Este trabalho investigou a obtenção de filmes de TiO2 por sol-gel e dipcoating (SGDC) e sua caracterização microestrutural e como fotocatalisador para a produção de hidrogênio a partir da água. Os precursores e reagentes utilizados foram: propóxido de titânio, ácido acético, etanol anidro, acetilacetona, Triton X-100 e polivinilbutiral (PVB). Foram preparadas 2 soluções precursoras, uma com PVB e outra sem. Foram produzidos filmes com 1, 2 e 3 camadas através da técnica de dip-coating. Os filmes foram tratados termicamente a 400, 500 e 600ºC, com uma taxa de 100ºC/h e um patamar de 2 h. O TiO2 sintetizado e os filmes produzidos foram caracterizados por difração de raios X (DRX) quanto à cristalinidade, fases presentes e tamanho de cristalito; microscopia eletrônica de varredura (MEV), adsorção de nitrogênio (método BET), análises termogravimétricas (ATG) e termodiferenciais (ATD), elipsometria espectroscópica, perfilometria óptica, espectroscopia Raman e de reflectância difusa (determinação do band gap). Após o tratamento térmico os filmes apresentaram uma microestrutura bastante irregular e com muitas trincas, com a presença da fase anatase em todas as temperaturas de tratamento térmico, e um teor de 3,7% de rutilo à 600ºC. O band gap dos filmes aumentou com a quantidade de camadas adicionadas, com a elevação da temperatura de tratamento térmico e adição de PVB. As medidas de fotocorrente foram realizadas no escuro e sob iluminação de lâmpada de Xe com 250W (simulador de luz solar de 1,5AM). A maior fotocorrente medida foi de 12 μA a 0,5V. A produção de H2 aumentou linearmente com o tempo de exposição para ambas as amostras com PVB. Foi possível relacionar a adição do PVB com o favorecimento da fotoatividade dos filmes de TiO2. / This work has investigated the effect of polyvinyl butyral addition in the synthesis of TiO2 films by sol-gel and dip-coating, their microstructural features and their photoelectrochemical activity for water-splitting hydrogen production. The precursors and reagents used were: titanium propoxide, acetic acid, anhydrous ethanol, acetylacetone, Triton X-100 and polyvinyl butyral (PVB). Two precursor solutions were prepared: one with PVB and another without it. The dip-coating technique was used to produce films with 1, 2 and 3 layers. The films were heat treated at 400, 500 and 600ºC, at a rate of 100°C/h and dwelling time of 2h. Afterwards the synthesized films were characterized by X-ray diffraction (XRD); scanning electron microscopy (SEM), nitrogen adsorption (BET method), thermogravimetric (TGA) and differential thermal analysis (DTA), spectroscopic ellipsometry, optical profilometry, Raman and diffuse reflectance spectroscopy (determination of the band gap). The films after heat treatment showed a very irregular microstructure with many cracks. The anatase phase was presented in all temperatures and a small content of rutile at 600 °C (around 3.7%) was identified. The band gap of the films increased with the number of layers, heat treatment and addition of PVB. The photocurrent measurements were carried out in the dark and under illumination with 250W Xe, using a sunlight simulator (1,5AM). The highest photocurrent was 12A at 0.5V. The H2 production increased linearly with time of exposure for both samples with PVB. Therefore, it was possible to relate the addition of PVB with improvement the photoactivity of TiO2 films.

To achieve sustainable production of H2 fuel through water splitting, low-cost electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are required to replace Pt and IrO2 catalysts. Here, for the first time, we present the interface engineering of novel MoS2/Ni3S2 heterostructures, in which abundant interfaces are formed. For OER, such MoS2/Ni3S2 heterostructures show an extremely low overpotential of ~218 mV at 10 mA cm-2, which is superior to that of the state-of-the-art OER electrocatalysts. Using MoS2/Ni3S2 heterostructures as bifunctional electrocatalysts, an alkali electrolyser delivers a current density of 10 mA cm-2 at a very low cell voltage of ~1.56 V. In combination with density function theory (DFT) calculations, this study demonstrates that the constructed interfaces synergistically favor the chemisorption of hydrogen and oxygencontaining intermediates, thus accelerating the overall electrochemical water splitting.

