Les objets mobiles connectés prennent une place prépondérante dans notre vie de tous les jours mais l’autonomie énergétique est à ce jour limitée. Ainsi, le développement de dispositifs de stockage d’énergie performants et miniaturisés est un domaine en pleine expansion. Les performances de ces systèmes dépendent des matériaux dont sont constituées leurs électrodes et de l’électrolyte utilisé. Cette thèse est consacrée à la fabrication de micro-supercondensateurs à électrodes interdigitées composées de films minces de nitrure de vanadium (VN) déposé par pulvérisation cathodique. La modulation des paramètres de dépôt a permis de densifier les dépôts afin d’augmenter la conductivité électrique ou, au contraire, de rendre poreuses les couches minces pour favoriser la capacité surfacique. La caractérisation operando par spectroscopie d’absorption X d’un film mince de VN cyclé en milieu aqueux KOH couplée à des analyses de surface (XPS / TOF-SIMS) montre que la capacité élevée du VN est due à l’oxyde de vanadium présent en surface du film. Des micro-supercondensateurs rapportant des performances à l’état de l’art en topologie interdigitée ou face / face ont été fabriqués en utilisant les films de VN optimisés dont nous avons fait varier l’épaisseur pour augmenter les densités d’énergie surfacique. Le dépôt de VN par ALD a été également mis au point dans le cadre de cette thèse afin de pouvoir assurer la formation de couches minces sur des substrats 3D de haute surface spécifique. Enfin, différents liquides ioniques ont été utilisés comme électrolytes afin de faire cycler des électrodes de VN, le but étant la formation d’électrolyte solide basé sur la technologie ionogels. / The mobile connected devices have a prominent place in our everyday life but energy autonomy is limited. Thus, the development of efficient and miniaturized energy storage devices is an expanding field. The performance of these systems depends on the used electrode materials and the electrolyte. This thesis is focused on the fabrication of micro-supercapacitors with interdigitated electrodes composed of sputtered vanadium nitride (VN) thin films. The modulation of the deposition parameters allows densifying the thin films in order to increase their electrical conductivity or, on the contrary, leads to the synthesis of porous thin films to increase the surface capacitance. X-ray absorption spectroscopy of VN thin films tested in aqueous KOH in operando configuration coupled with surfaces analyses (XPS/ ToF-SIMS) show that the high capacitance of the VN is due to the presence of thin layer of vanadium oxide at the VN surface. Micro-supercapacitors reporting state-of-art performance in interdigitated or face/face topologies were fabricated using optimized VN films: the film thickness was varied to increase the energy density. The Atomic Layer Deposition of VN layers was also achieved in the frame of this study in order to ensure the formation of thin layers on high specific surface area 3D substrates. Finally, different ionic liquids have been tested as electrolyte, the purpose being solid electrolyte formation based on ionogels technology.

