Dissertations / Theses on the topic 'Electrochemical apparatus'

The objective of this research was to design and evaluate an instrumental method for electroanalysis in highly resistive media. A coulostatic detector for high performance liquid chromatography was designed and constructed. Equations were developed to describe the detector's performance under regenerative and nonregenerative experimental conditions. With mobile phases of high resistance, the detector was found to respond to both electroactive and ionic electroinactive species with the magnitude of the observed signal depending on the recent history of the electrode. Thus, the elimination of iR drop by the coulostatic method does not provide a straightforward method for electroanalysis in highly resistive media. At low electrolyte concentrations, double-layer effects become prominent. A method was devised to quantitate the static double-layer effect at solid electrodes.

Recently, there has been a growing demand for electrode materials to serve as electrochemical capacitors (EC). It has been an important issue to come up with environment friendly electric power sources to reduce pollution caused by combustion engines of automotive systems. Even though conventional battery systems and fuel cells supply high energy, they lack the high specific power that would be required for hybrid power sources. The ECs can fill the gap between conventional capacitors and batteries.
Carbon nanotubes (CNTs), discovered by Iijima in 1991, attracted great attention in recent years for their unique properties, such as mesoporous character, excellent conductivity, moderate to high specific surface area as well as chemical and mechanical stability. These properties of CNTs make them useful in a wide of range applications including electrode materials for EC applications.
The preparation of CNT electrodes is accomplished by either pasting them onto metallic current collectors with the use of binder materials such as PVDF or growing them from deposited metal nanoparticles on substrates such as graphite paper. The deposition of metal nanoparticles is achieved via sputtering techniques or lengthy electrochemical deposition methods. The aim of this research was to simplify the preparation step by growing CNTs directly on metallic substrates and to study the relationship between surface area and electrochemical capacitance of CNTs. CNTs were produced on metal-alloy grids via chemical vapor deposition (CVD) of acetylene (C2H2). The physical characterization of the samples was achieved by Field Emission Scanning Electron Microscopy (FE-SEM), Raman spectroscopy and Single point BET surface area. The electrochemical performance of the samples was evaluated by cyclic voltammetry (CV) in a three electrode electrochemical cell with 1M sulfuric acid (H2SO4) solution as the electrolyte.

A new versatile computer controlled electrochemlcal/ESR data acquisition system has been developed for the Investigation of short-lived radicals with life-times of 20 milliseconds and greater, Different computer programs have been developed to monitor the decay of radicals; over hours or minutes, seconds or milliseconds. Signal averaging and Fourier smoothing is employed in order to improve the signal to noise ratio. Two microcomputers are used to control the system, one home-made computer containing the M6800 chip which controls the magnetic field, and an IBM PC XT which controls the electrochemistry and the data acquisition. The computer programs are written in Fortran and C, and call machine language subroutines, The system functions by having the radical generated by an electrochemical pulse: after or during the pulse the ESR data are collected. Decaying radicals which have half-lives of seconds or greater have their spectra collected in the magnetic field domain, which can be swept as fast as 200 Gauss per second. The decay of the radicals in the millisecond region is monitored by time-resolved ESR: a technique in which data is collected in both the time domain and in the magnetic field domain. Previously, time-resolved ESR has been used (without field modulation) to investigate ultra-short-lived species with life-times in the region of only a few microseconds. The application of the data acquisition system to chemical systems is illustrated. This is the first time a computer controlled system whereby the radical is generated by electrochemical means and subsequently the ESR data collected, has been developed.

Combined atomic force microscopy-scanning electrochemical microscopy (AFM-SECM) is capable of providing simultaneous topographical and electrochemical imaging at sample surfaces. Integration of amperometric biosensors at tip-integrated electrodes recessed from the apex of the AFM tip further enhances the versatility of such bifunctional probes. Of particular interest to this work was the detection of adenosine triphosphate (ATP) at a cellular level, since ATP is involved in many biologically relevant processes. There are challenges concerning the integration of biosensors into bifunctional AFM-SECM probes. This thesis focuses on addressing and advancing several of these limitations. Thin insulation layers are important for AFM-SECM based applications to enhance AFM and SECM performance. Plasma-polymerized fluorocarbon membranes are introduced as novel thin film insulation materials for AFM-SECM probes. Insulation layers with a thickness of < 300 nm were found to exhibit excellent insulating properties and satisfying temporal stability for successful application in AFM-SECM experiments. Furthermore new approaches for increasing the electrode area in conventionally focused ion beam (FIB) fabricated AFM-SECM probes were implemented, since enhancement of the current response in conjunction with biosensing experiments is required. Ion beam induced deposition (IBID) was used to generate platinum carbon (PtC) deposits at AFM-SECM probes, thereby successfully increasing the tip-integrated electrode area. PtC composites were thoroughly characterized in terms of their physical and electrochemical properties. Since a high carbon fraction in the PtC composite was inhibiting the charge transfer kinetics at the electrode surface for certain analytes, several pre-treatment strategies were investigated including annealing, UV/ozone treatment, and FIB milling. FIB milling proved to be the most promising procedure improving charge transfer properties at the electrode along with fabrication compatibility at AFM-SECM probes. The last part of this thesis aimed at providing fundamental studies on AFM-SECM application at live epithelial cell monolayers. AFM was used in different imaging modes to characterize the topography of epithelial cells. ATP detection at epithelial cells was achieved with amperometric biosensors combined with non-invasive SECM. Biosensors were further miniaturized at batch-fabricated AFM-SECM probes enabling laterally-resolved detection of ATP at epithelial cells. Additionally, PtC composite materials were evaluated for applicability as transducer platforms for enzymatic biosensors.

