The developments in mobile/portable electronics and alternative energy vehicles prompted engineers and researchers to develop electrochemical energy storage devices called supercapacitors, as the third generation type capacitors. Most of the research and development on supercapacitors focus on electrode materials, electrolytes and hybridization. Some attempts have been directed towards increasing the energy density by employing electroactive materials, such as metal oxides and conducting polymers (CPs). However, the high cost and toxicity of applicable metal oxides and poor long term stability of CPs paved the way to alternative electrode materials. The electroactive materials with carbon particles in composites have been used substantially to improve the stability of supercapacitors. Furthermore, the use of carbon particles and CPs could significantly reduce the cost of supercapacitor electrodes compared to metal oxides. Recent developments in carbon allotropes, such as carbon nanotubes (CNTs) and especially graphene (G), have found applications in supercapacitors because of their enhanced double layer capacitance due to the large surface area, electrochemical stability, and excellent mechanical and thermal properties. The main objective of the research presented in this dissertation is to increase the energy density of supercapacitors by the development of nanocomposite materials composed of graphene and different CPs, such as: (a) polyaniline derivatives (polyaniline (PANI), methoxy (-OCH3) aniline (POA) and methyl (-CH3) aniline (POT), (b) poly(3-4 ethylenedioxythiophene) (PEDOT) and (c) polypyrrole (PPy). The research was carried out in two phases, namely, (i) the development and performance evaluation of G-CP (graphene in conducting polymers) electrodes for supercapacitors, and (ii) the fabrication and testing of the coin cell supercapacitors with G-CP electrodes. In the first phase, the synthesis of different morphological structures of CPs as well as their composites with graphene was carried out, and the synthesized nanostructures were characterized by different physical, chemical and thermal characterization techniques, such as Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), UV-visible spectroscopy, Fourier Transform Infrared (FTIR) spectroscopy, Raman spectroscopy, BET surface area pore size distribution analysis and Thermogravimetric Analysis (TGA). The electrochemical properties of G-CP nanocomposite-based supercapacitors were investigated using Cyclic Voltammetry (CV), galvanostatic charge-discharge and Electrochemical Impedance Spectroscopy (EIS) techniques in different electrolytes, such as acidic (2M H2SO4 and HCl), organic ( 0.2 M LiClO4) and ionic liquid (1M BMIM-PF6) electrolytes. A comparative study was carried out to investigate the capacitive properties of G-PANI derivatives for supercapacitor applications. The methyl substituted polyaniline with graphene as a nanocomposite (G-POT) exhibited a better capacitance (425 F/g) than the G-PANI or the G-POA nanocomposite due to the electron donating group of G-POT. The relaxation time constants of 0.6, 2.5, and 5s for the G-POT, G-PANI and G-POA nanocomposite-based supercapacitors were calculated from the complex model by using the experimental EIS data. The specific capacitances of two-electrode system supercapacitor cells were estimated as 425, 400, 380, 305 and 267 F/g for G-POT, G-PANI, G-POA, G-PEDOT and G-PPy, respectively. The improvements in specific capacitance were observed due to the increased surface area with mesoporous nanocomposite structures (5~10 nm pore size distribution) and the pseudocapacitance effect due to the redox properties of the CPs. Further, the operating voltage of G-CP supercapacitors was increased to 3.5 V by employing an ionic liquid electrolyte, compared to 1.5 V operating voltage when aqueous electrolytes were used. On top of the gain in the operating voltage, the graphene nano-filler of the nanocomposite prevented the degradation of the CPs in the long term charging and discharging processes. In the second phase, after studying the material's chemistry and capacitive properties in three-electrode and two-electrode configuration-based basic electrochemical test cells, coin cell type supercapacitors were fabricated using G-CP nanocomposite electrodes to validate the tested G-CPs as devices. The fabrication process was optimized for the applied force and the number of spacers in crimping the two electrodes together. The pseudocapacitance and double layer capacitance values were extracted by fitting experimental EIS data to a proposed equivalent circuit, and the pseudocapacitive effect was found to be higher with G-PANI derivative nanocomposites than with the other studied G-CP nanocomposites due to the multiple redox states of G-PANI derivatives. The increased specific capacitance, voltage and small relaxation time constants of the G-CPs paved the way for the fabrication of safe, stable and high energy density supercapacitors.

