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Tailored fluoropolymers remain the leading choice for a wide variety of advanced high-performance applications, including electronic/optical and energy conversion, owing to their unique blend of complementary high-performance properties. Amorphous semi-fluorinated polymers exhibit improved solubility and melt processability when compared to traditional perfluoropolymers. A leading class of semi-fluorinated aryl ether polymers includes perfluorocyclobutyl (PFCB), perfluorocycloalkenyl (PFCA), and fluoroarylene vinylene ether (FAVE) polymers. Monomers containing aromatic trifluorovinyl ethers (TFVE) are used to synthesize PFCB polymers via radical-mediated [2+2] cyclodimerization. On the other hand, FAVE and PFCA polymers are polymerized via base-mediated nucleophilic addition/elimination of bisphenols with TFVE monomers and decafluorocyclohexene respectively. The use of different monomer cores (aromatic, aliphatic, contorted, and renewable) should help to develop general structure/property relationships for this versatile and expanding approach to semi-fluorinated aryl ether polymers. The enchainment of polycyclic aromatic hydrocarbon (PAH) cores with functional fluorocarbon groups (or segments) recently afforded a new class of semi- fluorinated polymers in the continuing quest for novel organic materials for potential applications in optoelectronic, gas-separation, and advanced composites. Chapter 2 details the incorporation of commercially available acenaphthenequinone was achieved to afford PFCB aryl ether polymers with excellent solubility, high thermal stability, and film-forming capability. Chapter 3 represents base-promoted nucleophilic addition/elimination of commercial bisphenols with TFVE-triphenylene monomers affording FAVE aryl ether polymers possessing excellent solution processability, high thermal stability and photostability. In addition, triphenylene-enchained FAVE polymers exhibit extreme thermal-oxidative photostability and emit blue light after heating in air at 250 °C for 24 h. Further, time-dependent density functional theory (TD-DFT) computations were performed to understand electronic polymer structures. In one case, post-polymerization Scholl coupling converted the central triphenylene core to afford a hexabenzocoronene containing semi-fluorinated polymer with new optoelectronic properties. Chapter 4 demonstrates synthesis and characterization of renewable semi-fluorinated polymers obtained using aliphatic diol isosorbide. This renewable diol readily polymerizes with bis-TFVE derivatives of bisphenol A and 6F to provide high molecular weight thermoplastics exhibiting excellent solubility and tough, transparent film-forming capability. Finally, Chapter 5 presents synthesis of TFVE enchained corannulene which gave blue-light emission and outstanding processability. Synthesis and characterization, including the new materials' optical, thermal, and electronic properties, is presented.

In this study, collected samples of nine different wells from the Middle East are used for various geochemical analyses to determine the hydrocarbon generation potential. The determination is carried out following the grain density, specific surface area, XRD, and Rock–Eval pyrolysis analyses. Four different types of kerogen are plotted based on the Rock–Eval analysis result. Kerogen type I usually has high hydrogen index (e.g., HI > 700) and low oxygen index, which is considered oil-bearing. Kerogen Type II has hydrogen index between type I and type II and oxygen index higher than type I (e.g., 350 < HI < 700) and is also considered to have oil-bearing potential. Kerogen type III has a lower hydrogen index (e.g., HI < 350) and is considered to have a primarily gas-generating potential with terrigenous organic matter origination. Kerogen type IV has a very low hydrogen index and higher oxygen index (compared with other types of kerogen), which is considered the inert organic matter. The kerogen quality of the analyzed samples can be considered as very good to fair; the TOC content ranges from 1.64 to 8.37 wt% with most of them containing between 2 and 4 wt%. The grain density of these examined samples is in the range of 2.3–2.63 g/cc. The TOC and density of the samples have an inversely proportional relationship whereas the TOC and the specific surface area (BET) has a positive correlation. The specific surface area (BET) of the examined samples is in the range of 1.97–9.94 m2/g. The examined samples are dominated by clay, primarily kaolinite and muscovite. Additionally, few samples have a higher proportion of quartz and calcite. The examined samples from the Middle East contain kerogen type III and IV. Only two samples (JF2-760 and SQ1-1340) contain type I and type II kerogen. Considering Tmax and Hydrogen Index (HI), all of the samples are considered immature to early mature. Rock–Eval (S2) and TOC plotting indicate that most of the samples have very poor source rock potential only with an exception of one (JF2-760), which has a fair-to-good source rock potential.

