Made available in DSpace on 2014-06-11T19:35:06Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-05-25Bitstream added on 2014-06-13T18:46:10Z : No. of bitstreams: 1 fraga_le_dr_araiq.pdf: 4782705 bytes, checksum: 60899f2f87b43194456d65efa0a6fc5b (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Nos anos mais recentes, o uso indiscriminado de corantes para tintura de cabelo tem despertado grande atenção em virtude de alguns aspectos toxicológicos e mutagênicos. Os efluentes provenientes de salões de beleza e esgotos domésticos quando não convenientemente tratados podem atingir estações de tratamento de água e mananciais, levantando preocupações com a saúde humana e proteção ambiental. O presente trabalho explora novos materiais a serem utilizados em tratamentos de efluentes contaminados por corantes de cabelo por técnicas fotocatalítica e fotoeletrocatalítica. Dentro deste contexto, investigou-se a síntese do eletrodo de Ti/TiO2 através do método sol-gel, e dos eletrodos de W/WO3 e W/WO3/TiO2, utilizando-se métodos eletroquímicos, visando ampliar a faixa de utilização destes eletrodos para a fotoexcitação na região do visível. Estes eletrodos foram caracterizados e aplicados na oxidação fotoeletrocatalítica e fotocatalítica dos corantes básicos de cabelo vermelho básico 51(VB51), marrom básico 16(MB16) e azul básico 99(AB99) presentes em formulações comerciais de tintura temporária e semi permanente. Para isto testou-se os processos sob irradiação nas regiões do ultravioleta e visível visando melhorar a eficiência destes processos e aproveitamento da luz solar. Utilizando-se concentração de 3,33x10-5 mol L-1 do corante em Na2SO4 0,10 mol L-1 pH= 2,0 sob densidade de corrente [ I ]= 1,25 mA cm-2 observa-se 100% de descoloração e 88% de remoção de COT para tratamento por oxidação fotoeletrocatalítica do corante VB51, sob radiação visível. No fotoanodo de W/WO3 observou-se 100% de remoção da cor e 83% de remoção de COT. O método foi testado para os corantes de cabelo MB16 e AB99 e, observou-se 100% de descoloração com 55% e 43% de remoção de... / In recent years, the indiscriminate use of dyes for hair dye has attracted great attention due to some toxicological and mutagenic aspects. As a result the effluent from beauty salons and domestic sewages when not properly treated can reach water treatment plants and water sources, raising concerns about human health and environmental protection. This work explores new materials to be used in the treatment of effluents contaminated with dyes hair for photocatalytic and photoelectrocatalytic techniques. Within this context, we investigated the synthesis of the Ti/TiO2 electrode through the sol-gel method, and the W/WO3 and W/WO3/TiO2 electrodes, using electrochemical methods in order to extend the range of use of these electrodes for photoexcitation in the visible region. These electrodes were characterized and applied in the photoeletrocatalytic and photocatalytic oxidation of basic hair dyes Basic Red 51(VB51), Basic Brown 16(MB16) and Basic Blue 99(AB99) present in commercial formulations of temporary and semipermanent dyeing. For this purpose, the processes were tested under irradiation in ultraviolet and visible regions, aiming to improve their efficiency to use on sunlight. Using 3.33 × 10 -5 mol L-1 dye solution in 0.10 mol L-1 Na2SO4 pH = 2.0 under current density [I] = 1.25 mA cm-2 shows 100% bleaching and 88% TOC removal for treatment by photoeletrocatalytic oxidation of the VB51 dye under visible irradiation. In W/WO3 photoanode showed 100% color removal and 83% TOC removal. The method was also tested for hair MB16 and AB99 dye, exhibiting 100% of discoloration with 55.37% and 43.11% TOC removal for W/WO3/TiO2 photoanode, and 100% and 75% of discoloration with 49% and 34% TOC removal for AB99 and MB16 dyes, respectively. The materials efficiency was also evaluated under UV irradiation and 100% of discoloration was obtained for the W/WO3/TiO2 photoanode... (Complete abstract click electronic a

Made available in DSpace on 2014-06-11T19:35:07Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-07-13Bitstream added on 2014-06-13T18:46:20Z : No. of bitstreams: 1 santos_dp_dr_araiq.pdf: 1188899 bytes, checksum: d68232ae67613f5466f8f1011c845d6e (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O Poli ácido glutâmico (PAG) é um poliaminoácido sintético formado por unidades repetitivas de glutamato, que apresentam grupos carboxilas ao longo de sua cadeia principal. A preparação de eletrodos de carbono vítreo modificados com filmes de PAG foi investigada utilizando-se três diferentes procedimentos: eletropolimerização do ácido glutâmico (MONO); deposição direta de poli ácido glutâmico (PAG) e poli ácido glutâmico:glutaraldeído (PAG:GLU) seguida de secagem a temperatura ambiente. Após secagem, o eletrodo modificado foi submetido a ciclos sucessivos entre -0,8 a +2,0 V sob velocidade de varredura de 100 mV s-1. O ácido