Dans le contexte actuel d’une demande énergétique croissante associée à un appauvrissement des ressources fossiles, il devient urgent de trouver des sources d’énergies alternatives, écologiquement et économiquement viables. La photocatalyse est une voie prometteuse et innovante pour produire de l’hydrogène (H2) à partir d’énergies renouvelables. Le but est de développer des matériaux stables et efficaces pour amener le procédé à un niveau de maturité suffisant pour de possibles développements à moyen terme.Cette thèse est axée sur l’élaboration et l’optimisation de nouveaux systèmes composites nanostructurés, Au / gC3N4 / TiO2, pour la production d’hydrogène par procédé photocatalytique à partir de l’eau et de l’énergie solaire. L’aspect innovant étant d’optimiser chaque composant de manière à tirer profit des avantages de chacun, puis à surmonter leurs limitations individuelles en les associant de manière intime dans des structure hiérarchisées afin d’obtenir des taux de production d’H2 compétitifs à température ambiante sous illumination solaire et visible. Une étude comparative a également été entreprise sur le photocatalyseur commercial TiO2 P25 « Evonik ® » et met en avant l’efficacité de ces nouveaux matériaux. Pour finir, les activités photocatalytiques de ces composites ont ensuite été corrélées avec leurs propriétés physico-chimiques. / Nowadays, energy demand is constantly increasing while fossil ressources are dwindling and has become imperative to find new alternative energy sources. Photocatalysis is a promising and innovative way to produce hydrogen (H2) from renewable energies. The ai mis to develop stable and efficient materials in order to bring the process towards sufficient efficiency for possible mid-term developments. This thesis focuses on the development and optimization of new nanostructured composite systems, Au / gC3N4 / TiO2, for hydrogen produciton by water-splitting. The innovative aspect is to optimize every components in order to take advantages of each and then to intimately associate them in hierarchical structure for obtaining competitive rates of hydrogen production at room temperature under solar and visible illumination. A comparative study was also undertaken on commercial photocatalyst TiO2 P25 « Evonik ® » to highlight the efficiency of these new materials. Finally, photocatalytic activities of these composites were correlated with their physico-chemical properties.

In 1972 Fujishima and Honda conceptualised a photoelectrochemical cell for hydrogen generation via PEC water splitting. Hydrogen as a clean energy carrier provides environmentally friendly energy storage solutions or can fuel certain applications. This idea has since then been further built upon with new materials and combinations with the aim of improving efficiency. In this project n-type cubic silicon carbide thick layers were grown by a sublimation method and characterised for water splitting performance. A generated photo-current density of 0.45 mA/cm2 was measured with no bias between the working and counter electrodes.

L’objectif de ce travail a été d’étudier des matériaux semiconducteurs de type p comme photocathode pour la réduction de protons dans le cadre de la photoélectrolyse de l’eau. Ainsi, deux types de matériaux ont été étudiés, des oxydes de cuivre, Cu2O et CuO, et des matériaux à structure pérovskite (ATiO3, A=Ca, Ba, Sr) dopées au fer et à l’azote. Les oxydes de cuivre ont été synthétisés par deux voies différentes afin d’obtenir des films : par voie sol-gel couplée au dip-coating et par électro-dépôt et anodisation du cuivre. La photocorrosion des oxydes de cuivre en milieu aqueux et sous illumination a été mise en évidence. La protection des oxydes de cuivre via une hétérojonction avec un semiconducteur de type n (TiO2 ou BaTiO3) a révélé une meilleure stabilité des électrodes au cours du temps ainsi que des photocourants élevés grâce à une composition et une architecture originales. Les pérovskites ont été synthétisées par voie sol-gel couplée au dip-coating. Ce sont des semiconducteurs de type n ; ainsi l’étude du dopage au fer, pour substituer le titane, et à l’azote, pour substituer l’oxygène, a mis en évidence un changement de nature de type n à type p, ainsi qu’une diminution de la largeur de bande interdite. Les propriétés physico-chimiques de toutes les électrodes synthétisées ont été caractérisées (structure cristalline, morphologie, propriétés optiques et électrochimiques) et discutées en fonction de leur composition et des paramètres de synthèse. Ces travaux ont permis d’élaborer des photocathodes originales, performantes et stables au cours du temps (oxydes de cuivre protégées), et de démontrer l’utilisation de pérovskites dopées pour cette application. / The aim of this work was to study p-type semiconducting materials as photocathodes for protons reduction into H2 for water splitting application. Two types of materials have been studied: copper oxides, Cu2O and CuO, and materials with a perovskite structure (ATiO3, A=Ca, Ba, Sr) doped by iron and nitrogen. Copper oxides have been synthetized by two different ways in order to obtain films: sol-gel process coupled with dip-coating and copper plating and anodization. Copper oxides photocorrosion has been highlighted in aqueous environment and under illumination. Their protection via a heterojunction with an n-type semiconductor (TiO2 and BaTiO3) improved electrodes stability over time and photocurrents, thanks to original composition and architecture. Perovskites have been synthetized by sol-gel process coupled with dip-coating. They are well-known as n-type semiconductors; so the study of doping with iron, to substitute titanium, and with nitrogen, to substitute oxygen, shows a change from n-type to p-type, and a reduction of the band gap. The physical and chemical properties of the synthetized electrodes were characterized (crystal structure, morphology, optical and photoelectrochemical properties) and discussed according to the composition and synthesis parameters. This work enables to obtain original, efficient, and stable over time, photocathodes (protected copper oxides) and to demonstrate the potential use of doped perovskites for this application.