<p>The ß-carbolines norharman and harman structurally resemble the synthetic compound 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP) that is known for its ability to damage neuromelanin-containing dopaminergic neurons of the substantia nigra and thereby induce parkinsonism. MPTP is, however, not normally present in the environment whereas the ß-carbolines are present in cooked food and tobacco smoke. </p><p>In this thesis it was demonstrated that norharman and harman had affinity to melanin and were retained in neuromelanin-containing neurons of frogs up to 30 days post-injection (the longest survival time examined). It was also demonstrated that norharman induced neurodegeneration, activation of glia cells and motor impairment in mice. Furthermore, this compound induced ER stress and cell death in PC12 cells. An in vitro model of dopamine melanin-loaded PC12 cells was developed in order to study the effect of melanin on norharman-induced toxicity. In this model, melanin seemed to attenuate toxicity induced by low concentrations of norharman. After exposure to the highest concentration of norharman, melanin clusters were disaggregated and there was an increased expression of stress proteins and caspases-3, known to be involved in apoptosis.</p><p>The polycyclic aromatic hydrocarbon, 7,12-dimethylbenz[<i>a</i>]anthracene was demonstrated to have a CYP1A1-dependent localization in endothelial cells in the choroid plexus, in the veins in the leptomeninges and in the cerebral veins of mice pre-treated with CYP1-inducers. </p><p>These results demonstrate that the distribution of environmental compounds could be influenced by the presence of neuromelanin and expression of CYP enzymes in the brain and that norharman may induce neurotoxic effects in vivo and in vitro.</p>

The ß-carbolines norharman and harman structurally resemble the synthetic compound 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP) that is known for its ability to damage neuromelanin-containing dopaminergic neurons of the substantia nigra and thereby induce parkinsonism. MPTP is, however, not normally present in the environment whereas the ß-carbolines are present in cooked food and tobacco smoke. In this thesis it was demonstrated that norharman and harman had affinity to melanin and were retained in neuromelanin-containing neurons of frogs up to 30 days post-injection (the longest survival time examined). It was also demonstrated that norharman induced neurodegeneration, activation of glia cells and motor impairment in mice. Furthermore, this compound induced ER stress and cell death in PC12 cells. An in vitro model of dopamine melanin-loaded PC12 cells was developed in order to study the effect of melanin on norharman-induced toxicity. In this model, melanin seemed to attenuate toxicity induced by low concentrations of norharman. After exposure to the highest concentration of norharman, melanin clusters were disaggregated and there was an increased expression of stress proteins and caspases-3, known to be involved in apoptosis. The polycyclic aromatic hydrocarbon, 7,12-dimethylbenz[a]anthracene was demonstrated to have a CYP1A1-dependent localization in endothelial cells in the choroid plexus, in the veins in the leptomeninges and in the cerebral veins of mice pre-treated with CYP1-inducers. These results demonstrate that the distribution of environmental compounds could be influenced by the presence of neuromelanin and expression of CYP enzymes in the brain and that norharman may induce neurotoxic effects in vivo and in vitro.