ascórbico foi usado como composto modelo para os eletrodos modificados, os quais apresentaram um efeito eletrocatalítico na oxidação do mesmo. Os eletrodos modificados foram caracterizados por microscopia de força atômica (AFM) e espectroscopia de impedância eletroquímica (EIS). O recobrimento sobre a superfície pela adição de PAG apresentou a melhor performance exibindo filmes nanoestruturados e uniformes com baixa resistência à transferência de carga. Os eletrodos modificados por filmes PAG foram usados para estudar a oxidação do flavonóide rutina. Os resultados mostraram um par de picos redox em +0,46/+0,43 V, usado para a pré-concentração da rutina. Uma curva analítica foi obtida no intervalo de 0,9 a 9,0 μmol L-1 e o método proposto foi aplicado para análise do antioxidante em formulação farmacêutica. Os eletrodos modificados por filmes PAG foram também usados para determinação de ácido cafêico. Um par de pico redox reversível em +0,42/+0,45 V foi obtido para o ácido cafêico em tampão B-R pH 3,5. O método foi aplicado para a determinação de ácido cafêico em amostra de vinho tinto, detectando nível de concentração de 34,8μg mL-1 sem tratamento... / The poly glutamic acid (PAG) is a syntetic poliamonacid composed by repetitive glutamate units that shows carboxylic groups in the long of the principal chain. Films of PAG on the glassy carbon electrode was investigated by three diferents procedures: glutamic acid eletropomelimerization (MONO), direct deposition of the poly glutamic acid (PAG) and poly glutamic acid:glutaraldehyde (PAG:GLU), followed by drying at room temperature. After solvent evaporation, the modified electrode was submitted by cycles sucessives from -0.8 to +2.0 V at scan rate of 100 mV s-1. The ascorbic acid was used as a model compound in the modified electrodes, which presented an electrocatitic effect in the oxidation of the ascorbic acid. The modified electrodes were characterized by atomic force microscopy (AFM) and electrochemistry impedance spectroscopy (EIS). Coantings by poly glutamic acid onto the surface presented best performance by addition of PAG films that exhibits films nanostructured and uniforms with lower resistance to charge transfer. The modified electrode by PAG films were investigated to oxidation of rutin flavonoid. The results showed a redox pair of peaks at +0.46/+0.43 V, and linear analytical curve at 0.9 to 9.0 x 10-6 mol L-1. The method proposed was successful applied for rutin determination in pharmaceutical formulation. The modified electrode by PAG films was also used to determine cafeic acid. A reversible redox peak pair at +0.42/+0.45 V was obtained for cafeic acid at B-R buffer pH 3,5. The method was applied for cafeic acid determination in the red...(Complete abstract click electronic access below)

The synthesis of cobalt and manganese phthalocyanine complexes bearing eight hexylthio and four amino substituents was carried out. The formation of thin films of these complexes using different modification methods was also studied. Hexylthio functionalized metallophthalocyanine complexes were immobilized onto gold electrode surfaces using the self-assembly techniques. Surface modifications using cobalt and manganese tetraamino phthalocyanine as polymers, monolayers (onto electrografted surfaces) and as carbon nanotube – metallophthalocyanine conjugates was also carried out. The new method of modifying gold electrodes with metal tetraamino phthalocyanine complexes was investigated. The modified electrode surfaces were studied for their electrocatalytic properties and as potential electrochemical sensors for the detection of hydrogen peroxide (H₂O₂). The limits of detection for the H₂O₂ were of the orders of ~10⁻⁷ M for all the modified electrodes. The modified electrodes gave very good analytical parameters; such as good sensitivity, linearity at studied concentration range and well-defined analytical peaks with increased current densities. The modification methods were reproducible, highly conducting thin films were formed and the modified electrodes were very stable. The design of electrochemical immunosensors for the detection of measles-specific antibodies was also carried out. The modified surface with measles-antigen as sensing element was accomplished using covalent immobilization for an intimate connection of the measles-antigen as a sensing layer onto an electrode surface. Two methods of detecting measles-specific antibodies were investigated and these methods were based on electrochemical impedance, i.e. label-free detection, and voltammetric method using horse-radish peroxidase (HRP) labeled antibody as a reporter. The detection of measles-specific antibodies was accomplished using both these methods. The potential applications of the designed immunosensor were evaluated in real samples (human and newborn calf serum) and the electrodes could detect the antibodies in the complex sample matrix with ease.