The separation of the expensive catalysts from the solvent and reaction products remains one of the major disadvantages of homogeneous catalytic reactions, which are otherwise advantageous because of their high activity, tuneable selectivity and ease of study. Ideally, the homogeneous reactions would be carried out in continuous flow mode with the catalyst remaining in the reactor at all times, whilst the substrates and products flow over the catalyst. The system we have been studying is one where the catalyst is dissolved in a thin film of an ionic liquid, and this is supported within the pores of a microporous silica. This supported ionic liquid phase (SILP) catalyst is then placed in a tubular flow reactor, similar to that used for heterogeneous reactions. The raw materials are then injected into the rig, pass through the reactor and the products and the raw materials that have not reacted are collected at the other end of the rig. Supercritical CO₂ is used to transport the raw materials and products along the catalyst bed, allowing a continuous flow mode with low leaching for both the catalyst and the ionic liquid. We have applied this procedure first to alkene metathesis catalysed by a ruthenium complex that has been especially designed to dissolve in 1-butyl-3-methyimidazolium triflamide (BMIM NTf₂), which was used as ionic liquid. Activity is observed for the ring closing metathesis of diethyl 2,2-diallylmalonate, but the catalyst is not stable, only allowing about 300 turnovers. This instability is attributed to the formation of Ru=CH₂ moieties, which dimerise to an inactive species. More success is achieved with internal alkenes such as 2-octene and especially methyl oleate. Self metathesis of methyl oleate continues for >10.000 turnovers over 10 h, with only small decreases in activity. The cross metathesis of methyl oleate with dimethyl maleate has also been studied. Cross metathesis dominates in the early stages of the reaction but the cross metathesis products diminish with time. Surprisingly, the catalyst does not deactivate since self metathesis of methyl oleate continues. The phase behaviour of the reaction was monitored and gave us an insight into the reasons for this change in selectivity. Methoxycarbonylation reactions in continuous flow proved to be a much more difficult process than the previous metathesis reactions. Higher catalyst loading was needed to reduce the reaction times. The first continuous flow reactions showed conversion predominantly, if not exclusive, of 1-octene isomerised products. The presence of ionic liquid (IL) in the SILP system was essential, otherwise the catalyst leached out of the reactor very quickly. Batch reactions showed that none of the studied parameters (absence of presence of either BMIM NTf₂, OMIM NTf₂, silica or CO₂) had any influence on the reaction, but when observing the results it was noticed that the reactions that gave the best results were performed in a close range of pressures between 55 and 70 bar, indicating that the reaction might be pressure dependent. Further continuous flow reactions in that range of pressures gave the best conversions to methoxycarbonylation products. Unfortunately, at these pressures and without CO₂ the reaction took place in a liquid phase and thus substantial IL and catalyst leaching was observed, causing a decrease in conversion and making the reaction not feasible under continuous flow conditions. Nevertheless, the catalyst system composed of Pd, 1,2-bis(di-tert-butylphosphinomethyl)benzene (DTBPMB) ligand and acid showed an excellent linear selectivity, usually higher than 90%, both in batch and continuous flow reactions. Hydrogenation reactions of dimethyl itaconate (DMI) and dibutyl itaconate (DBI) using Rh-MeDuPhos showed excellent activity and enantioselestivity in a batch mode. In a continuous flow mode IL leaching caused a decrease of the enantioselectivity. The best results were obtained when CO₂ was not present. On the other hand, the absence of CO₂ implied that the reaction was performed in a liquid phase and therefore abundant IL leaching was observed along with a decrease in the enantioselectivity. A study of the reaction behaviour when using CO₂ in its different phases (liquid, gas and supercritical) was carried out. Under supercritical conditions IL leaching was avoided but conversion was not observed. When using CO₂ in its liquid phase some conversion was observed and full conversion occurred in its gas phase, but abundant IL leaching caused a decrease in the enantioselectivity. Better results were obtained by immobilising a Rh-MeDuPhos catalyst onto alumina via heteropoly acids. The effect of pressure, H₂ flow and substrate flow were studied and the stability of the reaction in the long term was examined under optimal conditions. More than 12,900 TONs were achieved after 4 days of continuous reaction, with conversions higher than 90% during the 3 first days and e.e. higher than 99% during the 2 first days.