Aquesta tesi tracta sobre l'efecte de la contaminació per cru de petroli sobre l'ecosistema costaner mediterrani i sobre el paper fonamental dels sediments marins en la regulació i el manteniment dels processos biogeoquímics. L'estudi presta especial atenció a les comunitats bacterianes reductores de sulfat i la seva implicació en la degradació de contaminants orgànics. La diversitat, abundància i fisiologia dels bacteris reductors de sulfat que habiten el sediment arenós del nord de Mallorca (Illes Balears), van ser analitzades mitjançant un enfocament polifàsic, basat en la combinació d'experiments in situ i in vitro, biologia molecular clàssica i d’última generació, cultius i determinació d'activitats metabòliques. Els resultats obtinguts durant aquesta tesi demostren que el sediment mediterrani alberga una microbiota autòctona que podria prosperar després d'un vessament de cru de petroli i el paper de la qual podria ser crucial per a la transformació i l'eliminació de compostos orgànics xenobiòtics en aquest ambient. / Esta tesis trata sobre el efecto de la contaminación por crudo de petróleo en el ecosistema costero mediterráneo y sobre el papel fundamental de los sedimentos marinos en la regulación y el mantenimiento de los procesos biogeoquímicos. El estudio presta especial atención a las comunidades bacterianas reductoras de sulfato y a su implicación en la degradación de contaminantes orgánicos. La diversidad, abundancia y fisiología de las bacterias reductoras de sulfato que habitan el sedimento arenoso del norte de Mallorca (Islas Baleares), fueron analizadas mediante un enfoque polifásico, basado en la combinación de experimentos in situ e in vitro, biología molecular clásica y de última generación, cultivos y determinación de actividades metabólicas. Los resultados obtenidos durante esta tesis demuestran que el sedimento mediterráneo alberga una microbiota autóctona que podría prosperar después de un derrame de crudo de petróleo y cuyo papel podría ser crucial para la transformación y la eliminación de compuestos orgánicos xenobióticos en este ambiente. / This thesis discusses the fate and behave of crude oil contamination in the Mediterranean coastal ecosystem, and the essential role of the marine sediments in the regulation and maintenance of biogeochemical processes. The study pays particular attention to the role of sulphate reducing bacterial communities in the degradation of organic matter and pollutants entering the Mediterranean environment. A polyphasic approach based in the combination of in situ and in vitro experiments, next generation and classical molecular biology, cultivation, and the determination of metabolic activities, provided first insights into the diversity, abundance and physiology of sulphate reducing bacteria inhabiting the undisturbed sandy sediment at the north of Mallorca (Balearic Islands). The results obtained during the thesis demonstrate that the undisturbed Mediterranean sediment harbours an autochthonous microbiota that could prosper after a crude oil spill and which role might be crucial for the transformation and removal of hazardous organic compounds in this environment.

Canada has the second largest proven oil reserves next to Saudi Arabia which is mostly located in Alberta and Saskatchewan but is unconventional heavy oil and bitumen. The tar sands are found at the surface and are mined, yet 80% of the 173 billion barrels of heavy oil and bitumen exist in-situ according to the Canadian Association of Petroleum Producers (CAPP). Two factors inhibit the economic extraction and processing of Canadian heavy oil; its enormous viscosity ranging from 1000 to over 1 million mPa.s and the asphaltene content (high molecular weight molecules containing heavy metals and sulphur). Heavy oil and bitumen were only included in the reserves estimates through the efforts of Canadian enhanced oil recovery (EOR) research. Viscosity reduction is the one common element of in-situ methods of heavy oil recovery with the exception of cold production. Currently, steam assisted gravity drainage (SAGD) and cyclic steam stimulation (CSS) are being used commercially in the field where the oil’s viscosity is reduced by injecting steam. Thermal methods are energy intensive requiring vast volumes of water such that any improvement would be beneficial. Solvent extraction is one alternative requiring no water, the solvent is recoverable and reusable, and depending on the mode of operation the heavy oil is upgraded in-situ. Vapour Extraction (VAPEX) and enhanced solvent extraction (N-SolvTM) are two such methods. VAPEX and N-Solv reduce the bitumen’s viscosity via mass transfer and a combination of mass and heat transfer, respectively. A light hydrocarbon solvent (instead of steam) is injected into an upper horizontal well where the solvent mixes with the heavy oil, reduces its viscosity and allows the oil to drain under gravity