Orientadores: Christiane de Arruda Rodrigues, Rodnei Bertazzoli / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-13T04:07:37Z (GMT). No. of bitstreams: 1 Figueiredo_RaulSebastiao_M.pdf: 1948808 bytes, checksum: acfbf0288c329a83e88728677892f09c (MD5) Previous issue date: 2009 / Resumo: Neste trabalho investiga-se o desempenho de eletrodos de difusão gasosa modificado com partículas de Cu, para a redução do oxigênio no processo de produção de cloro durante a eletrólise da salmoura. Para a realização dos experimentos voltamétricos foi inicialmente estudada, a reação anódica relativa à oxidação do íon cloreto. Utilizada uma célula de compartimento único, com anodo do tipo DSA com área de 1,5 cm2, contra eletrodo de EDG e eletrodo de referência de calomelano saturado (solução de KCl saturada) em solução de NaClO4 0,05 mol L-1 para a identificação do potencial de desprendimento do oxigênio. Posteriormente adicionou-se 20g/L de NaCl à solução de NaClO4 para observar o potencial de desprendimento do gás cloro na superfície do DSA. Nesses ensaios duas temperaturas foram analisadas: 25 °C e 70 °C. Na preparação dos catodos de difusão de oxigênio, foi usada uma massa precursora, composta pelo pigmento carbonoso Printex e suspensão de pó de PTFE. O catalisador introduzido foi o Cu metálico na forma de pó. O Cu foi introduzido na massa precursora utilizando diferentes métodos, na proporção de 10% m/m. Para que fosse possível chegar na porcentagem ótima de catalisador, estudos foram realizados com diferentes porcentagens de Cu (5%, 10%, 15%, 20%, 25%, 30%) sendo que a melhor foi de 10% m/m. Após as massas terem sido preparadas, os eletrodos de difusão gasosa foram sinterizados. Para a sinterização dos eletrodos de difusão gasosa (EDG) foi pesada 0,2 g da massa precursora e colocada no molde. O molde foi aquecido a uma temperatura de 340 °C para a sinterização do eletrodo, sob pressão de 146 kgf/cm2, durante 2 horas. Após a sinterização, os eletrodos foram submetidos a ensaios de permeabilidade. Em etapa subseqüente, os eletrodos de difusão gasosa foram usados nos estudos voltamétricos tendo sido submetidos a varreduras lineares de potencial de 0 a -2 V vs. ECS. Para analisar a reação de redução do oxigênio no EDG, a solução de trabalho foi 320g/L de NaOH pH 13,6. A seguir, foram realizados ensaios de eletrólise a corrente constante usando o EDG ou grafite pirolítico como catodos e o DSA como anodo. Nestes ensaios, utilizou-se uma célula com dois compartimentos, separados por uma membrana catiônica NafionÒ N242. Cada compartimento possuía um volume de 40 ml. Os eletrodos tinham área de 3,14 cm2. O anólito foi uma solução de 250 g/L NaCl com pH 3 ajustado com HCl concentrado e o católito 320 g/L NaOH. Durante as eletrólises o cloro dissolvido na forma de hipoclorito e o gás cloro foram quantificados por meio de iodometria. Nos ensaios de voltametria linear o eletrodo que obteve um melhor desempenho, foi o EDG modificado com 10 % Cu tendo mostrado uma redução de 1.95 V na diferença de potencial da célula quando comparado ao carbono pirolítico. Já com temperatura de 70°C o potencial diminuiu cerca de 1.2 V. / Abstarct: This work is investigating the performance of electrodes modified with gaseous diffusion of particles of Cu, for reduction of oxygen in the production of chlorine during the electrolysis of brine. Initially, the reaction was studied on the anodic oxidation of chloride ion. Using a single cell compartment, with the type DSA anode with an area of 1.5 cm2 as work of reference and the calomel electrode in KCl solution saturated cyclic voltammetries were performed using the NaClO4 solution of 0.05 mol L-1 for identifying the potential for evolution of oxygen. By adding 20g / L of NaCl in the solution of NaClO4 to see the potential for evolution of chlorine gas on the surface of the DSA. In these two tests were analyzed temperature: 25 °C and 70 °C. In preparing the cathodes of