In der vorligenden Arbeit wurden Vanadium-abhängige Bromidperoxidase- (VBPO-) Modelle zur stereoselektiven Synthese funktionalisierter O-Heterocyclen entwickelt, die durch Vanadium-katalysierte Oxygenierung von Bishomoallylalkoholen mechanistisch untersucht wurden. Weiterhin wurden Bromcyclisierungen von Bishomoallylalkoholen auf enzymatischem (VBPO), oxidativem und radikalischem Weg für Referenzprodukte einer neuen Variante der Bromcyclisierung durch Vanadium-katalysierte Bromidoxidation durchgeführt. Die Selektivitätsmuster aus den Synthesen ß-hydroxylierter und ß-bromierter Tetrahydrofurane wurden anschließend innerhalb einfacher Naturstoffsynthesen genutzt. Anhand eigener Vorarbeiten wurden neue Vanadium(V)-Komplexe aus Triethoxyvanadat mit tridentaten Schiffbaseliganden, basierend auf Salicylaldehyd und Aminoalkoholen mit strukturell unterschiedlichen Seitenketten in quantitativen Ausbeuten synthetisiert und charakterisiert (51V-NMR, UV und IR). In Test-Cyclisierungen unterschiedlicher Bishomoallylalkohole eignete sich VO(salin)(OEt) mit hohen Umsätzen und guten Regio- wie Stereoselektivitäten am besten. Die relative Geschwindigkeitskonstante (krel = 120±20) der Vanadium-katalysierten Oxidation des Testsystems konnte über Konkurrenzkinetik (Alkenol versus Alken) ermittelt werden und weist deutlich auf eine Bindung des Alkenols an Vanadium während der Oxidation hin. Um die Regio- und Stereoselektivitäten Vanadium-Schiffbase-katalysierter Oxidationen von Bishomoallylalkoholen verstehen zu können, wurden stereochemische Studien anhand des Testsystems durchgeführt. Dessen Oxidation wird demnach im selektivitätsbestimmenden Schritt dem Metallzentrum abgewandt in like-Position bevorzugt gebildet und führt zu dem cis-konfigurierten Tetrahydrofuran als Hauptprodukt. Im Folgenden wurden Vanadium-katalysierte Oxidationen unterschiedlich substituierter bishomoallylischer Alkohole durchgeführt, sämtliche Oxidationen führten regioselektiv zu Tetrahydrofuranen als Hauptprodukte, die Oxygenierung Dimethyl-substituierter Pentenole lieferte durch Substitution an C-1 selektiv cis-konfigurierte Tetrahydrofurane, 2-Substitution führte ebenso wie 3-Substitution zu trans-konfigurierte Oxolanen. Alkohole nicht aktivierter Olefine wurden in der Reihenfolge C-1 ? C-3 mit höherer Selektivität zu trans-konfigurierten Tetrahydrofuranen gebildet. Die Regio- und Stereoselektivitäten der radikalischen Bromcyclisierungen folgen den schon in früheren Arbeiten unserer Arbeitsgruppe aufgestellten Richtlinien (5-exo-trig; 2,5-trans, 2,4-cis und 2,3-trans). Die ionischen Bromcyclisierungen 5,5-dimethylierter Bishomoallyl-alkohole mittels NBS verliefen komplementär zu den Radikal-Cyclisierungen regioselektiv und in Abhängigkeit der Phenylsubstituenten an C-1 - C-3 stereoselektiv zu den 2,5-trans-, 3,5-cis- und 4,5-trans-konfigurierten Tetrahydropyranen. Aus der Bromcyclisierung prochiraler Pentenole in Gegenwart eines Acetonpulvers aus Ascophyllum nodosum (A.n.A.P.) konnte das b-bromierte Tetrahydrofuran racemisch in 87proz. Ausbeute erhalten werden. Ebensowenig führte der Einsatz chiraler Liganden in der Vanadium-katalysierten Oxygenierung prochiraler Penten-1-ole bei guten Ausbeuten (>80%) zu Enantiomeren-angereicherten Tatrahydrofuranen. Innerhalb einfacher Naturstoffsynthesen wurden cis-Pityol, Linalooloxid sowie (-)-epi-Bisabololoxid selektiv unter Standardbedingungen der Vanadium-Schiffbase-katalysierten Oxidationen mit VO(salin)(OEt) und TBHP dargestellt. Die Stereoselektivitäten steigen proportional zu dem Größenunterschied der Substituenten an Position 1 der Bishomoallylalkohole. Abschließend wurde durch Vanadium-katalysierte Bromidoxiadtion mit TBHP eine neue dreistufige Totalsynthese der vier "natürlichen" Muscarin-Isomere ausgearbeitet. Die Gesamtausbeuten dieser Synthesen liegen zwischen 3.0 und 19.9%. / In the present work vanadium dependent bromoperoxidase- (VBPO-) models have been developed for the stereoselective synthesis of functionalized O-heterocycles, that were examined mechanistically by vanadium catalyzed oxygenation of bishomoallylic alcohols. Furthermore bromine cyclizations of pentenols were carried out in an enzymatic (VBPO), oxidative and radical version for reference products of a new variant of the bromine cyclization by vanadium catalyzed bromide oxidation. The selectivity models from these syntheses of ß-hydroxylated and ß-brominated tetrahydrofurans were then used within simple natural product syntheses. By means of own preleminary works new vanadium(V)-complexes were synthesized in quantitative yields from triethyl vanadate and tridentate Schiff-base ligands generated from salicylic aldehyde and amino alcohols with structurally differing side chains, and were characterized spectroscopically (51V-NMR, UV and IR). Cyclizations of different bishomoallylic alcohols indicated that VO(salin)(OEt) was the best among the catalysts tested since it afforded high yields and good regio- and stereoselectivities of oxidation products. The relative rate constant (krel = 120±20) for the vanadium catalyzed oxidation of a test system was determined by competition kinetics (alkenol vs. alkene) and is a clear indication for the coordination of the alkenol at vanadium within the oxidation step. In order to understand the regio- and stereoselectivities of the vanadium Schiff-base catalyzed oxidation of bishomoallylic alcohols stereochemical studies were carried out with the test pentenol. The oxidation of the alkenol double bond has to be the selectivity determining step, proceeding in like-fashion and leading to the cis-configured tetrahydrofuran as main product. Next, vanadium catalyzed oxidations of differently substituted bishomoallylic alcohols were performed, which all led regioselectively to tetrahydrofurans as main products. Oxygenation of 1-substituted pentenols resulted in cis-configured tetrahydrofurans, 2- and 3-substitution led to trans-configured oxolanes. Alcohols with non-activated olefins were converted into trans-substituted tetrahydrofurans with increasing selectivity in the order of C-1- ? C-3-substitution. The regio- and stereoselectivities of the radical bromine cyclization follow the guidelines already set up in former works of our group (5-exo-trig; 2,5-trans, 2,4-cis and 2,3-trans). The ionic bromine cyclizations of 5,5-dimethylated bishomoallylic alcohols by means of NBS ran regioselective complementarily to the radical cyclizations and stereoselective in dependence of the phenyl substituents at C-1 - C-3 to the 2,5-trans-, 3,5-cis- and 4,5-trans-configured tetrahydropyrans. Bromine cyclization of a prochiral pentenol in presence of A.n.A.P. gave rise to the ß-brominated tetrahydrofuran racemically in 87% yield. Even the use of chiral ligands in vanadium catalyzed oxygenation of prochiral pentenols led to no enantiomeric enriched tatrahydrofurans. Within simple natural product syntheses cis-pityol, linalool oxide as well as (-)-epi-bisabololoxid was synthesized selectively under standard conditions of the vanadium Schiff-base catalyzed oxidation with VO(salin)(OEt) and TBHP. The stereoselectivities increased proportionally with the size difference of the substituents in position 1 of bishomoallylic alcohols. Finally a new three-step total synthesis of the four "natural" muscarine isomers was developed by vanadium catalyzed bromide oxiadtion with TBHP. The overall yields of these syntheses range between 3.0 and 19.9%.

