Les capteurs de gaz électrochimiques sont l’un des moyens les plus directs pour convertir la composition chimique d’un gaz en signal électrique mesurable. A ce titre, ils ont été largement étudiés et font aujourd’hui partie des solutions de détection les plus courantes. Toutefois, ils sont souvent basés sur un électrolyte YSZ, ce qui implique des températures de travail élevées (600°C).Afin de pouvoir réaliser une cellule de capteur fonctionnant à plus basse température (300°C), les conditions de dépôt des électrolytes Bi4V2O11 et BITAVOX (Bi2TaxV1-xO5,5) par pulvérisation cathodique magnétron en conditions réactives (PVD) ont été étudiées. L’impact de l’épaisseur des films ainsi que celui du taux de substitution du vanadium par le tantale sur les propriétés structurale et de conduction ont été déterminés.Par la suite, deux types de cellules ont été réalisés en déposant des électrodes à la surface de l’électrolyte par PVD. Le premier utilise des électrodes de platine dense et de nanofils de LASCO (La1-x-yAgxSryCoO3). Néanmoins, le comportement de ce capteur aux plus basses températures est assez complexe. Aussi, des électrodes de platine et d’or ont ensuite été étudiées, amenant à une réponse plus simple et apparaissant dès 200°C. / Electrochemical sensors are one of the most direct ways to convert the chemical composition of a gas into measurable electric signals. As such, they have been widely investigated and are now one of the most common detection solutions. However, they are often based on YSZ electrolyte, which implies high working temperatures (600°C).In order to build a sensor cell which could operate at lower temperature (300°C), deposition parameters of Bi4V2O11 and BITAVOX (Bi2TaxV1-xO5.5) electrolytes by the mean of reactive magnetron sputtering (PVD) were investigated. The impact of film thickness and that of tantalum substitution rate on the V site on structural and conduction properties were determined.Then, two different kinds of cells were realised by depositing electrodes onto the electrolyte surface. The first one used dense platinum and LASCO (La1-x-yAgxSryCoO3) nanowires electrodes. Nevertheless, this sensor exhibited a rather complex behaviour at lowest temperatures. Then, gold and platinum electrodes were investigated, which led to a more simple response of the sensor. Furthermore, this response started at 200°C.

The goal of this thesis is the development of scalable, low cost synthesis of metal oxide nanostructures based electrodes and to correlate the chemical modifications with their energy conversion performance. Methods in energy conversion in this thesis have focused on two aspects; a potentiometric chemical sensor was used to determine the analytical concentration of some components of the analyte solution such as dopamine, glucose and glutamate molecules. The second aspect is to fabricate a photo-electrochemical (PEC) cell. The biocompatibility, excellent electro-catalytic activities and fast electron transfer kinetics accompanied with a high surface area to volume ratio; are properties of some metal oxide nanostructures that of a potential for their use in energy conversion. Furthermore, metal oxide nanostructures based electrode can effectively be improved by the physical or a chemical modification of electrode surface. Among these metal oxide nanostructures are cobalt oxide (Co3O4), zinc oxide (ZnO), and bismuth-zincvanadate (BiZn2VO6) have all been studied in this thesis. Metal oxide nanostructures based electrodes are fabricated on gold-coated glass substrate by low temperature (< 100 0C) wet chemicalapproach. X-ray diffraction, x-ray photoelectron spectroscopy and scanning electron microscopy were used to characterize the electrodes while ultraviolet-visible absorption and photoluminescence were used to investigate the optical properties of the nanostructures. The resultant modified electrodes were tested for their performance as chemical sensors and for their efficiency in PEC activities. Efficient chemically modified electrodes were demonstrated through doping with organic additives like anionic, nonionic or cationic surfactants. The organic additives are showing a crucial role in the growth process of metal oxide nanocrystals and hence can beused to control the morphology. These organic additives act also as impurities that would significantly change the conductivity of the electrodes. However, no organic compounds dependence was observed to modify the crystallographic structure. The findings in this thesis indicate the importance of the use of controlled nanostructures morphology for developing efficient functional materials.

Afin de contrôler l’émission totale des NOx dans l’échappement automobile, un capteur potentiométrique à base de zircone stabilisée à l’yttrium a été développé par la technique de sérigraphie. Il est montré que l’utilisation d’un filtre catalytique, déposé directement sur l’élément sensible, permet d’éliminer les interférences venant d’autres gaz réducteurs dans l’échappement, en particulier monoxyde de carbone (CO), hydrogène (H2), hydrocarbures (CxHy) et ammoniac (NH3). En plus, il est possible de fixer avec le filtre catalytique le rapport NO/NO2 correspondant à l’équilibre thermodynamique. Par conséquent la réponse du capteur n’est plus dépendante du rapport NO/NO2, mais seulement de la température. De plus, la sensibilité et la sélectivité du capteur à NO2 peut considérablement être améliorée en appliquant un courant de polarisation. / In order to monitor the total NOx emission in car exhausts, a potentiometric gas sensor based on yttria-stabilized zirconia (YSZ) has been developed by screen-printing technology. It is shown that the use of a catalytic filter directly deposited on the sensing element can successfully eliminate the interferences coming from other reducing gas species in the automotive exhaust such as carbon monoxide (CO), hydrogen (H2), hydrocarbons (CxHy) and ammoniac (NH3). Furthermore, another advantage of the catalytic filter is its capacity to fix the NO/NO2 ratio according to the thermodynamic equilibrium. In that way, the sensor response is no longer dependent on the NO/NO2 ratio in the exhaust, but only dependent on the temperature. Finally, the application of a polarisation current can enhance considerably the selectivity and sensitivity of the sensor towards NO2.

