The heart is one of the most important organs of the human body and cardiovascular diseases remain the biggest cause of deaths worldwide. Today, due to the aging of the population and the growing demand for cardiovascular implants, improving the performance of artificial surfaces of vascular prostheses is highly desired. The common material for fabricating prostheses, such as stents used to remedy narrow and weak arteries, is Fluorocarbon polymers or expanded Polytetrafluoroethylene (ePTFE, Gore-tex). Although these polymers are well known for chemical inertness, thermal stability and low friction, they can cause early thrombosis (forming clot) and coagulation in blood vessels and require periodic replacement. Modifying the surface properties of Polytetrafluoroethylene (PTFE) by coating with carbon-based materials may improve its blood compatibility. Carbon-based coatings have properties similar to biomedical components, such as low friction, bioinertness, high wear resistance and exceptional hardness. Plasma processing methods are commonly used for coating thin films on various materials including carbon-based components. Plasma-based processes are also widely used in the aerospace, automotive, steel and biomedical industries. For example, extending the lifetime of surgically implanted hip joints and cutting tools are biomedical and industrial applications of plasma-based material processing respectively. Plasma-assisted deposition techniques are commonly used for carbon-based coating including nitrogen-doped amorphous carbon (a-C) films. In this thesis, PTFE samples with different thickness and roughness characteristics are used as substrates and diamond-like carbon (DLC) is deposited on them by simultaneous plasma-assisted sputtering and chemical vapour deposition (CVD). Hot filament plasma and ICP (Inductively coupling plasma) are used to coat DLC on PTFE and silicon (Si) substrates under various plasma conditions. The latter is the first report on the techniques to coat DLC by ICP plasma sputtering. This new technique (ICP-sputtering) is developed to improve low deposition rate and high temperature deposition of previous method (Hot filament plasma sputtering). Advantageous of this new developed method (ICP-sputtering) are discussed and compared with the previous method in this thesis. Various amount of nitrogen is introduced to the plasma chambers and the effect of nitrogen dopant is also studied using different characterization techniques for chemical, electronic and morphological properties of coated films. sp2 and sp3 contents were also estimated in amorphous carbon (a-C) and nitrogenated amorphous carbon (a-CN) films. Characterization techniques used for in this thesis are including SEM (scanning electron microscopy), AFM (atomic force microscopy), Raman spectroscopy, XAS (x-ray absorption spectroscopy), XES (x-ray emission spectroscopy), XPS (x-ray photoelectron spectroscopy) and XRD (x-ray diffraction).

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第13834号 / 工博第2938号 / 新制||工||1434(附属図書館) / 26050 / UT51-2008-C750 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 井上 正志, 教授 江口 浩一, 教授 田中 庸裕 / 学位規則第4条第1項該当

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Screen printed electrodes (SPEs), which are prepared by patterning conductive inks or pastes onto an insulating support (e.g., plastic film), are widely employed as sensing and biosensing platforms due to their ease of fabrication and relatively low cost. This is especially applicable to electrodes of this nature prepared with carbon-based inks (SPCEs). To date, the most successful and significant commercial application of SPEs has been as test strips for glucose meters. Despite the maturity of this technology, SPE research remains very active as improvements in sensitivity and selectivity, which often involve modifying the electrode surface, hold the key to advancing their utility in routine applications and extending their benefits to other target analytes. Recent studies in the Bishop research group have demonstrated that nitrogen-doped SPCEs (N-SPCEs) exhibit enhanced electrochemical response towards hydrogen peroxide (H2O2), a product of oxidase enzyme (e.g., glucose oxidase, lactate oxidase, etc.) reactions and a common target in biosensing strategies. The presence of nitrogen heteroatoms on the carbon surface facilitates breakage of oxygen-oxygen bonds, a key step in reduction of H2O2. Since previous studies showed only modest incorporation of nitrogen species on SPCEs prepared from commercial ink, these studies aim to investigate the possibility of enhancing N-doping by performing a simple pre-treatment strategy that reportedly increases surface oxygen content of SPCEs prior to N-doping. Since surface oxygen sites have been previously reported to be preferentially modified with nitrogen during N doping strategies, this seems like a promising technique for improving sensitivity of N-SPCEs for H2O2 reduction. To quantify the actuality of these claims, experimental groups were fabricated having undergone no enhancement, pretreatment enhancement only, nitrogen-doping enhancement only, and a combination of the pretreatment and nitrogen-doping enhancements. Here the electrochemical behaviors of pretreated SPCEs, N-SPCEs, and pretreated N-SPCEs for the detection of H2O2 by completing comparative cyclic voltammetry (CV) experiments with and without the presence of H2O2 and with it present in varying concentrations is compared. It is projected that, if successful, the fabricated electrodes that have undergone both the pretreatment protocol and the nitrogen-doping process will have an increased sensitivity and detection limit towards H2O2.

