Thesis (M.S.)--Ohio University, March, 2006. / Title from PDF t.p. Includes bibliographical references (p. 57-58)

Ph.D. / This study explored the possible application of a relatively new electrode called exfoliated graphite electrode (EG electrode) in the electroanalysis of organic and inorganic water pollutants. This study also explored the applicability of this electrode in the removal of heavy metal pollutants in water. The EG material was successfully prepared by intercalating bisulphate ions into graphite flakes (>300 μm) followed by thermal shock at 800°C to obtain an exfoliated graphite. After compressing the EG at high pressure, the obtained circular sheets were used to fabricate electrodes. The electrochemical profiles of EG electrode and glassy carbon electrodes (GCE) were recorded and compared using cyclic voltammetryand square wave voltammetry in the presence of various supporting electrolytes and [Fe(CN)6]3-/4-, [Ru(NH3)6]2+/3+, ferrocene redox probes. In the supporting electrolytes (KCl, H2SO4, NaOH, tetrabutylammoniumtetraflouroborate, phosphate buffers), the potential windows of EG were found, in some cases, to be about 300 mV larger than that of GCE. The diffusion coefficients (cm2s-1) of the redox probes were calculated to be 3.638 x 10-6, 1.213 x 10-6 and 4.411 x 10-6 for [Fe(CN)6]3-/4-, [Ru(NH3)6]2+/3+ and ferrocene, respectively. These values are comparable to those obtained from GCE. Furthermore, EG was modified with various nanomaterials such as poly (propylene imine) dendrimer (PPI), gold nanoparticles, silver nanoparticles, dendrimer–gold nanoparticles composite, cobalt oxide and bismuth. The morphologies of the modified electrodes were studied using scanning electron microscopy and their electrochemical reactivities in the three redox probes were investigated. The current and the reversibility of redox probes were enhanced in the presence of modifiers in different degrees with dendrimer and gold nanoparticles having a favourable edge. The electrochemical determination of o-nitrophenol by square wave voltammetry using a nanocomposite of generation 2 poly(propyleneimine) dendrimer and gold nanoparticles modified GCEand EG electrode were compared. A characteristic reduction peak between -600 mV and -700 mV for o-nitrophenol was observed with enhanced current on both GCE and EG modified electrodes.

O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX) and O-isobutyl-S-2-diethylaminoethyl methylphosphonothioate (R-VX), are considered chemical warfare agents due to their strong acetylcholinesterase-inhibiting properties. Subsequent to terrorist use of these V-type nerve agents in both Japan and the United States of America (the September 11, 2001 attacks) and the limited capability of anti-terrorist groups to detect such weapons, there has been an increased obligation by the Chemical Weapons Convection for specific detection and identification methods for VX and R-VX. Chemical and/or enzymatic hydrolysis yields sulfhydryl mimic products, diethylaminoethanethiol (DEAET) and dimethylaminoethanethiol (DMAET). This thesis investigates the electrocatalytic parameters of DEAET and DMAET using basal plane pyrolytic graphite electrodes (BPPGEs) modified with: (a) single-wall carbon nanotube (BPPGE-SWCNT); (b) SWCNT functionalised with cobalt (II) tetra-aminophthalocyanine by (i) physical (BPPGE-SWCNT-CoTAPc(mix)), (ii) chemical (BPPGE-SWCNT-CoTAPc(cov)) and (iii) electrochemical adsorption (BPPGE-SWCNT-CoTAPc(ads)) processes; (c) nickel powder (BPPGE-Ni); (d) BPPGE-Ni decorated with SWCNT (BPPGE-Ni-SWCNT), and (e) SWCNT functionalised with nickel (II) tetra-aminophthalocyanine (BPPGE-SWCNT-poly-NiTAPc). Electrochemical studies (performed by voltammetric and electrochemical impedance spectroscopic techniques) revealed that the SWCNT and SWCNT-CoTAPc(mix) films showed comparable electrocatalytic responses towards the detection of DEAET and DMAET whereas competitive electrochemical behaviour was seen between SWCNT and SWCNT-NiTAPc modified BPPGEs. Using the BPPGE-SWCNT-CoTAPc(mix), the estimated catalytic rate constants (k) and diffusion coefficients (D) were higher for DEAET than for the DMAET. Also, the detection limits of approximately 8.0 and 3.0µM for DMAET and DEAET were obtained with sensitivities of 5.0×10−2 and 6.0×10−2 AM−1 for DMAET and DEAET, respectively. Unlike BPPGE-SWCNT-CoTAPc(mix) that detected the two sulfhydryls at slightly different potentials, BPPGE-SWCNT did not. The BPPGE-Ni gave enhanced Faradaic response for the redox probe ([Fe(CN)6]3−/4−) and also displayed enhanced electrocatalytic behaviour towards the detection of DMAET and DEAET with high sensitivity (~23x10−3 AM−1) and low detection limits (4.0 – 9.0 µM range). In comparison to other electrodes reported in the literature, BPPGE-Ni exhibits more promising features required for a simple, highly sensitive, fast and less expensive electrode for the detection of the hydrolysis products of V-type nerve agents in aqueous solution. The efficient response of the BPPGE-Ni is attributed to the high microscopic surface area of the nickel powder. The poor response of the BPPGE-Ni-SWCNT suggests that the nickel impurity in SWCNT did not show any detectable impact on the heterogeneous electron transfer kinetics of SWCNT. Unlike the nickel powder, SWCNT and CoTAPc-SWCNT, the NiTAPc-SWCNT hybrid did not show significant electrocatalysis towards the detection of the sulfhydryls. It is interesting, however, to observe for the first time that SWCNT induced crystallinity on the electropolymer of NiTAPc, and that such electropolymer exhibit charge-storage /-transfer properties that greatly enhance the electrochemical response of nitric oxide. / Dissertation (MSc (Chemistry))--University of Pretoria, 2008. / Chemistry / unrestricted

