L’obtention de nanoparticules d’or nécessite le contrôle de nombreux paramètres et la compréhension du mode d’interaction entre l’or et le support. Pour cela, le choix du support est très important. Le premier volet de la thèse concerne la préparation contrôlée des catalyseurs à base d’or supporté sur les oxydes mésoporeux réductibles TiO₂, CeO₂ et Fe₂O₃ synthétisés via deux stratégies Soft et hard template en utilisant respectivement comme agents structurants le tribloc copolymère (Pluronic 123) et la silice mésoporeuse SBA-15. Les différentes techniques de caractérisation mettent bien en évidence que le taux de dépôt de l’or dépend de la concentration initiale de HAuCl₄, de la méthode de préparation (DPU, DP NaOH), de la teneur en or visée et de la nature du support ; Ces résultats sont à relier à la spéciation des espèces or en solution en fonction du pH final de la solution. Les taux de dépôt de l’or sont plus importants sur CeO₂ et ceci quelle que soit la teneur en or visée dans ce travail. Une dispersion très élevée est obtenue (la taille moyenne des particules d’or est de 2nm) sur les catalyseurs à 1% et 2%Au/CeO₂ préparés par la méthode DPU et calcinés à 400°C. Le deuxième volet de cette étude concerne l’oxydation en phase gaz d’une molécule organique modèle le toluène et l’oxydation en phase liquide d’une molécule organique modèle le phénol par des réactions de type Fenton et photo Fenton. Dans l’oxydation du toluène en phase gazeuse, les catalyseurs à base d’or supportés sur oxydes mésoporeux sont totalement sélectifs en CO₂ et H₂O. Les performances catalytiques dépendent des conditions de synthèse des catalyseurs et de la nature de l’oxyde utilisé ; le catalyseur 1%Au/CeO₂ est très actif et très stable au cours de quatre cycles successifs et au cours du temps. L’oxydation en phase liquide d’une molécule organique modèle le phénol par des réactions de type Fenton et photo Fenton a été effectuée sur les catalyseurs FeSBA-15 synthétisés via différentes stratégies : introduction du fer par voie postsynthétique et par voie hydrothermale en milieu faiblement et fortement acide respectivement à pH=6 et pH=3. Les performances catalytiques dépendent du rapport Si/Fe et de la taille des particules des espèces de fer, la taille des particules étant directement liée à la stratégie de synthèse des catalyseurs. Le catalyseur FeSBA-15(Si/Fe=60) synthétisé à pH=6 est un candidat potentiel dans la dégradation de polluants organiques par procédé Fenton et photo-Fenton en milieu neutre. / Well dispersed gold nanoparticles are the key to obtain an active gold catalyst. Obtaining gold nanoparticles requires control of many parameters and understanding of the interaction mode between gold and the support. For this reason the choice of the support is very important. The first part of this thesis concerns the controlled preparation of gold catalysts supported on reducible mesoporous oxides TiO₂, CeO₂ and Fe₂O₃ synthesized via two strategies Soft and Hard template using respectively. triblock copolymer (Pluronic 123) and mesoporous silica SBA-15 as template. This study clearly shows that the gold loading depends on the initial concentration of HAuCl₄, the method of preparation (DPU DP NaOH), theoretical gold content and the nature of the support. These results are to relate to the gold speciation which is a function of pH of the solution. The gold loading is higher on CeO₂ than on TiO₂ and Fe₂O₃ whatever the theoretical gold content. Very high gold dispersion is obtained (the gold particle size is 2 nm) on 1wt% and 2wt% Au/CeO₂ prepared by DPU and calcined at 400°C. The second part of this study concerns the toluene oxidation in the gas phase on Au/mesoporous oxide catalysts and the Fenton and photo-Fenton degradation of phenolic aqueous solutions by H₂O₂ on FeSBA-15 catalysts prepared following different synthesis routes, direct synthesis by adjusting pH at 3 and 6 and with post synthesis procedure. In the toluene oxidation in the gas phase Au/mesoporous oxide catalysts are totally selective for CO₂ and H₂O. The catalytic performances depend on the synthesis conditions of catalysts and the support; the 1wt% Au/CeO₂ catalyst is very active and exhibits a long-term stability. In the