Screen printed electrodes (SPEs), which are prepared by patterning conductive inks or pastes onto an insulating support (e.g., plastic film), are widely employed as sensing and biosensing platforms due to their ease of fabrication and relatively low cost. This is especially applicable to electrodes of this nature prepared with carbon-based inks (SPCEs). To date, the most successful and significant commercial application of SPEs has been as test strips for glucose meters. Despite the maturity of this technology, SPE research remains very active as improvements in sensitivity and selectivity, which often involve modifying the electrode surface, hold the key to advancing their utility in routine applications and extending their benefits to other target analytes. Recent studies in the Bishop research group have demonstrated that nitrogen-doped SPCEs (N-SPCEs) exhibit enhanced electrochemical response towards hydrogen peroxide (H2O2), a product of oxidase enzyme (e.g., glucose oxidase, lactate oxidase, etc.) reactions and a common target in biosensing strategies. The presence of nitrogen heteroatoms on the carbon surface facilitates breakage of oxygen-oxygen bonds, a key step in reduction of H2O2. Since previous studies showed only modest incorporation of nitrogen species on SPCEs prepared from commercial ink, these studies aim to investigate the possibility of enhancing N-doping by performing a simple pre-treatment strategy that reportedly increases surface oxygen content of SPCEs prior to N-doping. Since surface oxygen sites have been previously reported to be preferentially modified with nitrogen during N-doping strategies, this seems like a promising technique for improving sensitivity of N-SPCEs for H2O2 reduction. To quantify the actuality of these claims, experimental groups were fabricated having undergone no enhancement, pretreatment enhancement only, nitrogen-doping enhancement only, and a combination of the pretreatment and nitrogen-doping enhancements. Here the electrochemical behaviors of pretreated SPCEs, N-SPCEs, and pretreated N-SPCEs for the detection of H2O2 by completing comparative cyclic voltammetry (CV) experiments with and with out the presence of H2O2 and with it present in varying concentrations is compared. It is projected that, if successful, the fabricated electrodes that have undergone both the pretreatment protocol and the nitrogen-doping process will have an increased sensitivity and detection limit towards H2O2.

Metal nanoparticles have been a primary focus in areas of catalysis and electrocatalysis applications as a result of their large surface area-to-volume ratios. While there is an increased interest in understanding the properties and behaviors of metal nanoparticles, they can become expensive over time. Recent research has incorporated the idea of using heteroatom-doped materials as a cheaper catalytic alternative to metal nanoparticles. In this study nitrogen-doping and phosphorous-doping techniques were applied to chemical vapor-deposited carbon ultramicroelectrodes in order to study the electrocatalytic properties toward the oxygen reduction reaction and the enhanced affinity for the deposition of gold nanoparticles onto the electrodes.

