon nanotubes (MWCNTs) were synthesized by chemical vapor deposition, using ultra-thin Fe layers as catalyst. The process parameters (temperature, gas flow and duration) were carefully refined to obtain the appropriate size and density of MWCNTs with a minimum decrease of the light harvesting in the cell. When used as anodes for organic solar cells based on poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM), the MWCNT-enhanced electrodes are found to improve the charge carrier extraction from the photoactive blend, thanks to the additional percolation paths provided by the CNTs. The work function of as-modified ITO surfaces was measured by the Kelvin probe method to be 4.95 eV, resulting in an improved matching to the highest occupied molecular orbital level of the P3HT. This is in turn expected to increase the hole transport and collection at the anode, contributing to the significant increase of current density and open circuit voltage observed in test cells created with such MWCNT-enhanced electrodes.