Fenton and photo-Fenton degradation of phenolic aqueous solutions the catalytic performances depend on the Si/Fe ratio and the particle size of the iron species, the particle size being directly related to the synthesis strategy of the catalysts. The catalyst FeSBA-15 (Si/Fe = 60) synthesized at pH = 6 is a potential candidate in the degradation of organic pollutants by Fenton and photo-Fenton process in neutral medium. / م لخصمسقني لمعلا يف هذه ةحورطألا ىلإ نيئزج:OiT 2ب وا سطة OeC 2و , Fe2O ي خ تص الاول ال ق سم ب تح ض يرمح فزات من ال ذهبن وع من م يزوب ري ة ب مواد مدعم 3ان واع مخ ت لف ال تح ض ير. ت شخ يص ف ي ال م س ت عم لة ال ت ق ن يات مخ ت لفت ب ين ال مح ضرة ل مح فزات انال دعم ط ب ي عة ك ذا و ال مح فز ت ح ض ير وطري قة HAuCl ت ر سب معدل ي ت ع لق ل ذه با ت رك يز ع لى 4ي ع ضو جزيء و سطغازي enèuloT أك سدة ف ي ال مواد هذه ب تط ب يق ي ت ع لق ال ثان ي ال ق سم ف يال مح فز ت ح ض ير Ò طرق ك ذا و ل ت فاعل هذا ع لى ال مؤث رة ل عوامل ب درا سة ق م نا سال فا ال مذك ورة ل لمح فزات ال ف عال ية ع لان واع مخ ت لف ب وا سطة FeSBA- ي ع ضو جزيء lonehP ت فاعل ب وا سطة notneF سائ ل و سط ف ي وعمن 51 ن مح فزات ع لىوHp ال و سط Si/Fe قلعتي ةبسنب FeSBA- ريضحتلا.ادأء 1515FeSBA-15, Fenton, Phenol, Toluène, TiO و 2 CeO2, Fe2O3, SBA- ال ك لمات ال م ف تاح ية ׃م يزوب وري ة ,

The bio-enabled syntheses of functional nano-structured metal oxide thin films is of importance for a range of applications, in photonics, electronics, sensing, cell engineering, and biochemical devices. This type of novel syntheses method can overcome problems common in conventional oxide processing. In general, conventional oxide processes often require thermal treatment, caustic chemicals, and mechanical processing when producing shape-controlled inorganic materials. In contrast, biological processes are usually carried out under mild conditions (low temperature, neutral pH, and atmospheric pressure) and are therefore promising for the development of benign processes. Functional materials synthesized at room temperature using biomolecules are promising due to their expediency. During recent years, significant discoveries and progress have been made in discovering, and finding new applications for such biomimetic oxide-based minerals. However, much of the research has focused on SiO- and TiO-bearing organic-inorganic hybrid materials, of which a significant limitation is that, there are relatively few water-soluble inorganic oxide precursors commercially available for such biological syntheses. Two common compounds that are used in the biomimetic syntheses of SiO₂ and TiO₂ are tetramethoxisilane (TMOS) and Ti(IV) -bis(ammonium lactato) dihydroxide ( TiBALDH ). As a result, approaches to synthesize new water-soluble transitional metal complexes for use as precursors in the biomineralization of the corresponding functional metal oxide thin films were explored in this work, in order to expand the range of functional oxide chemistries formed via bio-enabled methods. A Ti-containing compound was synthesized to compare the behavior of commercially-available and as-synthesized TiBALDH. Another titanium-containing complex with citrate ligands, instead of lactate, was also synthesized to investigate the influence of the ligand type on the deposition behavior of the precursors. Zirconium- and hafnium-containing complexes were also synthesized to demonstrate the feasibility and versatility of the idea of applying bio-enabled syntheses to the fabrication of functional mineral oxides other than the reported SiO₂ and TiO₂. The second part of this thesis focuses on developing a novel way to fabricate porous functional mineral oxide thin films with controlled pore size, which can be used in a variety of applications, such as dye loading for optical, photochemical, or electrochemical purposes. Commercially-available, carboxyl-group-terminated polystyrene spheres of different sizes were utilized as pore-size controllers in the bio-enabled syntheses of TiO₂ by protamine. This approach has been found to be an effective means of creating uniform pores in inorganic mineral oxide coatings. The accomplishments of this work have the potential to be integrated so as to expand the boundaries of biomineralization in materials science and engineering fields.

