This contribution explores the applicability of nickel-based metallic foams as active electrodes and as electrocatalyst support materials. A comprehensive characterization of Ni and multi-component Ni-based foams is presented and includes the analysis of their structural, chemical, and electrochemical properties. Several materials and surface science techniques as well as electrochemical methods are used to examine the structural characteristics, surface morphology, and surface-chemical composition of these materials. X-ray photoelectron spectroscopy is employed to analyze the surface and near-surface chemical composition. The specific and electrochemically active surface areas (As, Aecsa) are determined using cyclic voltammetry (CV). The foams exhibit structural robustness typical of bulk materials and they have large As, in the 200 – 600 cm2 g–1 range. In addition, they are dual-porosity materials and possess both macro and meso pores. Nickel foam electrodes are applied as electrocatalysts for the oxidation of isopropanol. The process is studied under well-defined experimental conditions using cyclic voltammetry. The outcome of these experiments demonstrates that isopropanol oxidation requires the presence of -NiOOH on the Ni foam electrode. This surface oxide is generated at potentials near the potential of the isopropanol oxidation; however, the two processes do not occur exactly at the same potentials. The Ni foam anodes sustain a current density of ca. 2.6 mA cm–2 throughout an electrolysis time of up to 600 minutes without significant loss of electrocatalytic activity. Isopropanol is converted to acetone at a rate of ca. 5.6 mM per hour. The applicability of Ni foams as support materials for Pt is investigated. Platinum particles are deposited on Ni foam in low loading amounts via the chemical reduction of Pt2+ and Pt4+ originating from aqueous Pt salt solutions. The resulting Pt / Ni foams are characterized using electrochemical, analytical, and materials analysis techniques, including SEM to examine the morphology of the deposited material, CV to evaluate the Aecsa of the deposited Pt, and inductively coupled plasma optical emission spectrometry (ICP-OES) to determine the mass of deposited Pt. The Pt / Ni foams are applied as electrocatalysts for hydrogen evolution, hydrogen reduction, oxygen evolution, and oxygen reduction reactions in alkaline electrolyte. / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-12-06 13:28:17.471

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This thesis is concerned with the electrochemical and spectroelectrochemical characterisation of cyano (CN) and trifluoromethyl (CF3) substituted polypyridine ligands and their metal complexes. The ligands investigated were X-CN-py (X = 3, 4 and 5, py = pyridine), X,X´-(CN)2-bpy) (X,X´ = 3,3´, 4,4´ and 5,5´ bpy = 2,2´- bipyridine) and X,X´-(CF3)2-bpy (X,X´ = 3,3´, 4,4´ and 5,5´). The Pt(II) complexes of the X-CN-py and X,X´-(CN)2-bpy ligands were studied along with the Fe(II) complexes of the X,X´-(CN)2-bpy and X,X´-(CF3)2-bpy ligands. Electrochemical studies of the X-CN-py ligands indicated that 2-CN-py and 4-CN-py have one reversible 1e- reduction and 3-CN-py has one quasi-reversible reduction. 4-CN-py is more easily reduced than 2-CN-py. EPR experiments on [2-CN-py]1- and [4-CN-py]1- combined with DFT calculations have indicated that the semi-occupied molecular orbital (SOMO) is delocalised over the entire molecule. The complex [Pt(4-CN-py)2Cl2] undergoes two reversible 1e- reductions, attributed to the sequential reduction of the two 4-CN-py ligands. [Pt(3-CN-py)2Cl2] was found to exhibit one irreversible reduction. The electrochemistry of the X,X´-(CN)2-bpy ligands indicated that 3,3´-(CN)2-bpy and 5,5´-(CN)2-bpy have two reversible 1e- reductions while 4,4´-(CN)2-bpy has only one reversible 1e- reduction. The reductions of 5,5´-(CN)2-bpy occur at significantly less negative potentials than those in 3,3´ or 4,4´ analogue. In-situ UV/Vis/NIR and EPR experiments on the X,X´-(CN)2-bpy ligands indicate that the reduction electron is delocalised over both the CN-py rings with the SOMO being spread across the entire molecule. [Pt(3,3´-(CN)2-bpy)Cl2] and [Pt(5,5´-(CN)2-bpy)Cl2] undergo two reversible 1e- reductions, attributed to the sequential reduction of the X,X´-(CN)2-bpy ligand. 4,4´-(CF3)2-bpy and 5,5´-(CF3)2-bpy, whose X-ray crystallographically determined structures are reported, both have one reversible 1e- reduction while 3,3´-(CF3)2-bpy exhibits an irreversible reduction. Again the 5,5´ analogue is the most easily reduced. Spectroelectrochemical results indicate that the reduction electron enters a SOMO that is delocalised over both the CF3-py rings. Substitution in the 5,5´ positions is determined to be electronically most significant. Complexes of the general formula [Fe(II)(X2-bpy)3][BF4] (where X = CN or CF3 in the 4,4´ or 5,5´ positions) exhibit three reversible ligand based reduction processes and a metal based oxidation. UV/Vis/NIR and EPR studies have confirmed that the reduction electron in each case enters a molecular orbital that is predominantly based on a bpy ligand. The redox potentials of 4-CN-py and 5,5´-(CN)2-bpy are solvent dependent with 1e- reduction of 4-CN-py and the two 1e- reductions of 5,5´-(CN)2-bpy moving to less negative potentials as the acceptor number (AN) of the solvent increases. A computational model has been developed for the study of the electronic properties of substituted bipyridines using DFT methods. This model has been used to aid the analysis of the EPR and UV/Vis/NIR spectra of the X2-bpys studied.