Abstract Electrochemical sensors are simple, fast, accurate, and low-cost analytical devices. They are especially important to the field of healthcare since they enable measurement of important indicators of patient health such as electrolytes and glucose in blood. Continued development and improvements in electrochemical sensors can result in more accessible, affordable, and effective diagnoses and treatment strategies. Electrochemical sensors employ electrodes, usually modified with a recognition agent specific for the analyte (the biomolecule of interest). The presence of the analyte at the electrode surface is typically measured through an electrochemical reaction that generates a signal in the form of an electric current or difference in electric potential. As an alternative, electrochemiluminescence, a phenomenon whereby an electrochemical reaction generates a product in an electronically excited state that is capable of emitting light, has great benefits due to its high sensitivity, selectivity, and extremely low background signal. Here we employ a camera equipped with a complementary metal-oxide semiconductor (CMOS) detector that is interfaced with a simple zoom lens to measure ECL generated at low-cost pencil graphite electrodes and small electrode arrays using tris(2,2′- bipyridyl) dichlororuthenium(II) hexahydrate ([Ru(bpy)3]2+) with tri-n-propylamine (TPA) as the coreactant. ECL signals produced at pencil graphite working electrodes were linear with respect to [Ru(bpy)3]2+ concentrations for 45–450μM [Ru(bpy)3]2+. The detection limit was found to be 2µM using the CMOS camera with exposure time set at 10s. This proof-of-concept work suggests the pencil graphite electrode with simple imaging system platform can be applied for ECL-based biosensing strategies.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24853号 / エネ博第462号 / 新制||エネ||87(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 野平, 俊之, 教授 萩原, 理加, 教授 佐川, 尚 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

Electrochemiluminescence (ECL) is a phenomenon whereby electrochemical reactions generate a product that is capable of emitting light. ECL’s high sensitivity, selectivity, extremely low background, and relatively simple instrumentation make it particularly well-suited for chemical sensing and biosensing strategies. Here we report a simple ECL imaging system based on a camera interfaced with a zoom lens to compare pencil graphite electrode (PGE) and screen-printed carbon electrode (SPCE) arrays as ECL platforms. With this system, ECL signals generated from tris(2,2′- bipyridine)ruthenium(II) chloride hexahydrate ([Ru(bpy)3]2+) using co-reactant tri-n-propylamine (TPA) were linear with respect to [Ru(bpy)3]2+ concentrations from 9 to 450 μM. Detection limits for [Ru(bpy)3]2+ were found to be 1.8 μM with PGEs and 0.9 μM with SPCEs. Immobilization of a thin polyvinylpyridine (PVP) film ECL reporter [Ru(bpy)2(PVP)10]2+ on SPCEs was also investigated. Overall, the combination of PGEs or SPCEs with the simple ECL imaging system offers a cost-effective approach to ECL-based sensing and biosensing.

