ANODIC-OXIDATION OF HYDRAZINE ON GLASSY-CARBON MODIFIED BY MACROCYCLIC TRANSITION-METAL COMPLEXES .1. COBALT PROTOPORPHYRIN DIMETHYL ESTER MODIFIED ELECTRODE

The electrocatalytic oxidation of hydrazine (N2H4) on a glassy carbon electrode (GC) modified by monolayer and polymer films of cobalt protoporphyrin dimethyl ester (CoPP) has been studied. Both the monolayer and polymer films of CoPP are very active to the anodic oxidation of N2H4. The activity of CoPP for the anodic oxidation of N2H4 is dependent on the pH of the solution, and the thickness of polymerized CoPP film. The oxidation kinetics were examined by methods of cyclic voltammetry, rotating disc electrodes and steady-state polarization measurement.

Involvement of incipient hydrous oxide species in electrocatalysis at some metal electrode surfaces

In this thesis a novel theory of electrocatalysis at metal (especially noble metal)/solution interfaces was developed based on the assumption of metal adatom/incipient hydrous oxide cyclic redox transitions. Adatoms are considered as metastable, low coverage species that oxidise in-situ at potentials of often significantly cathodic to the regular metal/metal oxide transition. Because the adatom coverage is so low the electrochemical or spectroscopic response for oxidation is frequently overlooked; however, the product of such oxidation, referred to here as incipient hydrous oxide seems to be the important mediator in a wide variety of electrocatalytically demanding oxidation processes. Conversely, electrocatalytically demanding reductions apparently occur only at adatom sites at the metal/solution interface - such reactions generally occur only at potentials below, i.e. more cathodic than, the adatom/hydrous oxide transition. It was established that while silver in base oxidises in a regular manner (forming initially OHads species) at potentials above 1.0 V (RHE), there is a minor redox transition at much lower potentials, ca. o.35 v (RHE). The latter process is assumed to an adatom/hydrous oxide transition and the low coverage Ag(l) hydrous oxide (or hydroxide) species was shown to trigger or mediate the oxidation of aldehydes, e. g. HCHO. The results of a study of this system were shown to be in good agreement with a kinetic model based on the above assumptions; the similarity between this type of behaviour and enzyme-catalysed processes - both systems involve interfacial active sites - was pointed out. Similar behaviour was established for gold where both Au(l) and Au(lll) hydrous oxide mediators were shown to be the effective oxidants for different organic species. One of the most active electrocatalytic materials known at the present time is platinum. While the classical view of this high activity is based on the concept of activated chemisorption (and the important role of the latter is not discounted here) a vital role is attributed to the adatom/hydrous oxide transition. It was suggested that the well known intermediate (or anomalous) peak in the hydrogen region of the cyclic voltanmogram for platinum region is in fact due to an adatom/hydrous oxide transition. Using potential stepping procedures to minimise the effect of deactivating (COads) species, it was shown that the onset (anodic sweep) and termination (cathodic sweep) potential for the oxidation of a wide variety of organics coincided with the potential for the intermediate peak. The converse was also shown to apply; sluggish reduction reactions, that involve interaction with metal adatoms, occur at significant rates only in the region below the hydrous oxide/adatom transition.

The basis for the formation of stable metal clusters on an electrode surface

Metal nanoclusters can be produced cheaply and precisely in an electrochemical environment. Experimentally this method works in some systems, but not in others, and the unusual stability of the clusters has remained a mystery. We have simulated the deposition of the clusters using classical molecular dynamics and studied their stability by grand-canonical Monte Carlo simulations. We find that electrochemically stable clusters occur only in those cases where the two metals involved form stable alloys.

A Study Of The Effect Of Electrode And Overlayer Films On The Electrical Properties Of Certain Metal Films

This thesis consists of a study of the effect of electrode films and overlayer films on the electrical properties of certain metal films. The films have been prepared on glass substrates by thermal evapouration in a vaccum 10 terr. The properties of Al films on Ag, Al,Au and Cu films on In electrodes ,and Bi/Ag bilayer films have been studied. The influence of annealing electrodes at higher temperature on the electrical properties of metal films has also been investigated. Further the effect of varying layer thickness in the bilayer films ,both annealed at higher temperature and annealed at room temperature have been examined.