Thesis (Ph. D.)--University of Hong Kong, 2006. / Title proper from title frame. Also available in printed format.

Graduation date: 1995

Petroleum coke (petcoke) has been burned at kraft pulp mills to partially substitute for natural gas and fuel oil used in lime kilns. Due to the high vanadium and sulfur contents in petcoke, there had been concerns over the impact of burning petcoke on kiln and chemical recovery operations. Laboratory studies were performed to examine the fate of vanadium and sulfur in lime kilns and chemical recovery cycle. The results suggest that most of the vanadium in petcoke quickly forms calcium vanadates with lime in the kiln, mostly 3CaO•V2O5. In the causticizers, calcium vanadates react with Na2CO3 in green liquor to form sodium vanadate (NaVO3). Due to its high solubility, NaVO3 dissolves in the liquor circulating around the chemical recovery system. V becomes enriched in the liquor, leading to vanadium build-up in the system. The S in petcoke would stay in the reburned lime, lower the lime availability, increase SO2 emissions from the kiln stack, alter the S balance, increase the liquor sulphidity, and potentially contribute to ring formation in the kiln.

Petroleum coke (petcoke) has been burned at kraft pulp mills to partially substitute for natural gas and fuel oil used in lime kilns. Due to the high vanadium and sulfur contents in petcoke, there had been concerns over the impact of burning petcoke on kiln and chemical recovery operations. Laboratory studies were performed to examine the fate of vanadium and sulfur in lime kilns and chemical recovery cycle. The results suggest that most of the vanadium in petcoke quickly forms calcium vanadates with lime in the kiln, mostly 3CaO•V2O5. In the causticizers, calcium vanadates react with Na2CO3 in green liquor to form sodium vanadate (NaVO3). Due to its high solubility, NaVO3 dissolves in the liquor circulating around the chemical recovery system. V becomes enriched in the liquor, leading to vanadium build-up in the system. The S in petcoke would stay in the reburned lime, lower the lime availability, increase SO2 emissions from the kiln stack, alter the S balance, increase the liquor sulphidity, and potentially contribute to ring formation in the kiln.

Thesis (Ph. D.)--School of Physics, Georgia Institute of Technology, 2004. Directed by Walter A. de Heer. / Vita. Includes bibliographical references (leaves 84-90).

Thesis--M. Phil., University of Hong Kong.

published_or_final_version / Physics / Master / Master of Philosophy

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