O presente projeto avaliou uma célula combustível microbiana (CCM) composta de um reator combinado (anaeróbio e aeróbio), operada em fluxo contínuo com tempo de detenção hidráulico de 12 horas, alimentada com esgoto sintético (487 \'+ OU -\' 115 mg DQO/L) e esgoto sanitário (631 \'+ OU -\' 213 mg DQO/L). A estabilidade da CCM variou conforme as características do substrato aplicado. A eficiência de remoção de DQO ficou em 61 \'+ OU -\' 17; 67 \'+ OU -\' 26%, para esgoto sintético e sanitário respectivamente. Em média tensão obtida com o esgoto sintético foi de 76 mV com picos - 112,5 e 409 mV, enquanto que com o esgoto sanitário foi possível obter 52,1 mV na média e pico de geração em 325 mV. A potência variou de 10-150 mW/\'M POT.2\' com resistências entre 50-650 \'ômega\'. A geração de energia elétrica não apresentou relação linear com a DQO consumida em nenhum dos casos. A aplicação de barras de grafite como eletrodos se mostrou satisfatória na condução da corrente elétrica, o fator limitante foi a transferência de massa, principalmente a transferência de prótons do anodo para o catodo e a difusão de oxigênio para o anodo. Contudo os resultados obtidos demonstraram que é possível gerar eletricidade e, simultaneamente, tratar esgoto sanitário. / This project evaluated a microbial fuel cell (MFC) consisting of combined reactor (anaerobic and aerobic), operated in continuous flow with hydraulic detention time of 12 hours, fed with synthetic wastewater (487 \'+ OR -\' 115 mg COD/L) and wastewater (631 \'+ OR -\' 213 mg COD/L). The stability of the CCM varied according to the characteristics of the substrate applied. The efficiency of COD removal was at 61 \'+ OR -\' 17; 67 \'+ OR -\' 26 for synthetic wastewater and sawage respectively. On a average voltage obtained with synthetic wastewater was 76 mV with peaks - 112.5 and 409 mV, while the wastewater was obtained 52.1 mV on average peaks generation at 325 power was varied from 10-150 mW/\'M POT.2\' with resistances between 50-650 \'ômega\'. The power generation showed no liner relationship with the COD consumed in any case. The application of graphite rods as electrodes were satisfactory in the conduction of electrical of protons from the anode to the cathode and the diffusion of oxygen to the anode. However the results showed that it is possible to generate electricity while simultaneously treating sewage.

O presente projeto avaliou uma célula combustível microbiana (CCM) composta de um reator combinado (anaeróbio e aeróbio), operada em fluxo contínuo com tempo de detenção hidráulico de 12 horas, alimentada com esgoto sintético (487 \'+ OU -\' 115 mg DQO/L) e esgoto sanitário (631 \'+ OU -\' 213 mg DQO/L). A estabilidade da CCM variou conforme as características do substrato aplicado. A eficiência de remoção de DQO ficou em 61 \'+ OU -\' 17; 67 \'+ OU -\' 26%, para esgoto sintético e sanitário respectivamente. Em média tensão obtida com o esgoto sintético foi de 76 mV com picos - 112,5 e 409 mV, enquanto que com o esgoto sanitário foi possível obter 52,1 mV na média e pico de geração em 325 mV. A potência variou de 10-150 mW/\'M POT.2\' com resistências entre 50-650 \'ômega\'. A geração de energia elétrica não apresentou relação linear com a DQO consumida em nenhum dos casos. A aplicação de barras de grafite como eletrodos se mostrou satisfatória na condução da corrente elétrica, o fator limitante foi a transferência de massa, principalmente a transferência de prótons do anodo para o catodo e a difusão de oxigênio para o anodo. Contudo os resultados obtidos demonstraram que é possível gerar eletricidade e, simultaneamente, tratar esgoto sanitário. / This project evaluated a microbial fuel cell (MFC) consisting of combined reactor (anaerobic and aerobic), operated in continuous flow with hydraulic detention time of 12 hours, fed with synthetic wastewater (487 \'+ OR -\' 115 mg COD/L) and wastewater (631 \'+ OR -\' 213 mg COD/L). The stability of the CCM varied according to the characteristics of the substrate applied. The efficiency of COD removal was at 61 \'+ OR -\' 17; 67 \'+ OR -\' 26 for synthetic wastewater and sawage respectively. On a average voltage obtained with synthetic wastewater was 76 mV with peaks - 112.5 and 409 mV, while the wastewater was obtained 52.1 mV on average peaks generation at 325 power was varied from 10-150 mW/\'M POT.2\' with resistances between 50-650 \'ômega\'. The power generation showed no liner relationship with the COD consumed in any case. The application of graphite rods as electrodes were satisfactory in the conduction of electrical of protons from the anode to the cathode and the diffusion of oxygen to the anode. However the results showed that it is possible to generate electricity while simultaneously treating sewage.