No description available.

Alternative energy research into hydrogen production via water electrolysis addresses environmental and sustainability concerns associated with fossil fuel use. Renewable-powered electrolyzers are foreseen to produce hydrogen if energy and cost requirements are achieved. Electrocatalysts reduce the energy requirements of operating electrolyzers by lowering the reaction kinetics at the electrodes. Platinum group metals (PGMs) tend to be utilized as electrocatalysts but are not readily available and are expensive. Ni1-xMox alloys, as low-cost and earth-abundant transition metal nanoparticles (NPs), are emerging as promising electrocatalyst candidates to replace expensive PGM catalysts in alkaline media. Pure-phase cubic and hexagonal Ni1-xMox alloy NPs with increasing Mo content (0–11.4%) were synthesized as electrocatalysts for the hydrogen evolution reaction (HER). In general, an increase in HER activity was observed with increasing Mo content. The cubic alloys were found to exhibit significantly higher HER activity in comparison to the hexagonal alloys, attributed to the higher Mo content in the cubic alloys. However, the compositions with similar Mo content still favored the cubic phase for higher activity. To produce a current density of -10 mA/cm2, the cubic and hexagonal alloy NPs require over-potentials ranging from -62 to -177 mV and -162 to -242 mV, respectively. The cubic alloys exhibited over-potentials that rival commercial Pt-based electrocatalysts (-68 to -129 mV at -10 mA/cm2). The cubic Ni0.934Mo0.066 alloy NPs showed the highest alkaline HER activity of the electrocatalysts studied and therefore a patent application was submitted. Bulk Ni–Mo phases have been known as electrocatalysts for the HER for decades, while recently transition metal phosphides (TMPs) have emerged as stable and efficient PGM alternatives. Specifically, Ni2P has demonstrated good HER activity and improved stability for both alkaline and acidic media. However, Ni2P electrocatalysts are a compromise between earth-abundance, performance (lower than Ni–Mo and PGMs) and stability. For the first time Ni–Mo–P electrocatalysts were synthesized with varying atomic ratios of Mo as electrocatalysts for alkaline HER. Specific phases, compositions and morphologies were studied to understand the intrinsic properties of TMPs leading to high HER activity. The Ni1.87Mo0.13P and Ni10.83Mo1.17P5 NPs were shown to be stable for 10 h at –10 mA cm-2 with over-potentials of –96 and –82 mV in alkaline media, respectively. The Ni1.87Mo0.13P and Ni10.83Mo1.17P5 NPs exhibited an improved performance over the synthesized Ni2P sample (–126 mV at –10 mA cm-2), likely a result of the overall phosphorous content and hetero-structured morphologies. A strong correlation between phase dependence and the influence of Mo on HER activity needs to be further investigated. Furthermore, understanding the intrinsic properties of electrocatalysts leading to high water splitting performance and stability can apply electrocatalysts in other research applications, such as photoelectrochemical (PEC) water splitting, water remediation and sustainable chemical processing applications. Contributions to photocatalytic water remediation and electrochemical chlorinated generation to halogenate pyridone-based molecules are reported. Electrochemical techniques were developed and reported herein to aid in understanding electrochemical performance, chemical mechanisms and the stability of electrocatalysts at the electrode-electrolyte interfaces.