No description available.

No description available.

The use of lignocellulosic materials to replace fossil resources for the industrial production of fuels, chemicals, and materials is increasing. The carbohydrate composition of lignocellulose (i.e. cellulose and hemicellulose) is an abundant source of sugars. However, due to the feedstock recalcitrance, rigid and compact structure of plant cell walls, access to polysaccharides is hindered and release of fermentable sugars has become a bottle-neck. Thus, to overcome the recalcitrant barriers, thermochemical pretreatment with an acid catalyst is usually employed for the physical or chemical disruption of plant cell wall. After pretreatment, enzymatic hydrolysis is the preferred option to produce sugars that can be further converted into liquid fuels (e.g. ethanol) via fermentation by microbial biocatalysts. However, during acid pretreatment, several inhibitory compounds namely furfural, 5-hydroxymethyl furfural, phenols, and aliphatic acids are released from the lignocellulose components. The presence of these compounds can greatly effect both enzymatic hydrolysis and microbial fermentation. For instance, when Avicel cellulose and acid treated spruce wood hydrolysate were mixed, 63% decrease in the enzymatic hydrolysis efficiency was observed compared to when Avicel was hydrolyzed in aqueous citrate buffer. In addition, the acid hydrolysates were essentially non-fermentable. Therefore, the associated problems of lignocellulose conversion can be addressed either by using feedstocks that are less recalcitrant or by developing efficient pretreatment techniques that do not cause formation of inhibitory byproducts and simultaneously give high sugar yields. A variety of lignocellulose materials including woody substrates (spruce, pine, and birch), agricultural residues (sugarcane bagasse and reed canary grass), bark (pine bark), and transgenic aspens were evaluated for their saccharification potential. Apparently, woody substrates were more recalcitrant than the rest of the species and bark was essentially amorphous. However, the saccharification efficiency of these substrates varied based on the pretreatment method used. For instance, untreated reed canary grass was more recalcitrant than woody materials whereas the acid treated reed canary grass gave a higher sugar yield (64%) than the woody substrates (max 34%). Genetic modification of plants was beneficial, since under similar pretreatment and enzymatic hydrolysis conditions, up to 28% higher sugar production was achieved from the transgenic plants compare to the wild type. As an alternative to the commonly used acid catalysed pretreatments (prior to enzymatic hydrolysis) lignocellulose materials were treated with four ionic liquid solvents (ILs): two switchable ILs (SILs) -SO2DBUMEASIL and CO2DBUMEASIL, and two other ILs [Amim][HCO2] and [AMMorp][OAc]. viii After enzymatic hydrolysis of IL treated substrates, a maximum amount of glucan to glucose conversion of between 75% and 97% and a maximum total sugar yields of between 71% and 94% were obtained. When using acid pretreatment these values varied between 13-77% for glucan to glucose conversion and 26-83% for total sugar yield. For woody substrates, the hemicellulose recovery (max 92%) was higher for the IL treated substrates than compared to acid treated samples. However, in case of reed canary grass and pine bark the hemicellulose recovery (90% and 88%, respectively) was significantly higher for the acid treated substrates