Nitrogen-doped carbon materials have garnered much interest due to their abilities to behave as electrocatalysts for reactions important in energy production (oxygen reduction) and biosensing (hydrogen peroxide reduction). Here, we demonstrate fabrication methods and determine electrocatalytic properties of nitrogen-doped screen-printed carbon (N-SPCE) electrodes. Nitrogen doping of graphite was achieved through a simple soft-nitriding technique which was then used in lab-formulated screen-printing inks to prepare N-SPCEs. N-SPCEs displayed good electrocatalytic activity, reproducibility and long term stability towards the electrochemical reduction of hydrogen peroxide. N-SPCEs exhibited a wide linear range (20 µM to 5.3 mM), reasonable limit of detection of 2.5 µM, with an applied potential of -0.4 V (vs. Ag/AgCl). We also demonstrate that nitrided-graphite can similarly be used as a platform for the deposition of electrocatalytic platinum nanoparticles, resulting in Pt-N-SPCEs with a lower limit of detection (0.4 µM) and better sensitivity (0.52 µA cm-2 µM-1) towards H2O2 reduction.

Supercapacitor is the best potential candidate of the energy storage system due to the superior charge or discharge efficiency, high power density (>10 kW kg-1), and long cycling life. Porous carbon materials as the promising electrode material have been widely used in supercapacitor. In fact, conventional porous carbon supercapacitor electrodes cannot fulfil the growing demand of high energy and power densities of supercapacitor. A large number of studies show that nitrogen doping can change the surface electronic structure of carbon materials, thus significantly improving the electrochemical properties. In addition to, the pore structure and morphology of carbon materials have great influence on the electrochemical performance. In this work, we firstly fabricated nitrogen-doped porous carbon nanotubes by using a simple mixed salts (NaCl/ZnCl2) activation strategy. The as-obtained porous carbon nanotubes exhibited excellent electrochemical performance in supercapacitor. Furthermore, two- dimension nitrogen-doping porous nanosheets were prepared by a salt template-assisted monomer deposition method. In this study, by optimizing the synthesis conditions, the as-obtained carbon nanosheets showed a high specific capacitance of 277 F g-1 at 1 A g-1 and excellent cycle stability retained 91 % after 10,000 cycles. / College of Engineering, Science and Technology / M. Tech.( Civil and Chemical Engineering

This study reports on the synthesis of N-doped carbon spheres (N-CSs) by a simple synthetic procedure. A horizontal CVD type reactor was used to synthesize N-CSs from pyridine. Depending on the dilution of the pyridine with toluene, a nitrogen content of 0.13-5 mol % was obtained. The use of a vertical CVD reactor gave N-CSs with a N-content of 0.19-3 mol % when an ammonium solution and acetylene were used as reactants. The diameters of carbon spheres were found to be in the range of 40 nm to 1000 nm for both CVD reactors. The diameter can be controlled by varying the flow rate, temperature, time, concentration and the reactor type. The samples were characterized by TEM, HRTEM, elemental analysis, Raman spectroscopy, TGA, PXRD and ESR. We have demonstrated that unsubstituted thiophene can be polymerized by Fe3+-catalyzed oxidative polymerization. The average particle size was about 50 nm, within a narrow particlesize distribution. The undoped carbon spheres (CSs) were reacted with thiophene to give polymer/carbon composites containing polythiophene and carbon nanospheres via chemical oxidative polymerization reaction. Polythiophene molecules were either chemically bonded or physically adsorbed to the surface of carbon spheres. The microstructure and properties of the two types of composites were compared. The thermogravimetric analysis data confirmed that the presence of CSs in the polymer\carbon composites is responsible for the higher thermal stability of the composite material in comparison with pristine polythiophene. The FTIR analysis showed that covalent functionalized nanocomposites exhibit a high intensity of a C-S bond This study reports on the synthesis of N-doped carbon spheres (N-CSs) by a simple synthetic procedure. A horizontal CVD type reactor was used to synthesize N-CSs from pyridine. Depending on the dilution of the pyridine with toluene, a nitrogen content of 0.13-5 mol % was obtained. The use of