diffusion of oxygen, was used a mass precursor, composed of carbonaceous pigment Printex and suspension of the PTFE powder. The catalyst was introduced in the form of Cu metal powder. The Cu was introduced in the mass precursor using different methods, the proportion of 10% m / m. What could be reached in the great percentage of catalyst, studies were made with different percentages of Cu (5%, 10%, 15%, 20%, 25%, 30%) and the best was 10% m / m. After the bodies were prepared, the electrodes of gaseous diffusion were synthesized. For the sintering of the electrodes of gaseous diffusion (GDS) was weighed 0.2 g of mass precursor and placed on the mold. The mold was heated to a temperature of 340 ° C for the sintering of the electrode, under pressure of 146 kgf/cm2 for 2 hours. After sintering, the electrodes were being tested for permeability. In subsequent stage, the electrodes of gaseous diffusion were used in voltammetric studies and submitted to linear potential sweeps from 0 to-2V vs. ECS. To examine the reactions of reduction of oxygen in the GDS, the solution of work was 320g / L NaOH pH 13.6. Then, tests were performed using constant current electrolysis to the GDS or pyrolytic graphite as cathode and DSA as anode. In these tests, using a cell with two compartments, separated by a membrane cationic Nafion N242. Each compartment has a volume of 40mL. The electrodes were area of 3.14 cm2. The anolyte was a solution of 250g / L NaCl at pH 3 adjusted with concentrated HCl and the catholyte was a solution of 320g / L NaOH. During the electrolyses the chlorine dissolved in the form of hypochlorite and chlorine gas were quantified by iodometry titration. The electrode that had a better performance as a cathode, the GDS was modified with 10% Cu having shown a reduction of 1.95 V difference in potential in the cell when compared to pyrolytic carbon. Already with a temperature of 70 °C decreased the potential 1.2 V. / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Tetra-carboxy acid chloride phthalocyanine complexes of cobalt, iron and manganese were synthesized and characterized using spectroscopic and electrochemical techniques. These complexes were fabricated as thin films on gold electrode following a covalent immobilization and self-assembling methods. Surface electrochemical and spectroscopic characterization showed that these complexes are surface-confined species. The characterization using spectroscopic and electrochemical methods confirmed the formation of thiol and MPc SAMs on gold electrode. The electrocatalytic behaviour of the SAM modified gold electrodes was studied for the detection of L-cysteine and hydrogen peroxide. The limits of detection (LoD) for Lcysteine were of the orders of 10[superscript -7] mol.L[superscript -1] for all the MPc complexes studied and the LoD for hydrogen peroxide at cobalt phthalocyanine modified gold electrode was of the orders of 10[superscript -7]mol.L[superscript -1] for both electrocatalytic oxidation and reduction. The modification process for gold electrodes was reproducible and showed good stability, if stored in pH 4 phosphate buffer solutions and can be used over a long period of time. The cobalt phthalocyanine modified gold electrode was also investigated for the fabrication of glucose oxidase (GOx)-based biosensor and as an electron mediator between the enzyme and gold electrode. The behaviour of the enzyme modified gold electrode towards the detection of glucose was studied and the results gave a limit of detection of the orders of 10[superscript -6] mol.L[superscript -1] with low binding constant (4.8 mM) of enzyme (GOx) to substrate (glucose) referred to as Michaelis-Menten constant. The practical applications, i.e. the real sample analysis and interference studies, for the enzyme modified gold electrodes were investigated. These studies showed that the enzyme electrode is valuable and can be used for glucose detection.