than the IL treated samples. To overcome the inhibitory problems associated with the lignocellulose hydrolysates, three chemical conditioning methods were used 1. detoxification with ferrous sulfate (FeSO4) and hydrogen peroxide (H2O2) 2. application of reducing agents (sulfite, dithionite, or dithiothreitol) and 3. treatment with alkali: Ca(OH)2, NaOH, and NH4OH. The concentrations of inhibitory compounds were significantly lower after treatments with FeSO4 and H2O2 or alkali. Using reducing agents did not cause any decrease in the concentration of inhibitors, but detoxification of spruce acid hydrolysates resulted in up to 54% improvement of the hydrolysis efficiency (in terms of sugar release) compared to untreated samples. On the other hand, application of detoxification procedures to the aqueous buffer resulted in up to 39% decrease in hydrolysis efficiency, thus confirming that the positive effect of detoxification was due to the chemical alteration of inhibitory compounds. In addition, the fermentability of detoxified hydrolysates were investigated using the yeast Saccharomyces cerevisiae. The detoxified hydrolysates were readily fermented to ethanol yielding a maximum ethanol concentration of 8.3 g/l while the undetoxified hydrolysates were basically non-fermentable.

Gas-expanded liquids (GXLs) are a unique class of tunable solvents with unlimited potential. A wide range of solvent properties and solvent interactions and complexes are possible by adjusting the amount of the gas component (in situ) or changing the organic liquid. Aside from solvent tunability, there are environmental and processing benefits to using GXLs. Organic solvent use is decreased, the gas component can be vented off facile separations, and the gas can act as an antisolvent for selective solute precipitation. As a result there are numerous reaction and extraction schemes and materials processing applications that could benefit from GXL use. Unfortunately, important molecular-level details that can drive a chemical process are largely unknown and limit GXL use in industrial and specialty applications. The work presented in this uses a synergistic study of experiments and computer simulations to explore solvation processes and molecular interactions in GXLs and the effects on macroscopic observables like spectroscopy, transport, and reactions. Steady-state solvation of a laser dye is studied with spectroscopy (UV/vis and fluorescence) and molecular dynamics simulations (MD). Both experiment and theory show that organic enrichment occurs in the vicinity of the solute called the cybotactic region. Subsequently, the solvent dynamics arising by electronically perturbing the solute are studied with MD simulation. Unexpected dynamics are observed and are dependent on the organic component and gas composition. The diffusion of heterocyclic compounds is studied with MD simulations and compared to the Taylor-Aris diffusion study of former group members. The experiments and simulations do not agree, but solvent structures obtained by simulation are shown to provide valuable insight into solvent-dependent absorption spectroscopy, or solvatochromism. Finally, dissociation constants of alkylcarbonic acids that form in situ in CO2/alcohol mixtures are presented from spectroscopic measurements. Spectroscopic techniques to measure dissociation constants are well known; however, the high-pressure and multiple equilibria associated with alkylcarbonic acids hinder straight-forward measurement and analysis.