to a bottom production well. The idea of using solvents for heavy oil extraction has been around since the 1970s and both VAPEX and N-Solv are patented processes. However, there is still much to be learned about how these processes physically work. Research to date has focused on varying system parameters (including model dimensions, permeability, heavy oil viscosity, solvent type and injection rate, etc.) to observe the effect on oil production from laboratory scale models. Based on an early mass balance model by Butler and Mokrys (1989) and an improvement by Das (1995), molecular diffusion alone cannot account for the produced oil rates observed from laboratory models. Until recently, very little progress had been made towards qualifying and quantifying the mass transfer mechanisms with the exception of the diffusivity of light hydrocarbons in heavy oil. Mass transfer can only be by diffusion and convection. Differentiating and quantifying the contribution of each is complex due to the nature and viscosity of the oil. The goal of this thesis is to investigate the mass transfer mechanisms during the solvent recovery of heavy oil. Quantifying the diffusion of light hydrocarbon solvents has been an active topic of research with limited success since the mid 1990’s. The experimental approach presented here focused on capturing the rate of solvent mass transfer into the bitumen by measuring the bitumen swelling and the butane uptake independently. Unlike early pressure decay methods, the pressure is held constant to not violate the assumed equilibrium solvent concentration at the interfacial boundary condition. The high solubility of solvent in heavy oil complicates the physical modeling because simplifying assumptions of a constant diffusion coefficient, constant density and a quiescent liquid should not be used. The model was developed from first principles to predict the bitumen swelling. The form of the concentration dependent diffusivity was assumed and the diffusivity coefficients initially guessed. The swelling (moving boundary) was fixed by defining a new dimensionless space coordinate and the set of partial differential equations solved using the method of lines. Using the non-linear regression (lsqnonlin) function in MATLAB®, optimising for the difference in predicted and experimentally found bitumen heights and independently validating the result using the solvent uptake, the diffusivity of butane in heavy oil (at 25oC) was found to be Dsb = 4.78 x 10-6ωs + 4.91 x 10-6 cm2/s where ωs is the solvent mass fraction. Diffusion alone has proven inadequate in predicting oil recovery rates from laboratory scale models. It is logical to assume that convective mass transfer plays a role at mixing the solvent and bitumen while draining via gravity through the reservoir porous matrix. Solvent extraction experiments were conducted in etched glass micromodels to observe the pore scale phenomena. The pore scale mechanisms were found to differ depending on how the solvent extraction was operated, with non-condensing (VAPEX) or condensing (N-SolvTM) solvent. Observations show increased convective mixing and an increased rate of interface advancement when the solvent condenses on the bitumen surface. Evidence of trapped butane vapour being mobilised with the draining live oil and a technique of observing solvent extraction using UV light confirm that the draining live oil is on average one pore deep. While the interface appears from a distance to be uniform, at the pore scale it is not. Live oil can drain from one to two pores via capillary displacement mechanisms in one section of the interface and via film flow only in another area (James and Chatzis 2004; James et al. 2008). This work also shows the detrimental impact of having a non-condensable gas present during solvent extraction (James and Chatzis 2008). In summary, this work emphasises the mass transfer and drainage displacement mechanisms of non-condensing (VAPEX) and condensing (N-Solv) solvent extraction methods of heavy oil recovery.

Canada has the second largest proven oil reserves next to Saudi Arabia which is mostly located in Alberta and Saskatchewan but is unconventional heavy oil and bitumen. The tar sands are found at the surface and are mined, yet 80% of the 173 billion barrels of heavy oil and bitumen exist in-situ according to the Canadian Association of Petroleum Producers (CAPP). Two factors inhibit the economic extraction and processing of Canadian heavy oil; its enormous viscosity ranging from 1000 to over 1 million mPa.s and the asphaltene content (high molecular weight molecules containing heavy metals and sulphur). Heavy oil and bitumen were only included in the reserves estimates through the efforts of Canadian enhanced oil recovery (EOR) research. Viscosity reduction is the one common element of in-situ methods of heavy oil recovery with the exception of cold production. Currently, steam