The future energy demand will require a change in the current energy supply. In this regard, the production of hydrogen by photoelectrochemical solar cells is a promising alternative because the fuel is obtained from water and, importantly, its combustion is free of carbon. Many metal oxides, including those having a complex stoichiometry (i.e. ternary oxides) behave as semiconductors and present good stability in aqueous environments, making them attractive candidates for water splitting devices. This thesis focuses on the preparation and study of ternary metal oxide materials as photoelectrodes for water splitting, with emphasis on photocathodes. These materials must meet the requirements for a practical device: low cost, non-toxicity, made of Earth abundant elements, environmentally friendly, etc. The thesis also aims at the study of strategies to improve their photoelectrochemical response. lt comprises the investigation of the kinetics of hydrogen generation reaction and the characteristics of the electrode solution interface by photoelectrochemical impedance spectroscopy. The main points can be summarized as: (i) the effect of an electrochemical oxidative pretreatment in CuFe2Ü4 photocathodes (ii) the investigation of water splitting mechanisms in CaFe2Ü4 photocathodes, (iii) the effect of metal doping in LaFeO3 photocathodes (iv) the study of the photoelectrochemistry of compact and nanoparticulate YFeO3 photocathodes and (v) the effect of a reductive electrochemical treatment in NiTiO3 photoanodes, and comparison with the effect of the treatment in anatase electrodes.

Increasing energy consumption and its environmental impacts make it necessary to look for alternative energy sources. Solar energy as huge energy source which is able to cover the terms sustainability is considered as a favorable alternative. Solar cells and solar fuels are two kinds of technologies, which make us able to harness solar energy and convert it to electricity and/or store it chemically. Metal oxide semiconductors (MOSs) have a major role in these devices and optimization of their properties (composition, morphology, dimensions, crystal structure) makes it possible to increase the performance of the devices. The light absorption, charge carriers mobility, the time scale between charge injection, regeneration and recombination processes are some of the properties critical to exploitation of MOSs in solar cells and solar fuel technology. In this thesis, we explore two different systems. The first one is a NiO mesoporous semiconductor photocathode sensitized with a biomimetic Fe-Fe catalyst and a coumarin C343 dye, which was tested in a solar fuel device to produce hydrogen. This system is the first solar fuel device based on a biomimetic Fe-Fe catalyst and it shows a Faradic efficiency of 50% in hydrogen production. Cobalt catalysts have higher Faradic efficiency but their performance due to hydrolysis in low pH condition is limited. The second one is a photoanode based on the nanostructured hematite/magnetite film, which was tested in a photoelectrochemical cell. This hybrid electrode improved the photoactivity of the photoelectrochemical cell for water splitting. The main mechanism for the improvement of the functional properties relies with the role of the magnetite phase, which improves the charge carrier mobility of the composite system, compared to pure hematite, which acts as good light absorber semiconductor. By optimizing the charge separation and mobility of charge carriers of MOSs, they can be a promising active material in solar cells and solar fuel devices due to their abundance, stability, non-toxicity, and low-cost. The future work will be focused on the use of nanostructured MOSs in all-oxide solar cell devices. We have already obtained some preliminary results on 1-dimensional heterojunctions, which we report in Chapter 3.3. While they are not conclusive, they give an idea about the future direction of the present research.

While photocatalysis is considered a promising sustainable technology in the field of heterogeneous catalysis as well as biocatalysis, figures of merit (FOM) for comparing catalytic performance, especially between disciplines, are not well established. Here, photocatalytic water splitting was conducted using a semiconductor (NiO/La-NaTaO3) and a bio-photocatalyst (Synechocystis sp. PCC 6803) in the same setup under similar reaction conditions, eliminating the often ill-defined influence of the setup on the FOMs obtained. Comparing the results enables the critical evaluation of existing FOMs and a quantitative comparison of both photocatalytic systems. A single FOM is insufficient to compare the photocatalysts, instead a combination of multiple FOMs (reaction rate, photocatalytic space time yield and a redefined apparent quantum yield) is superior for assessing a variety of photocatalytic systems.