Dans ce travail, l'oxydation totale du toluène et de la butanone sur des catalyseurs à base d'or et de palladium supportés sur un oxyde de titane macro-mésoporeux a été étudiée. Nous avons tout d'abord discuté l'effet bénéfique du dopage (V, Nb, Fe, Ce, Ni) du support TiO₂ macro-mésoporeux sur l'activité catalytique de ce matériau. Une interaction existant entre le dopant et le support a joué un rôle important dans l'augmentation de l'activité des matériaux dopés par rapport à celle du titane pure. Une phase active constituée d'or et/ou de palladium a été ensuite déposée sur les solides dopés et la performance des catalyseurs préparés a été suivie dans l'oxydation du toluène et de la butanone. La présence de la phase active a assuré une sélectivité totale pour le CO₂ avec la formation de sous-produits en particulier dans l'oxydation de la butanone. Par ailleurs, l'oxydation du mélange des deux COVs a montré l'existence d'une compétition entre les molécules en terme d'adsorption sur le support, ce qui a favorisé leur éliminationà de basses températures. Une étude operando DRIFT réalisée dans l'oxydation du mélange toluène/butanone a vérifié la présence de cette compétition. / In this work, the total oxidation of toluene and butanone over noble metal loaded doped titanium oxide supports has been investigated. The study focused firstly on showing the effect of doping a macro-mesoporous titania with metal oxide supports in the oxidation of VOCs. It seems that doping enhances the performance of the used solid in VOC oxidation reactions. We proved that this increase can be directly related to interactions between the dopants and the support. Then, an active phase made of noble metals has been loaded onto both best performing doped materials as to study the role played by this active phase in oxidation reactions. It appears that the presence of noble metals increases the catalytic performance of prepared materials and reduces the formation of toxic by-products such as CO. Butanone elimination proved to be harder that toluene oxidation, whereas when catalysts were exposed to a mixture of toluene and butanone, the presence of both VOCs prompted a competitive effect in the adsorption of both molecules onto the support, which facilitated their oxidation rate. An FTIR operando study illustrated the changes occuring in used catalysts in the oxidation of the VOC mixture, and verified the existence of this competitive effect.

Målet med examensarbetet var att utvärdera hur Gustavsberg AB i Vårgårda arbetar för en hållbar utveckling och identifiera utvecklingsmöjligheter. Lönsamhetsanalysen som även gjordes hade som syfte att utröna om företagets miljöinsatser inneburit kostnadsbesparingar. Målet var också att genom intervjuer med personer på företaget och genom rapporten tydliggöra begreppet hållbar utveckling. Rapporten innehåller även en diskussion kring hållbara utvecklingsstrategier och metoder för att utarbeta dessa. Utvärderingen hur företaget arbetar för en hållbar utveckling ur ett socialt och ekologiskt perspektiv var övergripande och utgick från de kriterier Folksam använder i sin årligt återkommande studie, Folksams Index för ansvarsfullt företagande. Kriterierna baseras på Global Compacts tio principer och OECD:s riktlinjer för företag samt Global Reporting Initiative´s (GRI) direktiv. Hur företaget arbetar för en ekonomisk hållbar utveckling har också utvärderats på en övergripande nivå, uteslutande baserad på valda delar i GRI:s direktiv. Gustavsberg AB i Vårgårda har länge och engagerat arbetat för att minska företagets negativa miljöpåverkan. Det har lett till betydande vinster i miljöprestanda. Flera nyckeltal till exempel som kontinuerligt följs upp visar på minskad förbrukning. Inte minst har miljöarbetet lett