The effect on conductivity of progressively substituting foreign alkali for host alkali in a series of lithium aluminoborate glasses has been studied. The shape of the conductivity isotherm in the dilute foreign alkali region was found to be the same for both Na+ and K+ dopants. Assuming a 'regular interstitialcy model' for ionic conduction conductivity data for a variety of glasses were subjected to isothermal analysis, allowing concentrations of mobile species and mobilities to be calculated. Conductivity changes were found to be largely attributable to changes in mobility, the concentration term remaining remarkably constant. The a.c. behaviour of aluminoborate glasses has also been studied and modulus spectra fitted using the Kohlrausch-Williams-Watts function for various beta-values. Decreasing the total alkali content and substituting foreign alkali for host alkali was observed to cause some narrowing of the modulus, mixed-alkali glasses behaving much as though only 'host' cations were present. 'Microscopic' activation energies (E_a) have been calculated from beta-values (Ea=beta Ead.c.). These are found to follow the trend in experimentally observed activation energies indicating that the mixed alkali effect occurs as the result of decreases in both long- and short-range ionic mobilities. A cluster-bypass model has been proposed in an attempt to reconcile the above results. The model assumes that the mobile species are to be found in a tissue material surrounding the clusters. A brief examination of the site preferences of spectroscopic probe ions (T1+ and Pb2+) in mixed cation glasses by u.v. spectroscopy indicated a dependence of the frequency of the absorption band on the reagents used in glass preparation. This result is thought to point towards some structural effects persisting in the melt which in turn may be important with respect to cluster formation in the glass.

A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy. / A quartz microbalance electrode (QME) was constructed for the investigation of the electrochemistry of electroless plating baths. To this end, the electronic oscillator circuitry required for the microbalance was developed from literature examples, and the techniques of forming electrodes and mounting the crystal in an appropriate holder were established. The device thus developed was compact, allowing for in situ frequency and electrochemical measurements to be made in a commercially available 100 mL Metrohm cell. The precision .and accuracy obtained with the home-built device were shown to be adequate for electrochemical research, and the sensitivity was found to be consistent with the value expected from the Sauerbrey equation.(Abbreviation abstract) / Andrew Chakane 2018

