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Study on growth mechanism and characteristics of transparent conductive boron doped diamond thin filmsYeh, Kuan-Hung 28 November 2012 (has links)
This thesis presents the fabrication of transparent conductive Boron-Doped CVD diamond (BDD) thin film with the appropriate processing parameters. The BDD shows the transmittance in the visible wavelength and good electrical conductivity. The depositing rate of Diamond films yields 0.37 £gm per hour with Hydrogen, Argon, Methane and oxygen as gas sources, and B(OCH3)3 was used as the doping source. Microwave plasma chemical vapor deposition (MWCVD) was performed for the BDD deposition. Also, PECVD was applied to grow diamond-like Carbon (DLC) film on silicon as substrate. Through systematical experiments, the influence of carrier gas flow rates of B(OCH3)3, the variation of ratio of Argon, and growth pressure of BDD on the transmittance in the visible light and electrical conductivity has been studied. In addition, dc bias was applied to synthesize diamond films and extend long depositing time shows the stable growth rate of diamond films. The thickness of BDD films increases and acquired more than 60% optical transmittance. BDD samples were analyzed by Raman Spectroscopy for the diamond quality, N & K Analyzer for the film thickness and optical properties. Van Der Pauw I-V Measurement and Hall Measurement were analyzed p-type diamond films carrier mobility, carrier concentration, electrical resistivity.
By increasing Argon and applying negative dc bias can improve the growth rate and transmittance of diamond films. And the quality of diamond films could be improved by the coating of DLC on Si substrates. This work has achieved fabricating a transparent conducting BDD successfully.
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Amperomotric detection of sulfur-containing amino acids by capillary electrophoresis using boron-doped diamond microelectrodeLiu, Jung-chung 02 August 2004 (has links)
The fabrication and characterization of boron-doped diamond
microelectrodes for use in electrochemical detection
coupled with capillary electrophoresis (CE-EC) is
discussed. They exhibited low and stable background
currents and sigmoidally shaped voltammetric
curves for cysteine, cystine and Fe(CN)63-/4- .
Evaluation of the CE-EC
system and the electrode performance were accomplished
using a 10 mM borate buffer, pH 8.8, run
buffer, and a 70-cm-long fused-silica capillary (10-mm
i.d.) with seven sulfur-containing amino acids
(methionine, cysteine, cystine, homocysyeine, homocystine,
glutathionine, glutathionine disulfide) as test analytes.
Reproducible separation (elution time) and detection (peak
current) of seven sulfur-containing amino acids were observed with response precisions of 5% or less.
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THE USE OF BORON-DOPED DIAMOND FILM ELECTRODES FOR THE OXIDATIVE DEGRADATION OF PERFLUOROOCTANE SULFONATE AND TRICHLOROETHYLENECarter, Kimberly Ellen January 2009 (has links)
The current treatment of water contaminated with organic compounds includes adsorption, air stripping, and advanced oxidation processes. These methods large quantities of water and require excessive energy and time. A novel treatment process of concentrating and then electrochemically oxidizing compound would be a more feasible practice. This research investigated the oxidative destruction of perfluorooctane sulfonate (PFOS), perfluorobutane sulfonate (PFBS) and trichloroethene (TCE) at boron-doped diamond film electrodes and the adsorption of PFOS and PFBS on granular activated carbon and ion exchange resins.Experiments measuring oxidation rates of PFOS and PFBS were performed over a range in current densities and temperatures using a rotating disk electrode (RDE) reactor and a parallel plate flow-through reactor. Oxidation of PFOS was rapid and yielded sulfate, fluoride, carbon dioxide and trace levels of trifluoroacetic acid. Oxidation of PFBS was slower than that of PFOS. A comparison of the experimentally measured apparent activation energy with those calculated using Density Functional Theory (DFT) studies indicated that the most likely rate-limiting step for PFOS and PFBS oxidation was direct electron transfer. The costs for treating PFOS and PFBS solutions were compared and showed that PFOS is cheaper to degrade than PFBS.Screening studies were performed to find a viable adsorbent or ion exchange resin for concentrating PFOS or PFBS. Granular activated carbon F400 (GAC-F400) and an ion exchange resin, Amberlite IRA-458, were the best methods for adsorbing PFOS. Ionic strength experiments showed that the solubility of the compounds affected the adsorption onto solid phases. Regeneration experiments were carried out to determine the best method of recovering these compounds from the adsorbents; however, the compounds could not be effectively removed from the adsorbents using standard techniques.The electrochemical oxidation of trichloroethene (TCE) at boron-doped diamond film electrodes was studied to determine if this would be a viable degradation method for chlorinated solvents. Flow-through experiments were performed and showed TCE oxidation to be very rapid. Comparing the data from the DFT studies and the experimentally calculated apparent activation energies the mechanism for TCE oxidation was determined to be controlled by both direct electron transfer and oxidation via hydroxyl radicals.