Point-of-Care diagnostic tests enable monitor health conditions and obtain fast results close to the patient, reducing medical costs, and allowing the control of infectious outbreaks. The interest in developing Point-of-Care devices is increasing due to they are suitable for a wide variety of applications. This doctoral thesis focuses on the development of Plug-and-Power electronic readers (e- readers) for electrochemical detections and the demonstration of their possibilities as Point-of-Care diagnostic testing. The solutions proposed in this study make it possible to improve Point-of-Care tests whose premises are laboratory decentralization, personalized medicine, rapid diagnosis, and improvement of patient care. Developed electronic readers can be powered from a conventional system, such as a USB port or a lithium battery, or can be defined as self-powered systems, capable of extracting energy from alternative energy sources, such as fuel cells, defining Plug-and-Power systems. The designed electrochemical detection devices in this thesis are based on low-power consumption electronic instrumentation circuits. These circuits are capable of controlling the sensing element, measuring its response, and representing the result quantitatively. The implemented devices can work with both electrochemical sensors and fuel cells. Furthermore, it is possible to adapt its measurement range, enabling its use in a wide variety of applications. Thanks to their reduced energy consumption, some of these developments can be defined as self-powered platforms able to operate only with the energy extracted from the biological sample, which in turn is monitored. These devices are easy-to-use and plug-and-play, enabling those unskilled individuals to carry out tests after prior training. Moreover, thanks to their user-friendly interface, results are clear and easy to understand. This doctoral dissertation is presented as an article compendium and composed of three publications detailed in chronological order of publication. The first contribution describes an innovative portable Point-of-Care device able to provide a quantitative result of the glucose concentration of a sample. The proposed system combines an e-reader and a disposable device based on two elements: a glucose paper-based power source, and a glucose fuel cell-based sensor. The battery-less e-reader extracts the energy from the disposable unit, acquires the signal, processes it, and shows the glucose concentration on a numerical display. Due to low-power consumption of the e-reader, the whole electronic system can operate only with the energy extracted from the disposable element. Furthermore, the proposed system minimizes the user interaction, which only must deposit the sample on the strip and wait a few seconds to see the test result. The second publication validates the e-reader in other scenarios following two approaches: using fuel cells as a power element, and as a dual powering and sensing element. The device was tested with glucose, urine, methanol, and ethanol fuel cells and electrochemical sensors in order to show the adaptability of this versatile concept to a wide variety of fields beyond clinical diagnostics, such as veterinary or environmental fields. The third study presents a low-cost, miniaturized, and customizable electronic reader for amperometric detections. The USB-powered portable device is composed of a full- custom electronic board for signal acquisition, and software, which controls the systems, represents and saves the results. In this study, the performance of the device was compared against three commercial potentiostats, showing comparable results to those obtained using three commercial systems, which were significantly more expensive. As proof of concept, the system was validated by detecting horseradish peroxidase samples. However, it could be easily extended its scope and measure other types of analytes or biological matrices since it can be easily adapted to detect currents a wide range of currents.
Las pruebas de diagnostico Point-of-Care permiten monitorizar las condiciones de salud y obtener resultados rápidos cerca del paciente, reduciendo los costes médicos y permitiendo controlar brotes infecciosos. El interés por desarrollar dispositivos de Point- of-Care está aumentando debido a que son aplicables a una amplia variedad de aplicaciones. Esta tesis doctoral se centra en el desarrollo de lectores electrónicos (e-readers) Plug-and- Power para detecciones electroquímicas y la demostración de sus posibilidades como pruebas de diagnóstico de punto de atención (Point-of-Care). Las soluciones propuestas en este trabajo permiten mejorar las pruebas Point-of-Care, cuyas premisas son la descentralización de laboratorio, la medicina personalizada, el diagnóstico rápido y la mejora de la atención al paciente. Los lectores electrónicos desarrollados pueden ser alimentados desde un sistema convencional, como puede ser un puerto USB o una batería de litio, o definirse como sistemas autoalimentados, capaces de extraen energía de fuentes alternativas de energía, como celdas de combustible (fuel cells), definiendo así sistemas Plug-and-Power. Los dispositivos de detección electroquímica diseñados se basan en circuitos de instrumentación electrónica de bajo consumo. Estos circuitos son capaces controlar el elemento de sensado, medir su respuesta y representar el resultado de forma cuantitativa. Los dispositivos implementados pueden trabajar tanto con sensores electroquímicos como con fuel cells. Además, es posible adaptar su rango de medida, permitiendo su utilización en una amplia variedad de aplicaciones. Gracias a su reducido consumo de energía, algunos de estos desarrollos pueden definirse como plataformas autoalimentadas capaces de operar solo con la energía extraída de la muestra biológica, que a su vez es monitorizada. Estas plataformas electrónicas son fáciles de usar y Plug-and-Play, permitiendo que personas no cualificadas puedan utilizarlas después de un previo entrenamiento. Además, gracias a su interfaz fácil de usar, los resultados son claros y fáciles de interpretar.