The first chapter of this thesis describes the motivation behind using room temperature ionic liquids (RTILs) in gas sensor research and reviews current applications of RTILs in various sensors. The second chapter describes electrochemical polymerization of aniline in room temperature 1-butyl-3-methylimmidazolium ionic liquids without addition of any acid. It is shown that the polymerization of aniline in BMI(BF4) does require small but controlled amounts of water whereas the polymerization in BMI(PF6) and in BMI(TF2N) does not require any water addition. The third chapter describes the construction of reference electrodes for RTIL applications that have a known and reproducible potential versus the ferrocene/ ferrocenium couple. They are based on reference electrodes of the first kind, Ag/Ag+ couple type, or of the second kind, based on Ag/AgCl in M+Cl-. The stability, reproducibility, and temperature behavior of the two reference systems have been characterized. The fourth chapter describes the electrochemical preparation and spectral analysis of gold clusters by adding gold atoms one-by-one through polyaniline s ability to form a strong complex with chloroaurate at the protonated imine sites. Our results confirm that both the amount and the size of gold clusters affects the properties of the composite material. The fifth chapter describes the development and characterization of a CHEMFET sensing layer based on a composite of CSA-doped polyaniline (PANI), and the room temperature ionic liquid BMI(TF2N) for the sensing of ammonia gas. The work function responses of the cast films with and without IL are analyzed by step-wise changes of ammonia gas concentration from 0.5 to 694 ppm in air as a function of the mole fraction of IL to PANI. The PANI CSA/BMI(TF2N) layers shows enhanced sensitivities, lower detection limit and shorter response times. The final chapter describes the preparation and characterization of field-effect transistors with mixed ionic-electronic conductors that have been created by varying the ratio of room temperature ionic liquid and emeraldine salt of polyaniline. Transistor with high electronic conductivity (32mol% ES-PANI) and Au gate contact exhibited theoretical behavior of an IGFET; whereas, the purely ionic gate behaved irreproducibly, indicating that a capacitive divider has been formed in the gate.

Το ολοένα και μεγαλύτερο πρόβλημα, της ολοκληρωτικής εξάντλησης των αποθεμάτων του πετρελαίου το οποίο παρουσιάζεται στην βιομηχανία τα τελευταία χρόνια όλο και περισσότερο, έχει σοβαρό αντίκτυπο όπως είναι λογικό και στα παράγωγα αυτού και στην βιομηχανία που τα χρησιμοποιεί σαν πρώτο υλικό. Πιο συγκεκριμένα, στα Δίκτυα Υψηλής Τάσης Εναλλασσόμενου Ρεύματος η μόνωση του εξοπλισμού και των εγκαταστάσεων υψηλής τάσης είναι απαραίτητη προκειμένου να διατηρηθεί η διαφορά δυναμικού μεταξύ των υπό υψηλή τάση αγώγιμων μερών, η μηχανική στήριξη των αγωγών, η ανταλλαγή θερμότητας, κ.ά. Στον τομέα των ηλεκτροτεχνικών υγρών που χρησιμοποιούνται για αυτό τον σκοπό, βασική μας μελέτη ήταν η αντικατάσταση των όποιων μονωτικών υγρών χρησιμοποιούνταν μέχρι τώρα (συνήθως ορυκτελαίων κ.ά.) με έλαια φυτικής προέλευσης τα οποία προφανώς δεν επηρεάζονται από την εξάντληση του πετρελαίου που προ αναφέραμε αλλά και παρουσιάζουν κάποια βασικά πλεονεκτήματα τα οποία παρουσιάζονται στην παρούσα εργασία. Βασική μας ενασχόληση ήταν να περιγραφεί η συμπεριφορά των μονωτικών υγρών μέσω του επιστημονικού κλάδου της αναγνώρισης προτύπων. Πιο συγκεκριμένα , μέσω πειραματικών διαδικασιών που πραγματοποιήθηκαν στο Εργαστήριο Υψηλής Τάσης , έγινε η διάσπαση των υγρών υπό την επίδραση Υψηλής Τάσης και στη συνέχεια η μάθηση και η Εκπαίδευση Τεχνητού Νευρωνικού Δικτύου. Τα τεχνητά νευρωνικά δίκτυα χρησιμοποιήθηκαν στην παρούσα διπλωματική εργασία καθώς μπορούν να περιγράψουν μη γραμμικές σχέσεις μεταξύ εισόδου και εξόδου κάτι το οποίο συμβαίνει στην διάσπαση υγρών διηλεκτρικών υπό υψηλή τάση καθώς και γενικεύοντας μπορούμε να μελετάμε την συμπεριφορά των υγρών υπό την έκθεση πολύ υψηλών τάσεων , όπου στο εργαστήριο θα είναι αδύνατη η εφαρμογή τους. Eκτενέστερα στο 1ο Κεφάλαιο , της διπλωματικής εργασίας ασχολούμαστε με τα μονωτικά υγρά και τις ιδιότητες αυτών. Η χρήση τους είναι απαραίτητη στους μετασχηματιστές ,πυκνωτές , καλώδια , μονωτήρες διέλευσης κ.