till utveckling av produkterna. Beräkningen som gjordes i detta arbete med avseende på två av nyckeltalen, vatten och propan, visade att kostnadsbesparingar kunnat göras, exklusive de investeringar företaget gjort för att minska förbrukningen. Utvärderingen visade att Gustavsberg AB i Vårgårda förutom miljöarbetet också enligt det sociala och ekonomiska perspektivet bidrar till en hållbar utveckling. Förbättringar är dock möjliga att göra. Speciellt kan företagets sociala bidrag utvecklas. Men framförallt kan företaget behöva värdera värdet i en hållbarhetsinriktad strategi och se till alla tre dimensionerna av hållbar utveckling. Hållbarhetsarbetet bör behandlas som en del i affärsverksamheten i strävan mot ökad försäljning och minskade kostnader samt ett ansvarsfullt företagande. / <p>Uppsatsnivå: D</p>

El processament convencional de materials d'òxid de titani (TiO2) inherentment implica un consum energètic important i ha esdevingut una limitació tecnològica per a la fabricació de dispositius emprant substrats termolàbils així com per a la preparació de materials híbrids orgànic/TiO2. Aquesta tesi doctoral tracta del desenvolupament de processos químics per a la preparació de capes i pols de TiO2 d'acord amb principis de Química Verda, posant especial èmfasi en el processament a baixa temperatura. Plantejaments simples, benignes amb el medi ambient i de baix cost són els desitjats sota aquestes directrius. A més a més, els mètodes a baixa temperatura (idealment fins a un màxim proper a 100ºC) haurien de donar lloc a materials que exhibeixin propietats similars a aquells processats a alta temperatura o tractats solvotermalment. S'ha focalitzat especial interès en la recerca d'aplicacions pràctiques dels materials produïts en camps com la conversió d'energia solar i materials actuadors. / El procesamiento convencional de materiales de óxido de titanio (TiO2) inherentemente implica un consumo energético importante y ha resultado una limitación tecnológica para la fabricación de dispositivos utilizando substratos termolábiles así como para la preparación de materiales híbridos orgánico/TiO2. Esta tesis doctoral trata el desarrollo de procesos químicos suaves para la preparación de capas y polvos de TiO2 de acuerdo con principios de Química Verde, poniendo especial énfasis en el procesamiento a baja temperatura. Planteamientos simples, benignos con el medioambiente y de bajo conste son los deseados bajo estas directrices. Además, los métodos a baja temperatura (idealmente hasta un máximo próximo a 100ºC) deberían dar lugar a materiales que exhiban propiedades similares a aquellos procesados a alta temperatura o tratados solvotermalmente. Se ha centrado especial interés en la búsqueda de aplicaciones prácticas de los materiales producidos en campos como la conversión de energía solar y materiales actuadores. / Conventional high-temperature processing of titanium dioxide (TiO2) materials inherently implies important energy consumption and has became a technological limitation for fabricating devices employing thermolabile substrates as well as preparing hybrid organic/TiO2 materials. This PhD thesis deals with the development of chemical processes for preparing TiO2 films and powders fitting Green Chemistry principles, putting special emphasis on low-temperature processing. Simple, environmentally benign and low-cost approaches are desired upon these guidelines. Moreover, low-temperature methods (ideally up to a maximum closer to 100ºC) should give rise to materials exhibiting properties similar than those processed at high temperature or solvothermally treated. Special interest has been focused on finding practical applications of the as-prepared materials in fields such as solar energy conversion and actuating materials.