assisted gravity drainage (SAGD) and cyclic steam stimulation (CSS) are being used commercially in the field where the oil’s viscosity is reduced by injecting steam. Thermal methods are energy intensive requiring vast volumes of water such that any improvement would be beneficial. Solvent extraction is one alternative requiring no water, the solvent is recoverable and reusable, and depending on the mode of operation the heavy oil is upgraded in-situ. Vapour Extraction (VAPEX) and enhanced solvent extraction (N-SolvTM) are two such methods. VAPEX and N-Solv reduce the bitumen’s viscosity via mass transfer and a combination of mass and heat transfer, respectively. A light hydrocarbon solvent (instead of steam) is injected into an upper horizontal well where the solvent mixes with the heavy oil, reduces its viscosity and allows the oil to drain under gravity to a bottom production well. The idea of using solvents for heavy oil extraction has been around since the 1970s and both VAPEX and N-Solv are patented processes. However, there is still much to be learned about how these processes physically work. Research to date has focused on varying system parameters (including model dimensions, permeability, heavy oil viscosity, solvent type and injection rate, etc.) to observe the effect on oil production from laboratory scale models. Based on an early mass balance model by Butler and Mokrys (1989) and an improvement by Das (1995), molecular diffusion alone cannot account for the produced oil rates observed from laboratory models. Until recently, very little progress had been made towards qualifying and quantifying the mass transfer mechanisms with the exception of the diffusivity of light hydrocarbons in heavy oil. Mass transfer can only be by diffusion and convection. Differentiating and quantifying the contribution of each is complex due to the nature and viscosity of the oil. The goal of this thesis is to investigate the mass transfer mechanisms during the solvent recovery of heavy oil. Quantifying the diffusion of light hydrocarbon solvents has been an active topic of research with limited success since the mid 1990’s. The experimental approach presented here focused on capturing the rate of solvent mass transfer into the bitumen by measuring the bitumen swelling and the butane uptake independently. Unlike early pressure decay methods, the pressure is held constant to not violate the assumed equilibrium solvent concentration at the interfacial boundary condition. The high solubility of solvent in heavy oil complicates the physical modeling because simplifying assumptions of a constant diffusion coefficient, constant density and a quiescent liquid should not be used. The model was developed from first principles to predict the bitumen swelling. The form of the concentration dependent diffusivity was assumed and the diffusivity coefficients initially guessed. The swelling (moving boundary) was fixed by defining a new dimensionless space coordinate and the set of partial differential equations solved using the method of lines. Using the non-linear regression (lsqnonlin) function in MATLAB®, optimising for the difference in predicted and experimentally found bitumen heights and independently validating the result using the solvent uptake, the diffusivity of butane in heavy oil (at 25oC) was found to be Dsb = 4.78 x 10-6ωs + 4.91 x 10-6 cm2/s where ωs is the solvent mass fraction. Diffusion alone has proven inadequate in predicting oil recovery rates from laboratory scale models. It is logical to assume that convective mass transfer plays a role at mixing the solvent and bitumen while draining via gravity through the reservoir porous matrix. Solvent extraction experiments were conducted in etched glass micromodels to observe the pore scale phenomena. The pore scale mechanisms were found to differ depending on how the solvent extraction was operated, with non-condensing (VAPEX) or condensing (N-SolvTM) solvent. Observations show increased convective mixing and an increased rate of interface advancement when the solvent condenses on the bitumen surface. Evidence of trapped butane vapour being mobilised with the draining live oil and a technique of observing solvent extraction using UV light confirm that the draining live oil is on average one pore deep. While the interface appears from a distance to be uniform, at the pore scale it is not. Live oil can drain from one to two pores via capillary displacement mechanisms in one section of the interface and via film flow only in another area (James and Chatzis 2004; James et al. 2008). This work also shows the detrimental impact of having a non-condensable gas present during solvent extraction (James and Chatzis 2008). In summary, this work emphasises the mass transfer and drainage displacement mechanisms of non-condensing (VAPEX) and condensing (N-Solv) solvent extraction methods of heavy oil recovery.