α. Επίσης , όσον αφορά τα μονωτικά υγρά που χρησιμοποιούνται ευρέως,τα ορυκτέλαια, αναφέρονται οι φυσικές και χημικές ιδιότητες τους και αναλύονται οι ηλεκτρικές τους ιδιότητες. Επιπλέον αναλύονται και οι ιδιότητες των φυσικών εστέρων ως μονωτικό μέσο σε μετασχηματιστές ισχύος και η γενική συμπεριφορά των υγρών υπό την επίδραση υψηλού ηλεκτρικού πεδίου. Στο 2ο Κεφάλαιο αναλύουμε τα τεχνητά νευρωνικά δίκτυα. Η αναγνώριση προτύπων σαν επιστημονικός κλάδος και οι τεχνικές του, όπως αυτή των νευρωνικών δικτύων μας εισάγουν στην δημιουργία συστημάτων τα οποία μπορούμε να δημιουργήσουμε, να εκπαιδεύσουμε και στην συνέχεια ελέγχοντας την αξιοπιστία τους μέσω της στατιστικής, να εργαστούμε πάνω σε αυτά. Η απαρχή των τεχνητών νευρωνικών δικτύων, οι βιολογικοί νευρώνες δηλαδή του εγκεφάλου, είναι η βάση όλων των συστημάτων και εν συνεχεία αφού περιγράφεται η ιστορική αναδρομή των τεχνητών δικτύων αναλύουμε την φύση των δικτύων οπισθοδρόμησης (Back Propagation) όπου είναι και τα δίκτυα που χρησιμοποιήθηκαν στην παρούσα διπλωματική εργασία . Στο 3ο Κεφάλαιο εισάγουμε την δημιουργία τεχνητών νευρωνικών δικτύων στο περιβάλλον Μatlab. Αφού δημιουργήσαμε το κατάλληλο νευρωνικό δίκτυο, και το εκπαιδεύσαμε μελετήσαμε την καταλληλότητα του δικτύου και κατά πόσο αυτό θα μπορεί να μας δώσει αξιόπιστα αποτελέσματα προσομοιώνοντας την πειραματική διαδικασία του εργαστηρίου σε συνθήκες κατάλληλες και ακατάλληλες , εξετάζοντας δηλαδή τα πειραματικά δεδομένα με εισαγωγή στοιχείων κατάλληλα για το εργαστήριο, αλλά και στοιχείων που δεν είναι δυνατή η πραγματοποίηση τους στο εργαστήριο . Στο Κεφάλαιο Συμπεράσματα , εν τέλει αναλύουμε και συνοψίζουμε την καταλληλότητα του πειράματος που πραγματοποιήσαμε καθώς και κατά πόσο το νευρωνικό δίκτυο είναι αξιόπιστο, καθώς και οι λόγοι που το καθιστούν . / The growing problem of complete exhaustion of oil reserves, which occurred in the industry in recent years increasingly has a serious impact as is reasonable to derivatives and in industry as they are used as first material. More specifically, networks Ac high-voltage insulation of equipment and installations of high voltage is necessary in order to maintain the potential difference between the high voltage conductive parts, mechanical support of pipelines, heat exchange.In the volume of liquids used for this purpose, our main study was the replacement of any insulating liquids used so far with vegetable oils which apparently are not affected by the depletion of oil before mentioned but also show some key advantages that occur in this task. Our main preoccupation was to describe the behaviour of insulation liquids through the scientific branch of pattern recognition. More specifically, through experimental procedures carried out in high-voltage Laboratory, became the Division of fluid under the influence of high voltage and then learning and education of artificial Neural Network. Artificial neural networks used in the present study together can describe nonlinear relationships between input and output something that happens in breaking liquid dielectrics under high voltage and whilst generally applying to studying the behavior of liquids in the report very high voltages in the laboratory, where it will be impossible to implement them. Furthermore in 1st Chapter of study we occupate with insulating fluids and properties. Their use is indispensable to transformers, capacitors, cables, insulators, transit etc. Also as regards insulating liquids that are widely used, mineral oils, referred to the physical and chemical properties and the electrical properties. Additional