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Electrochemical oxidation of Phenol –A Comparative Study Using Pulsed and Non-pulsed TechniquesSoma, Arpita January 2009 (has links)
No description available.
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Toxicity Evolution and Persistence from Electrochemical Treatment of Phenol with Various Electrode TypesSaylor, Greg 26 September 2011 (has links)
No description available.
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Modeling Electrochemical Water Treatment ProcessesHubler, David K. January 2012 (has links)
Several electrochemical processes are modeled at process levels and atomic scales. Processes are presented for acid generation and ion exchange media regeneration, along with corresponding process models. Transport and reaction processes in individual ion exchange beads are also modeled. Acids of mild strength (pH = ~1-2) are generated from electrolyte solutions and their strength is effectively modeled as a function of time. The regeneration of ion exchange media is also modeled, to close agreement with measurements, and the process model is reconciled with a model for solute flux from an individual ion exchange bead. Together, the models show that the "gentle" regeneration process is controlled by the plating rate. Processes interior to the particle are controlled by diffusion, but all processes are faster than the characteristic time for plating. In a separate process, an electrochemical method is used to produce hypochlorite for disinfection. The process generates perchlorate as a toxic byproduct. Density function theory is used to construct an atomic-scale model of the mechanism for producing perchlorate, as well as the aging of the boron-doped diamond anode used in the process. The mechanism shows that the boron-doped diamond surface plays an important role in chemisorbing and stabilizing radicals of oxychlorine anions, allowing the radicals to live long enough to react and form higher ions like perchlorate. Wear mechanisms that occur on the anode are shown to oxidize and etch the surface, changing its chemical functionality over time. As the surface ages, the overpotential for water oxidation is decreased, decreasing the efficiency of the electrode.
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Metal modified boron doped diamond electrodes and their use in electroanalysisToghill, Kathryn E. January 2011 (has links)
The experimental work discussed in this thesis explores the effects of metal modification on the electroanalytical ability of boron doped diamond electrodes. Boron doped diamond (BDD) electrodes have found increased application to electroanalysis in the past two decades, yet relatively little of the literature is focused on metal, nano and microparticle modification of the substrate. In this thesis three metals have been used to modify the BDD electrode; bismuth, antimony and nickel. Bismuth and antimony nanoparticle modified BDD electrodes were directly compared to unmodified BDD and a bulk bismuth electrodes in the determination of trace levels of cadmium and lead using anodic stripping voltammetry. In both instances, the modified electrode allowed for the simultaneous determination of each analyte that was otherwise unattainable at the unmodified BDD electrode. The nickel modified BDD (Ni-BDD) electrode was used in the determination of organic analytes, namely glucose, methanol, ethanol and glycerol. The nickel nano and microparticle electrodes gave the characteristic Ni(OH)₂/NiOOH redox couple in alkali pH, the oxidised form of which (NiOOH) catalysed the oxidation of the organic analytes. The chapter on glucose sensing with the Ni-BDD electrode is preceded by an extensive literature review on the advances of non-enzymatic glucose sensing, and the application of catalytic metals and nanomaterials in this field. Throughout the course of this DPhil, there has been a collaborative project between Asylum Research and myself within the Compton group to develop a commercial electrochemical atomic force microscope (EC-AFM) cell. The aim was to produce an adaptable EC-AFM cell capable of dynamic electrochemical experiments whilst simultaneously or instantaneously acquiring an AFM image of the modified surface, in-situ. This project was successful, and the EC-AFM cell has contributed to a number of chapters in this thesis, and has now been commercialised.