Magister Scientiae - MSc / In this work a modified polyol method was developed to synthesize in-house catalysts. The method was modified for maximum delivery of product and proved to be quick and efficient as well as cost effective. The series of IH catalysts were characterized using techniques such as UV-vis and FT-IR spectroscopy, TEM, XRD, ICP and CV. The polyol method developed effectively reduced and deposited Pt nanoparticles onto different carbon supports. Functionalization of some of the supports was also successfully carried out through acid oxidative treatment which introduced carboxylic acid and hydroxyl groups onto the surface of the supporting material, which was supported by FT-IR which demonstrated that there was a relative increase in absorbance of functionalities viz., carboxylic acid (1270 cm-1) and hydroxyl groups on the surface of the acid treated MWCNT’s-F compared to the untreated MWCNT’s. Addition of a sedimentation promoter proved to increase the amount of metal deposition on the support thereby improving the loading dramatically. It was also found that addition of a specific amount of water in the polyol method allowed one to control the particle growth during the deposition phase on the various carbon supports investigated namely; XC-72 carbon, MWCNT’s and MWCNT’s-F. The in-house catalysts synthesized namely; Pt/C-IH, Pt/MWCNT’s-IH and Pt/MWCNT’s-F-IH all displayed narrow particle size distributions with average mean particle sizes of 2-5 nm, 2-6 nm and 3-6 nm respectively which was in good agreement with particle size measurements obtained from XRD using the Scherrer formula. All measured CV’s obtained for the series of IH catalysts prepared by this protocol were comparable with the commercial catalyst. The IH catalysts displayed the characteristic XRD peaks associated with Pt on carbon supports in acidic media. The ORR measurements for Pt/MWCNT’s-F-IH (functionalised) proved to be slightly superior (0.058 A/cm2) compared to that of the commercial catalyst (0.047 A/cm2) at a potential of 0.3V. This was attributed to the fact that the addition of water effectively controlled particle growth and deposition onto the support, and the fact that MWCNT’s-F offered a larger surface area and with the functionalized surface offering anchorage sites for Pt nanoparticles through carboxylic and hydroxyl functional groups. Further attempts to modify the developed polyol method using NaOAc as an electrostatic stabilizer to control the growth of Pt nanoparticles were made. It was found that although the stabilizer employed effectively stabilized Pt nanoparticles supported on XC-72 carbon, in our hands we were not able to produce the same results in the case of Pt supported on the MWCNT’s. TEM images revealed that Pt/CNaOAc displayed narrow particle size distribution with a mean particle size of 2-5 nm whereas particle agglomeration was observed for Pt/MWCNT’s-NaOAc and Pt/MWCNT’s-F-NaOAc with a broader particle size distribution and average mean particle sizes of 2-7 and 2-8 nm in diameter respectively. The CV’s obtained for these modified IH catalysts were in the main comparable to that of the commercial catalyst. However ORR activities of the IH Pt/C-NaOAc catalysts when carefully compared to the commercial catalyst revealed that it was indeed slightly superior (0.064 A/cm2). This is mainly attributed to the narrow particle size and even distribution of particles on the carbon support and resembled the best particle required to provide maximum activity in the ORR as a consequence of the facial kinetics involved. / South Africa

The enantioanalysis of compounds of clinical and pharmaceutical became increasingly important because the enantiomers of the same substance may be markers for different disease or are having a different pathway in the body. The utilization of enantioselective, potentiometric membrane electrodes made the assay of a single enantiomer easier and faster. Also the reliability of the analytical information is higher than that obtained using chromatographic techniques. The proposed electrodes are made by mixing graphite powder with paraffin oil to give carbon paste, which is modified by the addition of a chiral selector (e.g., cylodextrins, maltodextrins, macrocyclic antibiotics and fullerenes). This design is reliable. The high sensitivity, selectivity, enantioselectivity, accuracy and precision made them suitable to be used for the enantioanalysis of different compounds of clinical and pharmaceutical importance (e.g., L-histidine, L-cysteine and R-clenbuterol) in pharmaceutical tablets, and/or serum and urine samples. Copyright / Dissertation (MSc)--University of Pretoria, 2010. / Chemistry / unrestricted