analyses and properties of natural esters as insulating power and instrument transformers in the General behaviour of liquids under high electric field. In the 2nd Chapter analyze the artificial neural networks. The recognition of standards as a scientific discipline and techniques, such as neural networks we introduce in creating systems that we can create, to educate them and then checking the reliability of statistics, to work on them. The beginnings of artificial neural networks, biological neurons of the brain, is the basis of all systems and subsequently after describes the history of artificial networks analyse the nature of networks backwards (Back Propagation) and networks where they are used in this thesis. In the 3rd Chapter introduce the creation of artificial neural networks in Matlab environment. After you have created the appropriate neural network, and then by training have judged the appropriateness of the network and whether it can give reliable results by simulating the experimental procedure of laboratory conditions appropriate and inappropriate, considering that the experimental data with input suitable for laboratory but also items that cannot be made in the laboratory. In chapter Conclusions, ultimately analysing and concluding the suitability of the experiment held and whether the neural network is reliable, and the reasons that make it.

Les piles à combustible microbiennes (PCMs) sont des dispositifs bio-électrochimiques qui utilisent des biofilms bactériens électroactifs afin de catalyser des réactions d'oxydoréduction anodique et/ou cathodique pour générer de l'énergie électrique. Afin de promouvoir le développement et la connexion des biofilms, points clé dans les performances des PCM, la surface de l'anode de graphite est fonctionnalisée par des unités pyridine. Celles-ci sont greffées de façon covalente via la réduction électrochimique de cations diazopyridinium, formés in situ à partir de précurseurs amine, en s'inspirant de la méthode d'électrogreffage des sels d'aryle diazonium. Cela permet d'obtenir une interface très robuste. En comparant la réactivité de différents dérivés aminopyridine et les propriétés des couches greffées résultantes, la réduction des cations para-diazopyridinium conduit à des films fins et compacts, bien adaptés pour favoriser l'adhésion bactérienne et le transfert d'électrons entre la surface de l'anode et les bactéries électroactives. La présence d'unités pyridine immobilisées en surface de l'anode permet un développement plus rapide du biofilm et des performances accrues de la PCM pour des biofilms jeunes. Par comparaison, une anode modifiée par des multicouches de polyphénylène puis colonisée par un biofilm bactérien se révèle moins efficace pour la catalyse de l'oxydation de l'acétate. La nature et les propriétés physicochimiques de l'électrolyte sont également un paramètre important dans le développement du biofilm bactérien. Les liquides ioniques à température ambiante présentent des propriétés uniques, notamment en termes de solvatation, et leur utilisation dans des applications biotechnologiques a récemment émergé. Toutefois, leurs effets sur les biofilms bactériens restent encore peu connus. L'ajout d'une sélection de liquides ioniques hydrophiles et hydrophobes à base de cations imidazolium ou pyridinium dans l'anolyte, même en très faible quantité, ou immobilisés à la surface de l'anode inhibe le développement du biofilm. / Microbial Fuel Cells (MFCs) are bio-electrochemical devices based on electroactive bacterial biofilms which catalyze the electron transfer both at the anode and cathode to generate electrical power. To enhance the biofilms development and to improve the biofilm-electrode connection, being both key features in the performance of the MFC, the graphite anode was functionalized by pyridine units. In order to ensure a robust interface, pyridine units are grafted covalently through the