The thin-layer flow-cell incorporated an array of 32 gold strip electrodes in a serial configuration opposite a platinum counter electrode. The cell body was made of Macor glass ceramic. A photolithographic procedure for etching the Macor and a simple method of applying a gold ink was devised. Resistive feedback current-to-voltage converters independently controlled the potential difference between the electrodes of the array and the common counter electrode. A microcomputer and a customized high speed data acquisition interface recorded the current response of each electrode. An expression for the faradaic response of a single electrode within a rectangular flow channel was modified to predict the behavior of the multi-electrode flow-cell. The quinone/hydroquinone redox system was used to evaluate the performance of the detector. Summing the signals from the array when all electrodes were held at the same potential improved the signal-to-noise ratio. Hydrodynamic curves were reconstructed from the currents measured at each electrode when a ramp potential profile was applied to the array.

Fluctuation in the demand for electrical power and the intermittent nature of the supply of energy from renewable sources like solar and wind have made the need for energy storage a dire necessity. Current storage technologies like batteries and supercapacitors fall short either in terms of power output or in their ability to store sufficient energy. Pseudocapacitors combine features of both and offer an alternative to stabilize the power supply. They possess high rates of charge and discharge and are capable of storing much more energy in comparison to a supercapacitor. In the quest for solutions that are economical and feasible, we have investigated Prussian Blue in aqueous electrolytes for its use as a pseudocapacitor. Two different active materials based on Prussian Blue were prepared; one that has just Prussian Blue and the other that contains a mixture of Prussian Blue and carbon nanotubes (CNTs). Four electrolytes differing in the valence of the cation were employed for the study. Cyclic voltammetry and galvanostatic charge-discharge were used to characterize the electrodes. Our experiments have shown specific capacitances of Prussian Blue electrodes in the range of 140-720 F/g and that of Prussian Blue-CNT electrodes in the range of ~52 F/g. The remarkable capacity of charge storage in Prussian Blue electrodes is attributed to its electrochemical activity ensuring surface redox and its tunnel-like structure allowing ease of entry and exit for ions like Potassium. Simple methods of synthesis have yielded specific capacitances of the order of hundreds of Farads per gram showing that Prussian Blue has promise as an electrode material for applications needing high rates of charge-discharge.

High temperature proton conducting perovskite oxides are very attractive materials for applications in electrochemical devices, such as solid oxide fuel cells (SOFCs) and hydrogen permeation membranes. A better understanding of the hydrogen oxidation mechanism over the metal/proton conductor interface, is critical for rational design to further enhance the performances of the applications. However, kinetic studies focused on the metal/proton system are limited, compared with the intensively studied metal/oxygen ion conductor system, e.g., Ni/YSZ (yttrium stabilized zirconia, Zr₁-ₓYₓO₂-δ). This work presents an elementary kinetic model developed to assess reaction pathway of hydrogen oxidation/reduction on metal/proton conductor interface. Individual rate expressions and overall hydrogen partial pressure dependencies of current density and polarization resistance were derived in different rate limiting cases. The model is testified by tailored experiments on Pt/BaZr₀.₁Ce₀.₇Y₀.₁Yb₀.₁O₃-δ (BZCYYb) interface using pattern electrodes. Comparison of electrochemical testing and the theoretical predictions indicates the dissociation of hydrogen is the rate-limiting step (RLS), instead of charge transfer, displaying behavior different from metal/oxygen ion conductor interfaces. The kinetic model presented in this thesis is validated by high quantitative agreement with experiments under various conditions. The discovery not only contributes to the fundamental understanding of the hydrogen oxidation kinetics over metal/proton conductors, but provides insights for rational design of hydrogen oxidation catalysts in a variety of electrochemical systems.

Han, Zuoyan.
Thesis (Ph.D.)--Chinese University of Hong Kong, 2011.
Includes bibliographical references (leaves 75-81).
Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Abstract also in Chinese.