This work describes, for the first time, the electrochemical and electrocatalytic properties of self-assembled layers of single-walled carbon nanotubes (SWCNTs) intergrated with selected organo-iron complexes and Cysteamine (Cys) forming a base on gold electrodes. The organo-iron complexes selected for this study were octa(hydroxyethylthio)phthalocyaninatoiron(II) (FeOHETPc), tetraaminophthalocyninatoiron(II) (FeTAPc), tetraaminophthalocyninatocobalt(II) (CoTAPc), ferrocene monocarboxylic acid (FMCA), ferrocene dicarboxylic acid (FDCA) or a mixture of SWCNT and FMCA or FDCA. The successful fabrication of these electrodes were established using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and electrochemical techniques such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), square wave voltammetry (SWV) and chronoamperometry (CA) The Au-Cys-SWCNT-FeOHETPc electrode exhibited strong dependence on the reaction of the head groups and the pH of the working electrolytes. The high electron transfer capability of the Au-Cys-SWCNT-FeOHETPc electrode over other electrodes as the Au-Cys-SWCNT or the Au-Cys-FeOHETPc or the Au-FeOHETPc suggests that SWCNT greatly improves the electronic communication between FeOHETPc and the bare gold electrode. The electron transfer rate constant (kapp) of Au-Cys-SWCNT-FeOHETPc in pH 4.8 conditions (~1.7 x 10-2 cm s-1) over that of the electrode obtained from SWCNT integrated with tetraaminophthalocyninatocobalt(II) (Au-Cys-SWCNT-CoTAPc) (5.1 x 10-3 cm s-1) is attributed to the possible effect of both the central metal on the phthalocyanine core and subsituents on the peripheral positions of the phthalocyanine rings. This work clearly proved that the aligned SWCNTs arrays exhibit much faster electron transfer kinetics to redox-active species in solutions compared to the randomly dispersed (drop-dried) SWCNTs. The advantageous electron transfer properties of the aligned Au-Cys-SWCNT-FeOHETPc electrode, coupled with its ease of fabrication and electrochemical stability, could be found useful in electrochemical sensing and catalysis. Thiocyanate ion was used as an analytical probe to examine the electrocatalytic properties of these modified gold electrodes. This work shows that SWCNT-FeOHETPc hybrid exhibits excellent sensitivity towards the detection of thiocyanate compared to electrodes containing SWCNT or FeTAPc or FeOHETPc only, indicating the ability of the SWCNTs to function as effective conductive nanowires for the detection of this important analyte. The electrochemical response of the FeOHETPc based electrodes was greater than their FeTAPc-based electrode counterparts, indicative of the impact of peripheral substituents on the phthalocyanine core towards electrocatalytic behaviour of these types of hybrids. Nevertheless, the exchange of the central metal as seen with the case of CoTAPc (see chapter 3), provide useful comparative electrochemical activity of this complexes versus FeTAPc with the same chemical environment with an indication of iron being the best as metal centre. FMCA or FDCA were covalently attached to the base Cysteamine monolayer to form the Au-Cys-FMCA and Au-Cys-FDCA, respectively. The same covalent attachment strategy was used to form the mixed SWCNTs and ferrocene-terminated layers (i.e., Au-Cys-SWCNT/FMCA and Au-Cys-SWCNT/FDCA). The impact of neighbouring SWCNTs on the electron transfer dynamics of the ferrocene molecular assemblies in acidic medium (0.5 M H2SO4) and in a solution (pH 7.2) of an outer-sphere redox probe ([Fe(CN)6]4-/ [Fe(CN) 6]3-) was explored. The electron transfer rate constants in both solution media essentially decrease as Au-Cys-FMCA > Au-Cys-SWCNT/FDCA > Au-Cys-FDCA > Au-Cys-SWCNT/FMCA. This trend has been interpreted in terms of several factors such as the locations of the ferrocene species in a range of environments with a range of potentials, the proximity /interactions of the ferrocenes with one another, and electrostatic interaction or repulsion existing between the negatively-charged redox probe and the modified electrodes. Square wave voltammetry was used to examine the catalytic behaviour of the electrodes. Au-Cys-SWCNT/FDCA proved to be the best electrode, possibly due to the repulsive interactions between the negatively charged SCN- and high number of surface –COOH species at the SWCNT/FDCA. This novel study has provided some useful insights as to how CNTs co-assembled with ferrocene-terminated thiols could impact on the heterogeneous electron transfer kinetics as well as the electrocatalytic detection of the self-assembled ferrocene layers. / Thesis (PhD)--University of Pretoria, 2010. / Chemistry / unrestricted

