L'utilisation intensive des combustibles fossiles et l’émission des produits de leur combustion (principalement du CO2) dans l'air ont déjà impacté le climat mondial. Trouver des solutions technologiques permettant la conversion de l'économie mondiale aux carburants propres et renouvelables devient urgent. Une de possibilités consiste en utilisation de l’hydrogène comme un vecteur d’énergie. Aujourd’hui elle est limitée par l’absence d’un matériau permettant son stockage à des températures ambiantes et à des pressions modérées.Dans ce projet, nous explorons la possibilité de préparer un nouveau matériau pour un stockage réversible de l’hydrogène par physisorption : les carbones nanoporeux substitués au bore. Nous montrons que la synthèse en arc électrique peut être optimisée pour produire des structures graphitisées, avec la variété de tailles, de formes et d'interconnexions entre les fragments de graphène. Leur morphologie, structure, composition chimique et homogénéité de la distribution de l’hétéroatome dans la structure carbonée ont été caractérisés par les techniques SEM, HRTEM, EELS, XRD et spectroscopie RMN. La porosité et propriétés adsorptives ont été étudiées en utilisant les mesures d’adsorption de l’azote à T= 77 K.Les deux paramètres essentiels pour un stockage efficace de l’hydrogène dans les conditions ambiantes sont la surface spécifique de l’adsorbant et l’énergie avec laquelle les molécules du gaz sont adsorbées sur cette surface. Nous montrons que la surface spécifique d’adsorption peut être contrôlée et augmentée par une activation thermique ou chimique pour optimiser le stockage, et que la présence du bore dans les structures carbonées permet de doubler l’énergie d'adsorption d'hydrogène du matériau. / The intensive use of fossil fuels and the emission of combustion products (mostly CO2) to air have already impacted global climate. We urgently need to find a technological solution to convert the global energy economy towards cleaner and renewable fuels. A possible solution consists in using hydrogen as energy vector. Today this technology is limited by the absence of material that could efficiently store hydrogen at ambient temperature and moderate pressures.In this project we explore the possibility to prepare a new material for reversible hydrogen storage by physisorption: boron-substituted nanoporous carbons. We show that electric arc discharge synthesis may be optimized to produce graphitized structures with a variety of graphene fragment sizes, forms, and interconnections between them. The morphology, structure, chemical composition, and homogeneity of boron distribution over the carbon samples were characterized using SEM, HRTEM, EELS, and XRD techniques, and HR solid state NMR. The porosity and adsorption parameters were determined from isotherms of nitrogen adsorption at T = 77 K.Two parameters that are essential for efficient hydrogen storage at ambient conditions are sorbent specific surface and the energy of gas adsorption at this surface. We show that material specific surface can be controlled and increased by thermal and/or chemical activation to enhance storage capacity, and that hydrogen adsorption energy in boron containing samples is twice as high as in all- carbon material.

The scarcity of freshwater is becoming a global challenge worldwide due to limited resources availability and increasing demand both for manufacturing and household use. For this reason, there is an important need to develop efficient, economic and sustainable desalination technologies able to take advantage of unconventional sources of water (seawater, brackish groundwater and wastewater) in order to produce freshwater. Sun is considered as the most promising abundant renewable (and free) energy source that can be employed in steam and vapor generation processes, which has a great importance in many applications such as: water desalination, domestic water heating, and power generation. This doctoral dissertation presents a study on the efficiency of different carbon based systems - nanofluids and hybrid natural composites - for the improvement of direct-solar evaporation systems, for the production of freshwater. The two main goals of this work consist of: (i) the synthesis and characterization of stable carbon-based nanofluids in water and of re-usable, economical and ecological hybrid composite materials, and (ii) the comparison of such carbon-based systems applied to water evaporation, understanding mechanisms, advantages and limitations. Carbon based materials (carbon black, graphene and multi-walled carbon nanotubes) were chosen because of their high sunlight absorption ability, unique thermal properties, as well as low cost and abundant availability. However, the hydrophobic character of such materials makes necessary to find efficient strategies to overcome this problem when dealing with water. In this work, the suspension stability of graphene-based nanofluids in water - a key parameter for the application of nanofluids in any field - was effectively improved by combining physical (by RF Sputtering coating) or chemical (by NaClO-NaBr solution) graphene surface modification treatments, and the use of common additives (Triton X-114, SDBS and gum arabic) showing different stabilization mechanisms. The best strategy to obtain long-time graphene suspension stability in water (both deionized water and saline solution with 3.5 wt% NaCl) turned out to be the combination of the easy chemical treatment with the electro-steric stabilization effect of gum arabic. In addition to nanofluids, a re-usable devices based on gum arabic cross-linked gelatin hydrogel were synthesized and characterized. Hydrophobic carbon-based materials were easily and uniformly embedded into the porous hydrogel matrix, thanks to the amphiphilic character of both gelatin and gum arabic. The effect of carbon-nanoparticles nature, morphology and concentration on the measured effective thermal conductivity of the composite material was studied and the thermal conductivity of the nanoparticles was evaluated applying several models based on the effective medium approach. The values obtained for the nanoparticles were far from the tabulated thermal conductivity values because of the combination of the composite features (such as nanoparticles concentration, Kapitza resistance) and the particles characteristics (such as aspect ratio, crystalline structure). The performance of carbon-based nanofluids and hybrid hydrogels on direct-solar evaporation of water was tested and compared to that of carbon-wood bilayer composite (which presents both hydrophilic character and natural channels for water transportation) under solar simulator. The effect of surface temperature, light-to-heat conversion efficiency of carbon-based materials, heat losses, water transport through a porous medium and suspension stability (in the case of nanofluids) were investigated in order to understand the advantages and limitations of such systems. All the tested systems were able to improve water evaporation rate and evaporation efficiency up to 70% and 82% under 1 sun and 2 suns respectively using a small amount of nanoparticles: the same amount of particles dispersed in nanofluid (0.01 wt%) was embedded into hydrogels or deposited onto wood. The high sunlight absorption ability of carbon-based nanoparticles appeared as a dominant parameter for the improvement of water evaporation rate. In fact, enhanced light absorption was directly related to a high photothermal conversion efficiency, which caused an improvement in the surface temperature, leading to a consequent enhancement in evaporation rate. It has been found that an adequate supply of water to the evaporation surface represents a fundamental parameter as well considering floating systems.

No description available.

Technologies laser pour l’élaboration de matériaux carbonés pour microsystèmes analytiques environnementaux. Pas de résumé en français fourni / Amorphous carbon nitride (a-CzN) material has attractor much attention in research and development. Recently, it has become a more promising electrode material than conventional carbon based electrodes in electrochemical and biosensor applications. Nitrogen containing amorphous carbon (a-C:N) thin films have been synthesized by femtosecond pulsed laser deposition (fs-PLD) coupled with plasma assistance through Direct Current (DC) bias power supply. During the deposition process, various nitrogen pressures (0 to 50 Pa) and DC bias (0 to -350 V) were used in order to explore a wide range of nitrogen content into the film. The structure and chemical composition of the films have been studied by using Multi-wavelength (MW) Roman spectroscopy, electron energy-loss spectroscopy (EELS), X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HRTBM). The surface morphology has been studied by Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). Increasing the nitrogen pressure or adding a DC bias induced an increase of the N content, up to 28 at.%. Nitrogen content increase induces a higher sp2 character of the film. However DC bias has been found to increase the film structmal disorder, which was detrimental to the electrochemical properties. Indeed the electrochemical measurern-ts, investigated by cyclic voltammetry (CV), demonstrated that the a-CzNfilms show better electron transfer kinetics, reversibility and excellent reproducibility than the pure a-C films. Electrochemical grafting from diazoniurn salts was successfully achieved on this film, with a surface coverage of covalently bonded molecules close to the dense packed monolayer of ferrocene

Solar thermal energy is emerging as an important source of renewable energy for meeting the ever-increasing energy requirements of the world. Solar selective coatings are known to enhance the efficiency of the photo thermal energy conversion. An ideal solar selective coating has zero reflectance in the solar spectrum region (i.e., 0.3-2.5 µm) and 100% reflectance in the infrared (IR) region (i.e. 2.5-50 µm). In this thesis, novel carbon nanotubes (CNT) and graphene based absorbers have been developed for photo thermal applications. Carbon nanotubes have good optical properties (i.e., α and ε close to 1), high aspect ratios (> 150), high surface area (470 m2/g) and high thermal conductivity (> 3000 W/mK), which enable rapid heat transfer from the CNTs to the substrates. Similarly, graphene also exhibits high transmittance (97%), low reflectance, high thermal conductivity (5000 W/mK) and high oxidation resistance behaviour. The major drawback of using CNTs for photothermal applications is that it exhibits poor spectral selectivity (i.e., α/ε = 1). In other words, it acts as a blackbody absorber. On the other hand, graphene exhibits poor intrinsic absorption behaviour (α - 2.3%) in a broad wavelength range (UV-Near IR). The main objective of the present study is to develop CNT and graphene based absorbers for photothermal conversion applications. The growth of CNT and graphene was carried out using chemical vapour deposition and sputtering techniques. An absorber-reflector tandem concept was used to develop the CNT based tandem absorber (Ti/Al2O3/Co/CNT). The transition from blackbody absorber to solar selective absorber was achieved by varying the CNT thicknesses and by using a suitable underlying absorber (Ti/Al2O3). A simple multilayer heat mirror concept was used to develop the graphene based multilayer absorber (SiO2/graphene/Cu/graphene). The transition from high transmitance to high absorptance was achieved by varying the Cu thickness. The refractive indices and the extinction coefficients of Ti/Al2O3, AlTiO and graphene samples were determined by the phase-modulated spectroscopic ellipsometric technique. Finally, the optical properties (i.e., absorptance and the emittance) of the CNT and graphene based absorbers were investigated. Chapter 1 gives a brief introduction about solar thermal energy, spectrally selective coating and photothermal conversion. The different types of absorbers used to achieve the spectral selectivity have also been discussed shortly. A brief description about the carbon-based materials/allotropes and their properties are outlined. The properties of carbon nanotubes and graphene which are the 1-D and 2-D allotropes of carbon, respectively are tabulated. A detailed literature survey was carried out in order to identify the potential candidates for the photothermal conversion applications. The objectives and the scope of the thesis are also discussed in this chapter. Chapter 2 discusses the deposition and characterization techniques used for the growth and the study of 1-D and 2-D carbon nanostructures. Atmospheric pressure chemical vapour deposition (CVD) and hot filament CVD techniques were used to grow CNT and graphene, respectively. The magnetron sputtering technique was used for the growth of ‘Ti’, ‘Al2O3’ and Co layers which were needed to grow the CNT based tandem absorber on stainless steel (SS) substrates. The important characterization techniques used to examine various properties of the 1-D and 2-D carbon nanostructures include: X-ray diffraction, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), phase modulated ellipsometry, UV-VIS-NIR spectrophotometer, Fourier-infrared spectroscopy (FTIR), micro-Raman spectroscopy and solar spectrum reflectometer and emissometer. Chapter 3 describes the design and development of Ti/Al2O3 coating for the growth of CNT-based tandem absorber on SS substrates. The power densities of the aluminum and titanium targets and the oxygen flow rates were optimized to deposit the Ti/Al2O3 coatings. The optimized Ti/Al2O3 coating with a Co catalyst on top was used as an underlying substrate to grow the CNT-based tandem absorber at 800°C in Ar+H2 atmosphere (i.e., CNT/Co/Al2O3/Ti/SS). The formation of aluminum titanium oxide (AlTiO) was observed during the CNT growth process and this layer enhances the optical properties of the CNT based tandem absorber. The optical constants of Ti, Al2O3 and AlTiO coatings were measured using phase modulated spectroscopic ellipsometry in the wavelength range of 300-900 nm. The experimentally measured ellipsometric parameters have been fitted with the simulated spectra using the Tauc-Lorentz model for generating the dispersion of the optical constants of the Al2O3 and the AlTiO layers. The Ti and Al2O3 layer thicknesses play a major role in the design of the CNT based tandem absorber with good optical properties. Chapter 4 describes the synthesis and characterization of the CNT based tandem absorber (Ti/AlTiO/CoO/CNTs) deposited on SS substrates. CNTs at different thicknesses were grown on Ti/AlTiO/CoO coated SS substrates using atmospheric CVD at various growth durations. The transition from blackbody absorber to solar selective absorber was achieved by varying the thicknesses of the CNTs and by suitably designing the bottom tandem absorber. At thicknesses > 10 µm, the CNT forest acts as near-perfect blackbody absorber, whereas, at thicknesses ≤ 0.36 µm, the IR reflectance of the coating increases (i.e., ε = 0.20) with slight decrease in the absorptance (i.e., α = 0.95). A spectral selectivity (α/ε) of 4.75 has been achieved for the 0.36 µm-thick CNTs grown on SS/Ti/AlTiO/CoO tandem absorber. Chapter 5 discusses the growth of graphene on polycrystalline copper (Cu) foils (1 cm × 1 cm) using hot filament CVD. The roles of the process parameters such as gas flow rates (methane and hydrogen), growth temperatures (filament and substrate) and durations on the growth of graphene were studied. The process parameters were also optimized to grow monolayer, bilayer and multilayer graphene in a controlled manner and the growth mechanism was deduced from the experimental results. The presence of graphene on Cu foils was confirmed using XPS, micro-Raman spectroscopy, FESEM and TEM techniques. The FESEM data clearly confirmed that graphene starts nucleating as hexagonal islands which later evolves into dendritic lobe shaped islands with an increase in the supersaturation. The TEM data substantiated further the growth of monolayer, bilayer and multilayer graphene. The intensity of 2D and G peak ratio (i.e., I2D/IG = 2) confirmed the presence of the monolayer graphene and the absence of the ‘D’ peak in the Raman spectrum indicated the high purity of graphene grown on Cu foils. The results show that the polycrystalline morphology of the copper foil has negligible effect on the growth of monolayer graphene. In Chapter 6, the design and development of graphene/Cu/graphene multilayer absorber and the study of its optical properties are discussed. The multilayer graphene grown on Cu foils has been transferred on quartz and SiO2 substrates in order to fabricate the graphene/Cu/graphene multilayer absorber. The sputtering technique was used to deposit copper on top of graphene/quartz substrates. The uniformity of the transferred multilayer graphene films was confirmed using Raman mapping. A simple multilayer heat mirror concept was used to develop the graphene/Cu/graphene absorber on quartz substrates and the transition from high transmittance to high absorptance was achieved. In order to further enhance the absorption, the graphene/Cu/graphene multilayer coating was fabricated on SiO2 substrates. The thickness of the Cu layer plays a major role in creating destructive interference, which results in high absorptance and low emittance. A high specular absorptance of 0.91 and emittance of 0.22 was achieved for the SiO2 graphene/Cu/graphene multilayer absorber. The specular reflectance of the multilayer absorber coatings was measured using the universal reflectance accessory of the UV-VIS-NIR spectrophotometer. Chapter 7 summarizes the major findings of the present investigation and also suggests future aspects for experimentation and analysis. The results obtained from the present work clearly indicate that both CNT and graphene based absorbers can be used as potential candidates for photothermal applications. In particular, the CNT based tandem absorber can be used for high temperature solar thermal applications and the graphene based multilayer absorber finds applications in the area of photodetectors and optical broadband modulators.

Les applications des nanoparticules métalliques nécessitent des assemblées monodisperses et stables sur un substrat tel que le graphène ou le graphite. Le graphène épitaxié sur métal (GEM) est étudié, car il facilite l'auto-organisation des adsorbats. La différence entre les mailles du graphène et du métal conduit à un effet de moiré contenant certaines régions favorables de l'adsorption. Ce travail est consacré surtout aux systèmes Ru-C et Pt-C où nous nous sommes intéressé au substrat du GEM nu, des agrégats y etant deposés et des agrégats métalliques sur graphite. Les potentiels d'ordre de liason permettent de mener des études en dynamique moléculaire sur des systèmes de taille réaliste à température finie. Dans le cas du système Pt-C une paramétrisation est disponible dans la littérature. Cependant, pour le système du Ru-C une paramétrisation sur la base de données DFT était nécessaire. Ce modèle atomistique néglige les forces de dispersion importantes pour des milieux étendus. Basé sur les modèles de Grimme, nous avons développé une description implicite tenant compte de la structure du substrat et son extension semi-infinie. De plus les effets d'écrantage importants pour des milieux métalliques sont pris en compte. Basé sur ce champ de force nous montrons des propriétés des adsorbats sur des substrats carbonés où nous évaluons le modèle de forces de dispersion. Grâce à des simulations de dynamique moléculaire, la stabilité des adsorbats et du graphène a été étudié dans le contexte de la dynamique vibrationnelle et de diffusion. En accord avec les expériences, la mobilité des adsorbats sur graphite s'avère élevée en comparaison avec des adsorbats sur GEM / Applications of metal nanoparticles require monodisperse and stable assemblies on a substrate such as graphene or graphite. Epitaxial graphene on metal (GOM) has attracted research interest because it contributes to the self-organisation of adsorbates. The difference in the lattice constants of graphene and metal leads to a moiré that contains certain regions that are favorable for adsorption. This work is mainly concerned with the Ru-C and Pt-C systems where we were interested in the bare substrate of GOM, adsorbates deposited thereon and metal clusters on graphite. Bond order potentials allow to carry out molecular dynamics studies for systems of realistic size and at finite temperature. In the case of the Pt-C, a parametrization is available in the literature. However, for Ru-C systems a custom parametrization effort based on data from electronic structure calculations was necessary. This atomistic model neglects long ranged dispersion forces that are important for adsorption phenomena on extended substrates. Based on the Grimme models, we developed an implicit description that takes the layered structure and the semi-infinite extension of the substrate into account. Also, screening effects that are important for metal materials are taken into account. Based on this force field, we show results concerning the properties of adsorbates on carbon substrates while evaluating the dispersion model. With the help of molecular dynamics simulations, the stability of adsorbates and graphene has been studied in the context of vibrational and diffusion dynamics. In agreement with experiments, the mobility of the adsorbates on graphite is high in comparison with adsorbates on GOM