Transition metal nitrides as electrode materials for supercapacitors

This data comprises a collection of Scanning Electron Microscope (SEM) images of transition metal nitrates. Research was conducted to assess the size and morphology of particles

Inhibiting localized corrosion of aluminum and aluminum alloy by rare earth metal compounds : behaviors and characteristics observed using an electrochemically integrated multi-electrode array

An electrochemically integrated multi-electrode array namely the wire beam electrode (WBE) has been used to characterize the behavior of cerium chloride (CeCl3) and lanthanum chloride (LaCl3) in inhibiting localized corrosion of AA2024-T3 and AA1100. CeCl3 has been found to inhibit AA2024-T3 corrosion in 0.005 M sodium chloride (NaCl) solution by suppressing galvanic corrosion activities and by creating a large number of insignificant anodes. It has also been shown to inhibit localized corrosion of AA1100 in 0.5 M NaCl solution by promoting the random distribution of minor anodes. LaCl3 has been found to inhibit localized corrosion of AA2024-T3 at 1000 ppm, although its efficiency dropped significantly when its concentration decreased to 500 ppm. The addition of CeCl3 and LaCl3 to corrosion testing cells at later stages was unable to effectively suppress existing corrosion anodes.

Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

Graphene nanodots-encaged porous gold electrode fabricated via ion beam sputtering deposition for electrochemical analysis of heavy metal ions

All rights reserved. A graphene nanodots-encaged porous gold electrode via ion beam sputtering deposition (IBSD) for electrochemical sensing is presented. The electrodes were fabricated using Au target, and a composite target of Al and graphene, which were simultaneously sputtered onto glass substrates by Ar ion beam, followed with hydrochloric acid corrosion. The as-prepared graphene nanodots-encaged porous gold electrodes were then used for the analysis of heavy metal ions, e.g. Cu2+ and Pb2+ by Osteryoung square wave voltammetry (OSWV). These porous electrodes exhibited enhanced detection range for the heavy metal ions due to the entrapped graphene nanodots in 3-D porous structure. In addition, it was also found that when the thickness of porous electrode reached 40 nm the detection sensitivity came into saturation. The linear detection range is 0.009-4 μM for Cu2+ and 0.006-2.5 μM for Pb2+. Good reusability and repeatability were also observed. The formation mechanism and 3-D structure of the porous electrode were also investigated using scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray photoelectron spectra (XPS). This graphene entrapped 3-D porous structure may envision promising applications in sensing devices.

Combined use of transcranial magnetic stimulation and metal electrode implants: a theoretical assessment of safety considerations

This paper provides a theoretical assessment of the safety considerations encountered in the simultaneous use of transcranial magnetic stimulation (TMS) and neurological interventions involving implanted metallic electrodes, such as electrocorticography. Metal implants are subject to magnetic forces due to fast alternating magnetic fields produced by the TMS coil. The question of whether the mechanical movement of the implants leads to irreversible damage of brain tissue is addressed by an electromagnetic simulation which quantifies the magnitude of imposed magnetic forces. The assessment is followed by a careful mechanical analysis determining the maximum tolerable force which does not cause irreversible tissue damage. Results of this investigation provide useful information on the range of TMS stimulator output powers which can be safely used in patients having metallic implants. It is shown that conventional TMS applications can be considered safe when applied on patients with typical electrode implants as the induced stress in the brain tissue remains well below the limit of tissue damage.

Lightweight metal halide and hydride fast Li ion conductors

This work was motivated by the extensive research on lithium solid state materials, which have attracted increasing interest for potential applications in hydrogen storage and/or lithium ion batteries due to their extraordinary properties. In this thesis, LiBH4-derived materials, LiInBr4 and complex phases based on lithium ammonia borane with potential use as solid state electrolytes were successfully synthesised and characterised.