Στην παρούσα διατριβή μελετήθηκε χρήση λεπτών καταλυτικών ηλεκτροδίων Pt/YSZ και Pt/TiO2/YSZ στην έκταση του φαινομένου της ηλεκτροχημικής ενίσχυσης, χρησιμοποιώντας την πρότυπη αντίδραση οξείδωσης αιθυλενίου, σε οξειδωτικές συνθήκες (μεταξύ 280oC και 375oC) σε αντιδραστήρα μονής πελέτας. Βρέθηκε ότι η παρουσία ενός διεσπαρμένου υμενίου TiO2 μεταξύ του καταλυτικού ηλεκτροδίου και του στερεού ηλεκτρολύτη (YSZ), έχει σημαντική επίδραση στην έκταση του μεγέθους του φαινομένου της ηλεκτροχημικής ενίσχυσης της κατάλυσης. Οι τιμές του λόγου προσαύξησης ρυθμού και της φαρανταϊκής απόδοσης υπολογίστηκαν περίπου 2.5 και 4 φορές μεγαλύτερες για το στοιχείο όπου η TiO2 ήταν παρούσα. Αυτή η προσαύξηση στα μεγέθη αυτά οφείλεται τόσο σε μορφολογικές παραμέτρους, όπως η αυξημένη διασπορά της Pt στον φορέα και του μήκους των τριών φάσεων, παρουσία του υμενίου TiO2, αλλά κυρίως λόγω ενός μηχανισμού ενισχυμένης μεταφοράς προωθητικών ειδών Ο2- προς την καταλυτική επιφάνεια που υφίσταται λόγω της μικτής αγωγιμότητας (ιοντικής-ηλεκτρονιακής) της TiO2 σε οξειδωτικές συνθήκες αντίδρασης. Επίσης, μελετήθηκε η χρήση λεπτών καταλυτικών ηλεκτροδίων Pt εναποτεθειμένων με τη μέθοδο sputtering στην έκταση του φαινομένου της ηλεκτροχημικής ενίσχυσης, χρησιμοποιώντας την πρότυπη αντίδραση οξείδωσης αιθυλενίου, σε έναν μονολιθικό ηλεκτροχημικά ενισχυόμενο αντιδραστήρα. Βρέθηκε ότι και τέτοιου τύπου ηλεκτρόδια – καταλυτικά υμένια είναι ιδιαίτερα καταλυτικά ενεργά και είναι δυνατό να ενισχυθούν ηλεκτροχημικά σε μεγάλο βαθμό. Επίσης, ο αντιδραστήρας λειτούργησε επιτυχώς και παρατηρήθηκε ηλεκτροχημική ενίσχυση, υπό υψηλές ογκομετρικές παροχές (25 l/min), με ταχύτητες χώρου αντιδραστήρα που είναι κοντά σε αυτές που λειτουργούν οι βιομηχανικοί αντιδραστήρες (12000 h-1). Τέλος, μελετήθηκε η αναγωγή του CO2 από Η2 σε ηλεκτρόδια Cu/TiO2/YSZ χρησιμοποιώντας τόσο έναν αντιδραστήρα μονής πελέτας όσο και έναν μονολιθικό ηλεκτροχημικά ενισχυόμενο αντιδραστήρα υπό ατμοσφαιρική πίεση. Χρησιμοποιώντας τον αντιδραστήρα μονής πελέτας βρέθηκε ότι η αντίδραση καταλήγει στην παραγωγή CO και CH4 με εκλεκτικότητα σε CH4 κοντά στο 17%. Η εφαρμογή θετικών και αρνητικών τιμών δυναμικού ενισχύουν τον ρυθμό της αντίδρασης σε μεγάλο βαθμό και επιπλέον μπορεί να τροποποιηθεί και η εκλεκτικότητά της σε CΗ4 που είναι και το επιθυμητό προϊόν. Επίσης, η προσθήκη μικρών ποσοτήτων CH3OH (~0.5 kPa) στο μίγμα τροφοδοσίας βρέθηκε ότι τροποποιεί σημαντικά τον ρυθμό παραγωγής του CH4, η εκλεκτικότητα του οποίου αγγίζει το 100% ακόμη και από τους 280οC. Χρησιμοποιώντας τον μονολιθικό ηλεκτροχημικά ενισχυμένο αντιδραστήρα, MEPR, εξοπλισμένο με 20 πλάκες Cu/TiO2/YSZ τα προϊόντα της αντίδρασης ήταν CO, CH4 και C2H4. Η εκλεκτικότητα στην παραγωγή του CH4 και του C2H4 έφτασε έως το 80% και το 2%, αντίστοιχα ενώ η μέγιστη μετατροπή του CO2 έφτασε έως και το 40% στους 380οC. Όπως και στον αντιδραστήρα μονής πελέτας, η προσθήκη CH3OH στο μίγμα τροφοδοσίας είχε ως αποτέλεσμα η εκλεκτικότητα στην παραγωγή CH4 να αυξηθεί στο 100%. Τα αποτελέσματα αυτά δείχνουν ότι είναι εφικτή η απευθείας αναγωγή του CO2 προς χρήσιμους υδρογονάνθρακες σε ατμοσφαιρική πίεση. / In the present work the electrochemical promotion of Pt/YSZ and Pt/TiO2/YSZ catalyst-electrodes has been investigated, for the model reaction of C2H4 oxidation in an atmospheric pressure single chamber reactor, under oxygen excess between 280 and 375oC. It has been found that the presence of a dispersed TiO2 thin layer between the catalyst electrode and the solid electrolyte (YSZ), results in a significant increase of the magnitude of the electrochemical promotion of catalysis (EPOC) effect. The rate enhancement ratio upon current application and the faradaic efficiency values, were found to be a factor of 2.5 and 4 respectively, higher than those in absence of TiO2. This significantly enhanced EPOC effect via the addition of