Orientador: Alexandre Luiz Souto Borges / Co-orientador: Anderson de Oliveira Lobo / Banca: Alberto Noriyuki Kojima / Banca: João Paulo Barros Machado / Resumo:A eletrofiação é um método para a síntese de fibras poliméricas. Neste sentido, a quitosana é um polímero que por meio deste processo origina biomateriais com boas propriedades biológicas. Já a hidroxiapatita é a principal de reserva de cálcio dos vertebrados. Assim, o presente estudo fabricou mantas de nanofibras a partir de solução de quitosana pura 7% (m/v)(Ch) e de solução de quitosana com adição de cristais de nanohidroxiapatita 0,5% (m/v)(ChHa), na tentativa de unir, sob diferentes parâmetros de eletrofiação (distância, tensão elétrica e fluxo da solução), as propriedades do biopolímero e do complexo de fosfato de cálcio. Ambas soluções foram eletrofiadas e, as mantas obtidas, caracterizadas de acordo com a morfologia (diâmetro médio das fibras), topografia superficial (perfilometria e AFM) e características físicas, químicas, estruturais e térmicas (EDS, FTIR, DRX, ângulo de contato, taxa de degradação, termogravimetria). As amostras Ch, quanto à análise morfológica, apresentaram maior diâmetro de fibras (690,3±102,5nm) em relação às ChHa (358,7±49,2nm) e quanto à topografia, Ch mostrou maior homogeneidade, lisura superficial do que ChHa. O EDS foi capaz de identificar presença de Cálcio nas amostras de ChHa. A partir do FTIR, verificou-se bandas caracteríscas de formação de sal de TFA, respaldando a instabilidade de todas as amostras em meio aquoso, sofrendo imediata dissolução sob os testes de molhabilidade e taxa de degradação. As análises térmicas mostraram que, tanto em Ch como em ChHa, três principais estágios de degradação, sendo a primeira, representação de uma grande perda de água / Abstract: The electrospinning is a method used to synthesize polymeric fibers. Chitosan polymer was the one used by this process that originates a biomaterial with good biological properties. The hydroxyapatite is a important calcium reserve of vertebrates. The synthesize process to create nanofibers were made using pure chitosan solution 7% (w/v) (Ch) and chitosan solution added with nanohydroxyapatite (0,5%, w/v) (ChHa), as an attempt to unite, under different electrospinning parameters (distance, electric tension and flow rate), the properties of the biopolymer and calcium phosphate complex. Both solutions were electrospun and the specimens obtained were characterized according to the superficial morphology (mean diameter) topography (profilometry and atomic force microscopy) and physico-chemical characteristics (EDS, FTIR, DRX, contact angle and thermogravimetry). The Ch samples showed from the morphology analysis, a higher mean diameter (690,3±102,5nm) in comparison to ChHa (358,7±49,2nm) and the topograpghy analysis indicated a greater homogeneity and surface smoothness. The EDS was able to identify the presence of calcium in samples of ChHa. From the FTIR, it was verified characteristic peaks of TFA salt formation, which explains the instability of all samples in aqueous solution, with immediate dissolution under the contact angle and degradation rates tests. The thermal analysis presented three main stages of degradation in Ch and ChHa nanofibers with a higher water loss / Mestre

Joseph Chung-Yin Lam. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2000. / Includes bibliographical references (leaves 62-64). / Abstracts in English and Chinese. / Contents --- p.i / Acknowledgements --- p.ii / Abstract --- p.iii / Abbreviations --- p.v / Chapter Chapter I. --- Introduction / Chapter (1) --- General background of dendrimers --- p.1 / Chapter (2) --- Electrochemically active dendrimers --- p.2 / Chapter (3) --- Electrochemically active dendrimers as models for studying the redox behaviour of complex proteins --- p.11 / Chapter Chapter II --- . Synthesis and Characterization / Chapter (1) --- Structure of the electrochemically active dendrimers --- p.16 / Chapter (2) --- Retrosynthetic analysis --- p.17 / Chapter (3) --- Synthesis --- p.18 / Chapter (4) --- Structural Characterization --- p.26 / Chapter (5) --- Conclusion --- p.33 / Chapter Chapter III. --- Physical and Electrochemical Properties / Chapter (1) --- Physical appearance and solubility properties --- p.34 / Chapter (2) --- Cyclic voltammetry studies --- p.34 / Chapter Chapter IV. --- Summary --- p.40 / Chapter Chapter V. --- Experimental --- p.41 / References --- p.62 / Spectra --- p.65

Thesis (Ph.D.)--Boston University

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