a vertical CVD reactor gave N-CSs with a N-content of 0.19-3 mol % when an ammonium solution and acetylene were used as reactants. The diameters of carbon spheres were found to be in the range of 40 nm to 1000 nm for both CVD reactors. The diameter can be controlled by varying the flow rate, temperature, time, concentration and the reactor type. The samples were characterized by TEM, HRTEM, elemental analysis, Raman spectroscopy, TGA, PXRD and ESR. We have demonstrated that unsubstituted thiophene can be polymerized by Fe3+-catalyzed oxidative polymerization. The average particle size was about 50 nm, within a narrow particlesize distribution. The undoped carbon spheres (CSs) were reacted with thiophene to give polymer/carbon composites containing polythiophene and carbon nanospheres via chemical oxidative polymerization reaction. Polythiophene molecules were either chemically bonded or physically adsorbed to the surface of carbon spheres. The microstructure and properties of the two types of composites were compared. The thermogravimetric analysis data confirmed that the presence of CSs in the polymer\carbon composites is responsible for the higher thermal stability of the composite material in comparison with pristine polythiophene. The FTIR analysis showed that covalent functionalized nanocomposites exhibit a high intensity of a C-S bondThis study reports on the synthesis of N-doped carbon spheres (N-CSs) by a simple synthetic procedure. A horizontal CVD type reactor was used to synthesize N-CSs from pyridine. Depending on the dilution of the pyridine with toluene, a nitrogen content of 0.13-5 mol % was obtained. The use of a vertical CVD reactor gave N-CSs with a N-content of 0.19-3 mol % when an ammonium solution and acetylene were used as reactants. The diameters of carbon spheres were found to be in the range of 40 nm to 1000 nm for both CVD reactors. The diameter can be controlled by varying the flow rate, temperature, time, concentration and the reactor type. The samples were characterized by TEM, HRTEM, elemental analysis, Raman spectroscopy, TGA, PXRD and ESR. We have demonstrated that unsubstituted thiophene can be polymerized by Fe3+-catalyzed oxidative polymerization. The average particle size was about 50 nm, within a narrow particlesize distribution. The undoped carbon spheres (CSs) were reacted with thiophene to give polymer/carbon composites containing polythiophene and carbon nanospheres via chemical oxidative polymerization reaction. Polythiophene molecules were either chemically bonded or physically adsorbed to the surface of carbon spheres. The microstructure and properties of the two types of composites were compared. The thermogravimetric analysis data confirmed that the presence of CSs in the polymer\carbon composites is responsible for the higher thermal stability of the composite material in comparison with pristine polythiophene. The FTIR analysis showed that covalent functionalized nanocomposites exhibit a high intensity of a C-S bond at 695 cm-1 , which is not observed in the noncovalent functionalized nanocomposites

Le couplage direct de la séparation et de la photo-catalyse en utilisant des membranes à base de dioxyde de titane, est une approche intéressante habituellement appliquée dans les dispositifs de traitement de l'eau, et récemment envisagée pour d’autres applications, telle que la production d’hydrogène par photo-électrolyse de l’eau. En effet, le dioxyde de titane (TiO2) est bien connu pour ses propriétés photo-catalytiques. En outre, s’il est immobilisé sur support membranaire plutôt qu’utilisé en suspension, son intégration en procédé de séparation est facilitée, sans compter les gains apportés au procédé en termes de compacité, d’intégrité et de capacité séparative. Pour une telle application, des cellules originales sous forme de multicouches sont requises. Certains systèmes sont décrits dans la littérature mais aucun d’entre eux n’est réellement intégré (c’est-à-dire basé sur une géométrie de type multicouche micro-architecturée), ni formé de couches minces obtenus par procédés plasma. Or les procédés plasma sont généralement compétitifs pour l’obtention de systèmes multicouches de hautes intégrité et compacité. Dans le cadre de récents travaux menés à l’IEM, différents types de couches minces ont été préparés par PECVD (Plasma Enhanced Chemical Vapor Deposition), à savoir des films de TiO2 connus pour leurs propriétés photo-catalytiques et des