Conducting diamond electrodes provide unique advantages for electrochemistry such as a wide potential window, low baseline current, chemical inertness and resistance to fouling. De Beers boron-doped diamond electrodes, manufactured by chemical vapour deposition and containing varying amounts of boron, were therefore investigated in order to determine their suitability for future electrochemical applications. These electrodes were initially characterised using techniques such as SEM, LA-ICP-MS, Raman spectroscopy and XPS. The electrochemical behaviour of these electrodes was investigated in two redox systems (potassium iron (III) cyanide and cerium (III) sulphate) and two biological systems (dopamine and ascorbic acid). These results were compared against that of the conventional glassy carbon electrode. Porous boron-doped diamond, a novel electrode material, was used for the electrochemical detection of thyroid hormones (L-T3 and L-T4). These hormones have never previously been investigated using a boron-doped diamond electrode. The De Beers boron-doped diamond electrode was found to outperform the conventional glassy carbon electrode, which fouled very easily, in the detection of dopamine. Peak separation between dopamine and the interfering ascorbic acid was attained at a pretreated boron-doped diamond electrode. The feasibility of detecting thyroid hormones using a porous boron-doped diamond electrode was demonstrated, and the electrode material was patented. / Dissertation (MSc (Chemistry))--University of Pretoria, 2006. / Chemistry / unrestricted

The direct methanol fuel cell (DMFC) is considered to be a promising power source for portable electronic applications and transportation. At present there are several challenges that need to be addressed before the widespread commercialization of the DMFC technology can be implemented. The methanol electro oxidation reaction is sluggish, mainly due to the strong adsorption of the reaction intermediate carbon monoxide on platinum. Further, methanol crosses over to the cathode, which decreases the fuel utilization and causes cathode catalyst poisoning. Another issue is the accumulation of the reaction product CO₂ (g) in the anode, which increases the Ohmic resistance and blocks reactant mass transfer pathways. A novel anode configuration is proposed to address the aforementioned challenges. An extended reaction zone (thickness = ∼100-300 µm) is designed to facilitate the oxidation of methanol on sites that are not close to the membrane-electrode interface. Thus, the fuel concentration near the membrane may decrease significantly, which may mitigate adverse effects caused by methanol cross-over. The structure of the fibrous electrode, with its high void space, is believed to aid the disengagement of CO₂ gas. In this thesis the first objective was to deposit dispersed nanoparticle PtRu(Mo) catalysts onto graphite felt substrates by surfactant mediated electrodeposition. Experiments, in which the surfactant concentration, current density, time and temperature were varied, were conducted with the objective of increasing the active surface area and thus improving the reactivity of the electrodes with respect to methanol electro-oxidation. The three-dimensional electrodes were characterized with respect to their deposit morphology, surface area, composition and catalytic activity. The second objective of this work was to utilize the catalyzed electrodes as anodes for direct methanol fuel cell operation. The fuel cell performance was studied as a function of methanol concentration, flow rate and temperature by using a single cell with a geometric area of 5 cm². Increased power densities were obtained with an in-house prepared 3D PtRu anode compared to a conventional PtRu catalyst coated membrane. Coating graphite felt substrates with catalytically active nanoparticles and the utilization of these materials, is a new approach to improve the performance of direct fuel cells. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate