Thin nanoporous films are attractive for many potential uses for example gas separation, catalysis, filtration of viruses, ore flotation, or as low-dielectric-constant materials. Zeolite and mesoporous materials are the two important nanoporous material classes. In this thesis, we synthesized and characterized two different thin nanoporous films; (i) mesostructured films at the mica-solution interface; (ii) mechanical exfoliated zeolites. The mesoporous materials are well-defined pore shoe and size, and exhibit various morphologies, such as thin films, etc. In contrast, zeolites are a kind of perfect crystal and the morphologies are strongly related to their structures and are difficult to control. Therefore, first we synthesis mesostructured films at mica-solution interface in acidic solution. In-situ Atomic Force Microscopy (AFM) has been used to reveal the formation process of organic and inorganic mesophase films at the molecular level. Then, we synthesized two-dimensional zeolite structures via mechanical exfoliation process that does not involve any chemical intervention and can be applicable to a wide variety of structures with different chemical makeup. Three different zeolite structure nanosheets related to the structure code MWW, UTL, and MFI have been prepared. AFM and TEM have been used to characterized the exfoliated single nanosheet. In order to broaden the application of the single zeolite nanosheet, platinum nano-clusters are encapsulated within mechanical exfoliated zeolite MFI nanosheets by ion exchange from aqueous solution of [Pt(NH3)4](NO3)2. High-angle annular dark field scanning transmission electron microscopy has been used to indicate the Pt clusters in the zeolite MFI structures. Because of the property of the mechanically as-synthesised exfoliated MFI nanosheets that is the long hydrocarbon chains are essentially intact on both sides of the inorganic layer, and can prevent thickening of the zeolite MFI nanosheets along b-axis, we use the mechanically exfoliated MFI as seeds for further growth to form large scale MFI membrane with uniform nano-thickness. Encapsulating noble metals within the channels or cavities of zeolites has already drawn numerous attentions because the well-defined zeolite structure is able to constrain the metal nanoparticle (NPs) aggregation size and enhance the diversity and activity for catalysis. We use the organic surfactant (C22-6-6Br2) and [Pt(NH3)4](NO3)2 as the structure and metal precursor to form Pt-containing nanowires; and use F- to inhibit the premature precipitation of Pt precursors. After involving F-, the Pt-containing nanowire structures were generated.

L’étude et la compréhension des interactions existantes entre semi-conducteur et nanoparticules métalliques sous irradiation est primordiale pour l’amélioration de leurs performances. Dans cette étude, trois composites oxydes semi-conducteur-métal ont été synthétisés : TiO2-Ag, Fe2O3-Ag et WO3-Ag. La synthèse des films mésoporeux de TiO2, Fe2O3 et WO3 a été effectuée par voie sol gel à l’aide de copolymères à bloc, avec la méthode d’auto-assemblage induit par évaporation (EISA). Les nanoparticules d’argent sont formées dans un deuxième temps par réduction chimique de sels dans la porosité des films. L’étude photo-électrochimique de ces composites a permis de mettre en évidence différents phénomènes : le potentiel d’électroréduction des ions Ag+ dans une matrice de TiO2 mésoporeuse peut être modulé par l’effet de la lumière. Ce phénomène semble résulter d’un effet de passivation des NP Ag par TiO2 qui dépend des conditions d’insolation. Des effets de rechargement de l’électrode poreuse en espèce Ag+ ont aussi été observés, sous l’action simultanée de la chrono-ampérométrie et de l’irradiation / The study and understanding of existing interactions between semiconductor and metal nanoparticles under irradiation is essential for improving their performance. In this study, three semiconductor-metal oxide composites were synthesized: TiO2-Ag, Fe2O3-Ag and WO3-Ag. The synthesis of the mesoporous films of TiO2, Fe2O3 and WO3 was carried out by gel sol method using block copolymers, with the method of self-assembly induced by evaporation (EISA). The silver nanoparticles are formed in a second time by chemical reduction of silver salts in the porosity of the films. The photo-electrochemical study of these composites made it possible to highlight various phenomena: the electroreduction potential of Ag+ ions in a mesoporous TiO2 matrix can be modulated by the effect of light. This phenomenon seems to result from a passivation effect of the NP Ag by TiO2, which depends on the insolation conditions. Charging effects of the porous electrode in Ag+ species have also been observed, under the simultaneous action of chrono-amperometry and irradiation

Mesoporous thin films are promising architectures for positive electrodes in Li-ion battery applications. A particular challenge in this field has been successful templating of vanadium-based oxides, materials known for their ability to host lithium, since their thermal instability and complex vanadium chemistry hinder templating through traditional soft-chemistry approaches. To address these technical problems we here develop the soft-templating of vanadium and niobium mixed oxides based on Evaporation Induced Micelles Packing using thermally stable polystyrene-b-polyethyleneoxide structuring agents. In-situ thermal monitoring via ellipsometry allows successful navigation of the thermal stability landscape. TEM and AFM analyses reveal homogeneous wormlike mesoporous structures whose pore and inorganic wall sizes can be tuned from 15 to 100 nm by changing the hydrophobic/hydrophilic surfactant chain lengths. Ellipsometric porosimetry shows that 100 nm thick films with a 15 nm pore size displays 30% electrolyte accessible porosity. The interconnected tridimensional mesoporous network has been highlighted by electronic tomography. Thicker films up to 1.3 µm are prepared by a multidipping process. The superiority of such nanoarchitectures compared to non porous materials in terms of electrochemical properties such as capacity are revealed using cyclic voltammetry.

Lateral self-exchange of charge across dye-sensitized film is a phenomenon that may play animportant role in effectivizing H2 production from water via solar energy, and shows potential forother interesting applications. The rate of charge movement via lateral self-exchange across afilm is often quantified in terms of apparent diffusivity of charge, Dapp. In this project, it wasinvestigated how Dapp varies with applied potential, as preliminary results had shown resultsinconsistent with current theoretical understanding. To examine this discrepancy, Dapp wascalculated for different applied overpotentials on a ZrO2 film sensitized with the dye D35. It wasconcluded that values of Dapp vary with overpotential close to the dye’s redox potential, aspredicted by theory. Different dyes may yield other results, and further research on the subject isneeded. Interesting and unexplained differences in kinetics for oxidation and re-reduction of thedye were found, which prompts further studies on the matter.