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Využití bórem dopované diamantové filmové elektrody k voltametrické a ampérometrické detekci aminobifenylů / The utitilization of boron-doped diamond thin film electrode for the voltammetric and amperometric determination of amino derivatives of biphenylMaixnerová, Lucie January 2010 (has links)
The aim to this work was to develop methods for the determination of 2 aminobiphenyl (2-AB), 3 aminobiphenyl (3-AB), and 4-aminobiphenyl (4-AB) in model mixtures. Concretely, the direct determination of the mixture of studied analytes has been tested using spectrophotometry and differential pulse voltammetry (DPV). Furthermore, separation and detection of 2-AB, 3-AB, and 4-AB have been performed using high performance liquid chromatography with electrochemical detection (HPLC-ED) with boron-doped diamond film thin electrode (BDDFE) in ,,wall-jet" configuration and using high performance liquid chromatography with UV detection (HPLC-UVD). It was found out that the spectrophotometric determination of 2-AB, 3-AB, and 4-AB is impossible in their mixture because of nearby values of local absorption maxima wavelengths of all three analytes studied. Upon the determination of 2-AB, 3-AB, and 4-AB in their mixture using DPV in BR buffer pH 2.0, the difference in peak potentials of 2-AB and 3-AB is too low for their determination in mixture. Upon the determination of mixture containing 2-AB and 4-AB in BR buffer pH 12.0, the limits of determination (LDs) were obtained in the concentration order of 10-6 mol.l-1 for 2-AB and 10-7 mol.l-1 for 4-AB. LDs for the mixture containing 3-AB and 4-AB were obtained in the...
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Produção eletroquímica de ozônio: investigação de aspectos fundamentais e práticos / Electrochemical ozone production: investigation of fundamental and practical aspectsSantana, Mário Henrique Palis 14 April 2005 (has links)
A caracterização ex situ e in situ de eletrodos constituídos de IrO2-Nb2O5 revelou que a morfologia, a atividade eletrocatalítica para a reação de desprendimento de O2 (RDO) e a performance para a reação de formação de O3 (RFO) são fortemente dependentes da composição nominal da camada ativa. Baseados em estudos preliminares, escolheu-se a composição IrO2-Nb2O5 (45:55 % mol) para uma extensiva investigação da RDO/RFO, avaliando a influência das variáveis de preparo do eletrodo, da temperatura e da composição do eletrólito. Propôs-se um mecanismo eletródico para RDO/RFO, considerando a influência da composição do eletrólito e dos sítios ativos superficiais. Demonstrou-se que a introdução de PF6- no eletrólito de suporte aumenta significativamente o rendimento da RFO através da inibição da RDO no domínio dos elevados sobrepotenciais. O segundo material eletródico investigado foi o eletrodo de diamante dopado com boro (DDB) de origem comercial. Este material apresenta área superficial e rugosidade sensivelmente maiores que os reportados na literatura, sendo que as diversas análises demonstram um filme de boa qualidade. O pré-tratamento da superfície de DDB resulta na remoção de impurezas e na oxidação da superfície, alterando o caráter hidrofóbico do eletrodo. Sua condutividade e comportamento eletroquímico são dependentes da concentração superficial de transportadores de carga, relacionado diretamente ao potencial aplicado. Desta forma, este eletrodo de DDB altamente dopado apresenta comportamento próximo ao de um metal em potenciais mais anódicos. Os estudos cinéticos em diversos eletrólitos e temperaturas demonstram que o eletrodo de DDB caracteriza-se pela quase ausência de sítios de adsorção ? causa dos elevados sobrepotenciais e energias de ativação para a RDO. De forma surpreendente, a introdução de flúor-ânions no eletrólito resulta na diminuição da energia de ativação para a RDO e da eficiência de corrente para a RFO. Este último parâmetro é função direta da ?eletronegatividade absoluta? dos flúor-ânions. Altas concentrações de NaF alteram a condutividade do eletrólito e a hidrofobicidade do eletrodo, afetando o comportamento cinético do ânodo. Em eletrólitos contendo KPF6, entretanto, a entropia de ativação eletroquímica parece exercer um pronunciado efeito sobre a energia de ativação da RDO. No mecanismo proposto para o eletrodo de DDB, destaca-se a importância da interação entre o principal intermediário da RDO/RFO, HO·, e a superfície do filme. / Ex situ and in situ characterisation of IrO2-Nb2O5 