TiO2 suggests that the presence of the porous TiO2 layer enhances the transport of promoting O2- species onto the Pt catalyst surface. This enhancement may be partly due to morphological factors, such as increased Pt dispersion and three-phase-boundary length in presence of the TiO2 porous layer, but appears to be mainly caused by the mixed ionic-electronic conductivity of the TiO2 layer which results to enhanced O2- transport to the Pt surface via a self-driven electrochemical promotion O2- transport mechanism. Also, the use of thin catalytic Pt sputtered electrodes (Pt/YSZ/Au) was examined in the MEPR for the model reaction of C2H4 oxidation. It was found that such thin electrodes are catalytically active and can be electropromoted even under high gas flow rates (25 l/min) or high space velocity (HSV~12000 s-1), close to those that the industrial reactors operate. A single chamber reactor equipped with a Cu/TiO2/YSZ electrode and a monolithic electropromoted reactor (MEPR) with up to 20 thin Cu/TiO2/YSZ plate cells were also used to investigate the hydrogenation of CO2 at atmospheric pressure. Utilizing the single chamber reactor CO and CH4 was produced with selectivity to CH4 up to 17%. Both positive and negative applied potential significantly enhance the hydrogenation rate and selectivity to CH4. It was found that the addition of small (~0.5kPa) amounts of CH3OH in the feed has a pronounced promotional effect on the reaction rate and selectivity of the Cu/TiO2/YSZ cells. The selective reduction of CO2 to CH4 starts at 280oC (vs 350oC in absence of CH3OH) with near 100% CH4 selectivity at open-circuit and under polarization conditions at temperatures 280–380oC. Utilizing a MEPR equipped with 20 Cu/TiO2/YSZ cells CO, CH4 and C2H4 were produced with selectivities to CH4 and C2H4 up to 80% and 2%. The maximum CO2 conversion reached 40% at 380oC. The addition of small (~0.5 kPa) amounts of CH3OH in the feed has also a pronounced promotional effect on the reaction rate and selectivity to CH4 (near 100%) at open-circuit and under polarization conditions at temperatures 220–380oC. The results show the possibility of direct CO2 conversion to useful products in a MEPR via electrochemical promotion at atmospheric pressure.

Commercial fuels are mixtures with large numbers of components. Continuous thermodynamics is a technique for modelling fuel mixtures using a probability density function rather than dealing with each discreet component. The mean and standard deviation of the distribution are then used to model the chemical reactions of the mixture. This thesis develops the necessary theory to apply the technique of continuous thermodynamics to the oxidation reactions of hydrocarbon fuels. The theory is applied to three simplified models of hydrocarbon oxidation: a global one-step reaction, a two-step reaction with CO as the intermediate product, and the four-step reaction of Müller et al. (1992), which contains a high- and a low-temperature branch. These are all greatly simplified models of the complex reaction kinetics of hydrocarbons, and in this thesis they are applied specifically to n-paraffin hydrocarbons in the range from n-heptane to n-hexadecane. The model is tested numerically using a simple constant pressure homogeneous ignition problem using Cantera and compared to simplified and detailed mechanisms for n-heptane. The continuous thermodynamics models are able not only to predict ignition delay times and the development of temperature and species concentrations with time, but also changes in the mixture composition as reaction proceeds as represented by the mean and standard deviation of the distribution function. Continuous thermodynamics is therefore shown to be a useful tool for reactions of multicomponent mixtures, and an alternative to the "surrogate fuel" approach often used at present.