membranes phosphoniques de conduction protonique avérée. En outre, des films minces de platine efficaces pour la réduction catalytique des protons en hydrogène peuvent être également déposés par un autre procédé plasma, la pulvérisation cathodique. Au cours de ce travail de thèse, des films de TiO2 obtenus par PECVD Basse Fréquence sont optimisés en termes d’activité photo-catalytique et de propriétés séparatives; cette optimisation, qui concerne le dopage à l’azote du TiO2 (permettant le déplacement de la bande interdite de la région UV vers la région visible), est le premier objectif de ce projet de thèse. Les films minces sont caractérisés du point de vue de leurs propriétés structurales et fonctionnelles. Le second objectif de la thèse est de montrer l’intérêt de ces films de TiO2 dans la production/séparation d’hydrogène par voie solaire. Dans ce but, la photo-activité des films dans le noir, sous UV et sous visible est étudiée dans une cellule mono-compartiment où les deux électrodes baignent dans un électrolyte liquide. Des études électrochimiques plus poussées en présence d’une membrane électrolyte commerciale et d’une cathode de platine (dont les caractérisations en propre sont portées en annexes de ce travail), sont aussi abordées. Le dernier objectif de cette thèse est le transfert de la technologie des procédés plasma de l’Institut Européen des Membranes de l’Université de Montpellier vers le Laboratoire Chimie-Physique des Matériaux de l’Université Libanaise. Les détails de l’installation du réacteur au Liban font l’objet du dernier chapitre de la thèse ainsi que les résultats des premiers tests de dépôt sur la base de conditions opératoires précédemment optimisées à l’Institut Européen des Membranes. / Direct coupling of separation and photo-catalysis using membranes based on titanium dioxide, is an interesting approach usually applied in water treatment devices, and recently considered for other applications, such as hydrogen production by water photo-electrolysis. Indeed, titanium dioxide (TiO2) is well-known for its photo-catalytic properties. In addition, if it is immobilized on membrane supports rather than used in suspensions, its integration in the separation process is facilitated and some advantages of the process in terms of compactness, integrity and separation capacity are provided. For such an application, original multilayered cells are required. Some systems are described in the literature but none of them is truly integrated (that is to say based on a micro-architecture geometry of multi-layer type) or formed of thin layers obtained by plasma processes. Now plasma processes are generally competitive for obtaining multilayered systems with high integrity and compactness. As part of recent works at IEM, various types of thin films were prepared by PECVD (Plasma Enhanced Chemical Vapor Deposition) to include TiO2 films known for their photo-catalytic properties and phosphonic acid membranes with average protons conductivity. In addition, effective platinum thin films for the protons catalytic reduction into hydrogen could also be deposited by another plasma process, sputtering. In this work, TiO2 films obtained by Low Frequency PECVD are optimized in terms of photo-catalytic activity and separation properties; this optimization, regarding the nitrogen doping of TiO2 (for the band gap shifting from the UV region to the visible region), is the first objective of this thesis project. The thin films structural and functional properties are characterized.The second aim of this thesis is to demonstrate the competitiveness of these films for the Hydrogen production/separation by solar energy. To this end, the layers photo-response has been tested in the dark, under UV and under visible light in a mono-compartment cell where both electrodes are immersed in a liquid electrolyte. Further studies integrating the TiO2 layers in contact with a commercial electrolyte membrane and a platinum counter-electrode (whose characterizations are presented in annexes), are also performed. The last aim of this work is the Plasma technology transfer from the European Membrane Institute of University of Montpellier to the Laboratory of Physical Chemistry of Materials of Lebanese University. The installation and configuration details are presented in the last chapter as well as the results of the first depositions based on operating conditions already optimized at European Membrane Institute.