electrochemical reduction of diazopyridinium cations in situ formed from aminopyridine precursors, following the well-known electrografting method for aryl diazonium salts. By comparing the reactivity of various aminopyridine derivatives and the resulting grafted layers properties, the para-diazopyridinium cations reduction results in a thin and compact layer, which is the best suited for promoting bacterial adhesion and favorable electron transfer between the anode surface and electroactive bacteria. The presence of pyridine units immobilized on the anode surface leads to a faster biofilm development together with increased MFC performances for young biofilms. In contrast, anode modified with polyphenylene multilayers and then colonized by a bacterial biofilm has been proved to be less effective for the catalysis of acetate oxidation. On the other hand, the nature of the electrolyte and the physicochemical properties are also important parameters for the bacterial biofilm development. Room temperature ionic liquids have unique properties, particularly in terms of solvation, and their use in biotechnological applications has recently emerged. However, their effects on bacterial biofilms remain little known. The addition of a selection of hydrophilic and hydrophobic ionic liquids based on imidazolium or pyridinium cations in the anolyte, even in very small quantities, or immobilized at the anode surface inhibited the biofilm development.

Dans ce travail, nous avons modifié deux carbones activés (grain AC et tissu T0) par divers traitements chimique (H2O2, NaOCl et un traitement thermique sous azote) et par des traitements ultrasonores à 20 et 500 kHz en présence de différents solvants (eau ultrapure, peroxyde d'hydrogène et acide formique). Ces carbones (bruts et modifiés) ont été caractérisés du point de vue de leur chimie de surface et de leur texture. Nous avons étudié l'adsorption d'ibuprofène (IBP) aux différents pH et températures. Le processus d'adsorption de l'IBP sur (AC ou T0) est avéré endothermique à pH 3. L'oxydation par NaOCl crée des groupes phénoliques qui défavorisent l'adsorption d'IBP tandis que l'oxydation par H2O2 augmente la teneur en groupe carbonyles et carboxyles responsable d'une contribution à l'adsorption de l'IBP. Le traitement ultrasonore de AC a augmenté son adsorption d'IBP par rapport au charbon brut. La cinétique d'adsorption de deux liquides ioniques synthétisés (LI1 : bromure de 4-tertiobutyl-1-propylpyridinium et LI2 : bromure de 4-tertiobutyl-1(2-carboxy-ethyl)pyridinium ) sur T0 est beaucoup plus rapide que la cinétique d'adsorption de l'IBP à pH 7,5. La compétition d'adsorption sur T0 entre les trois molécules (IBP et les deux liquides ioniques) a montré que l'IBP s'adsorbe en plus grande quantité sur le T0 que le LI1 et le LI2. / In this work, two activated carbons (granular AC and fabric T0) were modified either by chemical treatment (H2O2, NaOCl and thermal treatment under N2) or by ultrasonic irradiation at 20 kHz or 500 kHz in different solvents (UHQ water, H2O2 and HCOOH). The raw and modified materials were characterized by different methods. We studied the ibuprofen (IBP) adsorption at different pH and temperatures. The adsorption of IBP by (AC or T0) was an endothermic process at pH 3. Oxidation with NaOCl creates phenol groups that led to a decrease of the adsorption uptake while oxidation by H2O2 increases the carbonyl group content and carboxyl that induce an increase in the adsorption of IBP. The ultrasonic treatment of AC increases the adsorption capacity of ibuprofen in comparison with the raw AC. The adsorption of the two ionic liquids (LI1 : the 4(tert-butyl)-1propylpyridinium bromide and LI2 : 4(tert-butyl)-1(2-carboxy-ethyl)pyridinium bromide ) onto T0 was found much faster than the adsorption kinetic of IBP at pH 7.5. The competitive adsorption of mixture of IBP and the two ionic liquids showed that IBP is the most adsorbed by T0.