electrodes reveal morphology, electrocatalytical activity for the oxygen evolution reaction (OER) and electrochemical ozone production (EOP) performance are strongly dependent on nominal composition of the oxide film. Based on preliminary studies, the electrode IrO2-Nb2O5 (45:55 mol%) composition was chosen to conduct an extensive OER/EOP investigation, analysing the influence of: electrode preparation procedure, temperature and electrolyte composition. An electrode mechanism for OER/EOP is proposed taking into account the influence of the electrolyte composition and the active surface sites. It is demonstrated that the introduction of PF6- into the electrolyte increases significantly the EOP performance due to inhibition of the OER in the high overpotential domain. The second electrode material investigated is a commercial sample of the boron doped diamond electrode (BDD). This material presents surface area and roughness considerably higher than those reported in literature, however several analyses demonstrate the good quality of the film. The pre-treatment of the BDD surface results in the removal of impurities and surface oxidation, which alters the hydrophobic character of the film. Its conductivity and electrochemical behaviour depend on the surface charge carriers concentration that is directly related to the applied potential. Therefore, this heavily doped BDD sample presents a behaviour resembling a metal at more anodic potentials. Kinetic investigations of several electrolytes and temperatures show BDD electrode is characterised by the almost absence of adsorption sites ? the main cause of the high overpotentials and activation energies for OER. Surprisingly, the introduction of fluoro-anions into the electrolyte results in lower activation energies for OER and lower EOP current efficiency. The latter parameter is directly related to the ?absolute electronegativity? of the fluoro-anions. High NaF concentrations modify the electrolyte conductivity and electrode hydrophobicity. However, in electrolytes containing PF6-, the electrochemical activation entropy seems to exert a pronounced effect on the activation energy for OER. In the proposed OER/EOP mechanism at BDD electrode, a key parameter is the interaction between the main intermediate, HO·, and the electrode surface.
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Production of Expendable Reagents from Raw Waters and Industrial WastesDavis, Jake Ryan January 2014 (has links)
A couple of processes for electrosynthetic production of expendable reagents, namely acids, bases, and oxidants, from the native salt content of raw waters and industrial wastes were investigated, and the composition of mixed acids and bases made of sodium sulfate or sodium chloride salts were predicted using a model predicated on conservation principles, mass action relations, and Pitzer equations. Electrodialysis with bipolar membranes (BMED) was used to produce acids and bases in a single pass. Product concentration was limited only by the salt content of the feed water. The current efficiency for acid production was slightly higher than that for base, but neither dropped below 75%. Acid and base current utilization showed the same trends with respect to feed salt content and flow velocity, with higher efficiency at higher feed salt concentrations and flow velocities. Operating the BMED stack near the limiting current density of the bipolar membrane (BLCD) or above the limiting current density of the diluate compartment (LCD) decreased current efficiency and increased electrical power dissipation. Electrodialytic acid and base production was approximately10 times cheaper than the chemicals' f.o.b. unit costs as quoted on Alibaba.com. The mechanism and cost of on site peroxodisulfuric acid production by electrolysis of sulfuric acid solutions with boron doped diamond film anodes was investigated experimentally and with molecular dynamics (MD) and density functional theory (DFT) simulations. The cost of on site peroxodisulfate production was approximately 4 times less expensive than purchasing a 25 lb bag. It was shown that direct discharge of sulfate species produces sulfate radicals, which subsequently combined to form peroxodisulfuric acid. The likely hood of these reactions was dependent on electrode surface condition. Sulfate radicals could also be produced in solution by reaction with hydroxyl radicals generated by water discharge.
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