Bakgrund: Baby Friendly Hospital Initiativ bygger på Tio steg till lyckad amning och lanserades år 1991 i Sverige. Efter detta sågs en ökning av amningsfrekvensen. Nu 20 år efter införandet av Tio steg till lyckad amning sjunker amningsfrekvensen. Studier har visat att amningsutfallet påverkas av hur amningen initieras samt det stöd kvinnan får från vårdpersonal, partner och närstående. Syfte: Syftet med denna studie var att beskriva nyblivna mödrars erfarenheter av förberedelse och initiering av amning. Metod: En enkätstudie med slutna frågor där det fanns möjlighet till egna kommentarer på ett flertal av frågorna. Enkäten delades ut till nyblivna mödrar vid efterkontrollen på kvinnohälsovårdsmottagningen. Det var 98 kvinnor som deltog i studien. Svaren analyserades med statistikprogrammet SPSS version 18. Resultatet beskrivs med deskriptiv statistik och Chi-2 test användes. Resultat: Totalt ammade 64,9 % av kvinnorna helt vid efterkontrollen och 23,7 % ammade delvis. På kvinnohälsovårdsmottagningen hade de flesta kvinnorna diskuterat amning med sin barnmorska. Kvinnorna sökte även information själva på internet, i böcker, tidningar och hos närstående. Förstföderskorna sökte information i större utsträckning än omföderskorna. Drygt hälften av kvinnorna hade upplevt ett tillräckligt stöd från vårdpersonalen kring amningen och majoriteten av kvinnorna uppgav att deras partner var positivt inställd till amning. På BB hade 42,8 % av barnen tillmatats med bröstmjölksersättning och av dessa hade ca hälften fått det på medicinska indikationer och hälften hade fått det utan medicinsk indikation. Majoriteten av barnen använde tröstnapp vid efterkontrollen. Slutsats: Till stor del följs Tio steg till lyckad amning, men på vissa punkter ses brister i följsamheten. Kvinnorna hade önskat mer information och stöd i initieringen av amningen. Nyfödda barn tillmatades med bröstmjölksersättning utan medicinsk indikation och många barn introducerades för tröstnapp inom 2 veckor från födelsen.

The phase transformation of anodized Ti film has been studied. Although X-ray diffraction detected only the amorphous TiO2 phase, transmission electron microscopy analysis showed that TiO nanocrystallites less than 10 nm in size were also present, which was further supported by x-ray photoelectron spectroscopy analysis. Anatase was found to appear gradually by annealing the as-anodized specimen in air at 500¡V550 oC, which was accompanied by a simultaneous disappearance of TiO nanocrystallites. In contrast, only rutile is formed by annealing the Ti film at the same temperatures. The results indicate that TiO can induce the formation of anatase, which is explained by the close similarity between their structures. (Chapter 1) Anatase phase of TiO2 has been shown to have very good biocompability. It was frequently observed on Ti surfaces after anodizing and thermal annealing treatments. In this report the mechanisms of the Ti to TiO and the TiO to anatase phase transitions in anodizing and annealing treatments of Ti have been studied by transmission electron microscopy. Ti thin films of two strong textures were first grown on the (001)NaCl substrates. In addition to amorphous TiO2, the anodization treatment caused the formation of TiO with an orientation relationship of (11-20)Ti // (220)TiO with Ti. The subsequent thermal annealing treatment caused the TiO to anatase transition with an orientation relationship of {200}TiO //{200}A. Pure anatase film was prepared by this method. (Chapter 2)

Abstract Recently, titanium dioxide¡]TiO2¡^ is one of the most extensively studied transition-metal oxides because of its remarkable photocatalyst efficiency and electronic properties. In this paper, thin films ware obtained by dual ion beam sputtering. By different processes, these samples can be classified into three categories. Firstly, thin films, deposited on 200 mash copper grids for 15 minutes, were investigated that many TiO grains is about 5 nm in size by transmission electron microscopy¡]TEM¡^. Next, TiO2 thin films, sputtered on si wafers and glass for 180 minutes in an O2 environment by using titanium target, were initially identified by X ray diffraction instrument¡]XRD¡^. The result shows that some thin films have good orientations. By TEM, TiO2 grains on bottom of films are about 20 nm. By scanning electron microscopy¡]SEM¡^, TiO2 grains on the surface are about 1~2 £gm in size and are oblong in shape. The last, TiO thin films were directly deposited on si wafer for 180 minutes in no O2 environment by using titanium target and then annealed to transform from TiO to TiO2. By XRD, the thin film, annealed at 600¢J for 1hr, has good orientation. By TEM, TiO2 grains, annealed at 1000¢J for 24hr, grow up to 1-2 £gm in size and are oblong in shap.