The monitoring of pharmaceuticals, heavy metal, pH and free chlorine concentration in drinking water is important for public health and the environment. However, conventional laboratory-based analytical methods are labor-intensive, expensive, and time consuming. This thesis focuses on developing an integrated, highly sensitive, easy-to-use, and low-cost pharmaceuticals, heavy metal, pH and free chlorine sensing system for drinking water quality monitoring. A low-temperature, solution-processed modification of multi-walled carbon nanotubes (MWCNT) with β-cyclodextrin (βCD) on glassy carbon electrode is developed for detecting low levels of acetaminophen. The adsorption properties of βCD are combined with the high surface area of carbon nanotubes towards enhanced electrochemical sensing of acetaminophen with a limit of detection of 11 nM and linear range from 0.05-300 μM. Also, a systematic investigation is carried out using four types of modified MWCNT-βCD. A novel, one-step approach called Steglich esterification modified MWCNT-βCD results in large effective surface area, and fast electron transfer towards sensitive detection of acetaminophen and 17β-estradiol (E2, primary female sex hormone) in the range of 0.005–20 and 0.01–15 μM, with low detection limits of 3.3 and 2.5 nM, respectively. The similar MWCNT-βCD modified electrodes can also detect heavy metal ion (lead, Pb2+) with a limit of detection of <10 ppb. Low frequency noise behavior of these sensors are studied. A spin-coated Pd/PdO based pH sensor, and amine-modified carbon electrode-based free chlorine sensor are fabricated on a common substrate together with the pharmaceuticals and heavy metal sensors. A Wheatstone-bridge temperature sensor is fabricated based on silicon and PEDOT:PSS on another substrate. All the sensors are connected to an Arduino microcontroller based data acquisition system with a smartphone application interface. The integrated sensing system is easy-to-use, low-cost, and can provide accurate monitoring data with real drinking water samples. / Dissertation / Doctor of Philosophy (PhD) / Low-cost, easy-to-use, and sensitive monitoring system for pharmaceuticals, heavy metal, pH and free chlorine in drinking water is crucial for public health safety. In this thesis, we develop solution-based synthesis of multi-walled carbon nanotubes modified by β-cyclodextrin for electrochemical sensing of pharmaceuticals and heavy metal. The modification approaches are compared and characterized to analyze their electrochemical behavior and sensing performances. The developed sensors are highly sensitive toward the detection of acetaminophen (a widely used pain-killer) and estrogen hormone in drinking water. We also develop a modified spin-coating technique to deposit palladium/palladium oxide films for potentiometric pH sensor, a calibration-free free chlorine sensor based on modified carbon electrode, and a resistive temperature sensor. The developed pH, free chlorine and temperature sensors are highly sensitive, and stable with fast response time. All the sensors are integrated and interfaced with a custom-made and smartphone-controlled electronic readout system for accurate and on-site drinking water quality monitoring at low cost.

This work reports on the cobalt pyridinoporphyrazinate (CoTmtppa) as a platinum-group metal-free catalyst for hydrogen evolution and oxidation reactions with the possibility of use in hydrogen energy and hydrogen potentiometric sensing. A different interaction of CoTmtppa with various electrode substrates, highly oriented pyrolytic graphite (HOPG) and annealed gold (Au(111)), affects its electrocatalytic behaviour in hydrogen reactions. The formation of a hydride-type complex with the bonding of hydrogen atoms to cobalt centre is supposed to be the rate-determining step. In the case of hydrogen evolution, the maximum catalytic activity of mediator was reached at pH = 11,0, when the HOPG/CoTmtppa showed overpotential decrease by 300 mV and an almost 60-fold increase of current densities compared to HOPG. The electrocatalytic activity of Au(111)/CoTmtppa resulted in a further decrease of overpotential by 175 mV in comparison with HOPG/Co(I)Tmtppa. The electrochemical oxidation of hydrogen was found to depend on hydrogen source which was electrochemically generated on-site or molecular hydrogen supplied from an external source. In the case of electrochemically generated hydrogen, the maximum activity of HOPG/CoTmtppa was reached at pH = 2.1 and an additional it was observed 50 % increase in current...