Lithium-ion batteries play a crucial role in portable electronics, but require further innovation for electric vehicle and grid storage applications. To meet this demand, significant emphasis has been placed on developing safe, inexpensive, high energy density cathode materials. LiFePO₄ is a candidate cathode material for electric vehicle and grid storage applications. Vanadium-doped LiFePO₄ cathodes of the form [chemical formula] (0 ≤ x ≤ 0.25) were synthesized here by a facile, low-temperature microwave-assisted solvothermal (MW-ST) method. Such an approach offers manufacturing-energy and cost savings compared to conventional synthesis. Additionally, although [chemical formula] has been synthesized previously by conventional methods, it is shown here that the MW-ST method allows much higher doping levels than can be achieved at conventional temperatures, indicating that metastable phases can be isolated through the low-temperature microwave-assisted synthesis. LiFePO₄ suffers from poor ionic conductivity, but this limitation can be minimized by microwave-assisted synthesis through a tuning of the particle size, allowing for decreased Li⁺ diffusion paths. LiVOPO₄ is another polyanion material with higher energy density than LiFePO₄, but similar ionic conductivity limitations. It has not been previously synthesized by MW-ST. Thus, a MW-ST method was developed here to prepare LiVOPO₄. By varying reaction conditions, three polymorphic modifications of LiVOPO₄ were accessed and the electrochemical performance was optimized. LiVOPO₄ can be further discharged to Li₂VOPO₄, which has been suggested in the literature, but the structural transformation that accompanies this process has not been detailed. To this end, the delithiation process was studied by ex situ XRD measurements to better understand how the second lithium is accommodated. Finally, MW-ST has also been exploited to grow thin films of anatase TiO₂ phase on indium tin oxide (ITO)-coated glass substrates. The microwave field is selectively absorbed by the conductive ITO layer on the glass substrates, leading to ohmic heating. The resulting heated ITO layer acts as a favorable site for nucleation and growth. TiO₂ thin films have widespread applications in the energy and electronics sectors. Such selective microwave-assisted ohmic heating of solid materials within a growth solution represents a promising new avenue for microwave synthesis, which has been minimally explored in the literature. / text

Developing a fundamental understanding of photocurrent generation processes at organic-inorganic interfaces is critical for improving hybrid solar cell efficiency and stability. This dissertation explores processes at these interfaces by combining data from photovoltaic device performance tests with characterization experiments conducted directly on the device. The dissertation initially focuses on exploring how morphologically and chemically modifying the organic-inorganic interface, between poly(3-hexylthiophene) (P3HT) as the electron donating light absorbing polymer and titanium dioxide (TiO₂) as the electron acceptor, can result in stable and efficient hybrid solar cells. Given the heterogeneity which exists within bulk heterojunction devices, stable interfacial prototypes with well-defined interfaces between bilayers of TiO₂ and P3HT were developed, which demonstrate tunable efficiencies ranging from 0.01 to 1.6 %. Stability of these devices was improved by using Cu-based hole collecting electrodes. Efficiency values were tailored by changing TiO₂ morphology and by introducing sulfide layers like antimony trisulfide (Sb₂S₃) at the P3HT-TiO₂ interface. The simple bilayer device design developed in this dissertation provides an opportunity to study the precise role played by nanostructured TiO₂ surfaces and interfacial modifiers using a host of characterization techniques directly on a working device. Examples introduced in this dissertation include X-ray photoelectron spectroscopy (XPS) depth profiling analysis of metal-P3HT and P3HT-TiO₂ interfaces and Raman analysis of bonding between interface modifiers like Sb₂S₃ and P3HT. The incompatibility of TiO₂ with P3HT was significantly reduced by using P3HT derivatives with -COOH moieties at the extremity of a polymer chain. The role of functional groups like -COOH in interfacial charge separation phenomena was studied by comparing the photovoltaic behavior of these devices with those based on pristine P3HT. Finally, for hybrid solar cells discussed in this dissertation to become commercially viable, high temperature processing steps of the inorganic TiO₂ layer must be avoided. Accordingly, this dissertation demonstrates the novel use of electromagnetic radiation in the form of microwaves to catalyze growth of anatase TiO₂ thin films at temperatures as low as 150 °C, which is significantly lower than that used in conventional techniques. This low temperature process can be adapted to a variety of substrates and can produce patterned films. Accordingly, the ability to fabricate TiO₂ thin films by the microwave process at low temperatures is anticipated to have a significant impact in processing devices based on plastics. / text