Dominique Begin

Nitrogen-doped carbon nanotubes as a highly active metal-free catalyst for selective oxidation.

Catalytic reactions are generally carried out on supported metals or oxides, which act as an active phase and require impregnation and thermal treatment steps. During tests, the metal or oxide nanoparticles could be further sintered, which would induces deactivation. Direct incorporation of the active phase into the matrix of a support could be an elegant alternative to prevent catalyst deactivation. Here, we report that nitrogen-doped carbon nanotubes (N-CNTs) can be efficiently employed as a metal-free catalyst for oxidative reactions that allow the selective transformation of the harmful, gaseous H(2)S into solid sulfur. The catalyst exhibits a high stability during the test at high space velocity. The macroscopic shaping of the catalyst on the silicon carbide foam also increases its catalytic activity by improving the contact between the reactants and the catalyst. Such macroscopic shaping allows the avoidance of problems linked with transport and handling of nanoscopic materials and also reduces the pressure drop across the catalyst bed to a large extent.

Preparation, electrical and elastic properties of new anisotropic expanded graphite-based composites

Abstract New composite materials with application to catalyst supports or adsorbents are presented. They are made of compressed expanded graphite of various densities first impregnated by polyfurfuryl alcohol and next pyrolyzed and activated. The resultant materials are monoliths comprising a graphite backbone coated by a thin layer of active carbon. The electrical conductivity and the dynamic elastic moduli are measured on each kind of material, namely before and after carbonization, and finally after activation. The results are shown to be consistent with a percolation phenomenon: the conductivity and the rigidity thresholds are derived, and several theoretical considerations and comparisons with pure expanded graphite are made. The discussion leads to a better understanding of the structure of the materials before and after impregnation, namely the graphite backbone and the graphite–polymer or carbon composites. Besides, their conductive and elastic properties are shown to be very good. Hence, the materials are expected to have fair thermal conductivities, to be electrically regenerable (application as adsorbents) and to have an interesting life time (application as catalyst supports).

Carbon Nanotube Degradation in Macrophages: Live Nanoscale Monitoring and Understanding of Biological Pathway

Despite numerous applications, the cellular-clearance mechanism of multiwalled carbon nanotubes (MWCNTs) has not been clearly established yet. Previous in vitro studies showed the ability of oxidative enzymes to induce nanotube degradation. Interestingly, these enzymes have the common capacity to produce reactive oxygen species (ROS). Here, we combined material and life science approaches for revealing an intracellular way taken by macrophages to degrade carbon nanotubes. We report the in situ monitoring of ROS-mediated MWCNT degradation by liquid-cell transmission electron microscopy. Two degradation mechanisms induced by hydroxyl radicals were extracted from these unseen dynamic nanoscale investigations: a non-site-specific thinning process of the walls and a site-specific transversal drilling process on pre-existing defects of nanotubes. Remarkably, similar ROS-induced structural injuries were observed on MWCNTs after aging into macrophages from 1 to 7 days. Beside unraveling oxidative transformations of MWCNT structure, we elucidated an important, albeit not exclusive, biological pathway for MWCNT degradation in macrophages, involving NOX2 complex activation, superoxide production, and hydroxyl radical attack, which highlights the critical role of oxidative stress in cellular processing of MWCNTs.

Design of covalently functionalized carbon nanotubes filled with metal oxide nanoparticles for imaging, therapy, and magnetic manipulation.

Nanocomposites combining multiple functionalities in one single nano-object hold great promise for biomedical applications. In this work, carbon nanotubes (CNTs) were filled with ferrite nanoparticles (NPs) to develop the magnetic manipulation of the nanotubes and their theranostic applications. The challenges were both the filling of CNTs with a high amount of magnetic NPs and their functionalization to form biocompatible water suspensions. We propose here a filling process using CNTs as nanoreactors for high-yield in situ growth of ferrite NPs into the inner carbon cavity. At first, NPs were formed inside the nanotubes by thermal decomposition of an iron stearate precursor. A second filling step was then performed with iron or cobalt stearate precursors to enhance the encapsulation yield and block the formed NPs inside the tubes. Water suspensions were then obtained by addition of amino groups via the covalent functionalization of the external surface of the nanotubes. Microstructural and magnetic characterizations confirmed the confinement of NPs into the anisotropic structure of CNTs making them suitable for magnetic manipulations and MRI detection. Interactions of highly water-dispersible CNTs with tumor cells could be modulated by magnetic fields without toxicity, allowing control of their orientation within the cell and inducing submicron magnetic stirring. The magnetic properties were also used to quantify CNTs cellular uptake by measuring the cell magnetophoretic mobility. Finally, the photothermal ablation of tumor cells could be enhanced by magnetic stimulus, harnessing the hybrid properties of NP loaded-CNTs.

A few-layer graphene–graphene oxide composite containing nanodiamonds as metal-free catalysts

We report a high yield exfoliation of few-layer-graphene (FLG) with up to 17% yield from expanded graphite, under 5 h sonication time in water, using graphene oxide (GO) as a surfactant. The aqueous dispersion of GO attached FLG (FLG–GO), with less than 5 layers, is used as a template for further decoration of nanodiamonds (NDs). The hybrid materials were self-organized into 3D-laminated nanostructures, where spherical NDs with a diameter of 4–8 nm are homogeneously distributed on the surface of the FLG–GO complex (referred to as FLG–GO@NDs). It was found that GO plays a dual role, it (1) mediated exfoliation of expanded graphite in aqueous solution resulting in a FLG–GO colloid system, and (2) incorporated ND particles for the formation of composites. A high catalytic performance in the dehydrogenation of ethyl-benzene on FLG–GO@ND metal-free catalyst is achieved; 35.1% of ethylbenzene conversion and 98.6% styrene selectivity after a 50 h reaction test are observed which correspond to an activity of 896 mmolST gcatalyst−1 h−1, which is 1.7 and 5 times higher than those of the unsupported NDs and traditional catalysts, respectively. The results demonstrate the potential of the FLG–GO@ND composite as a promising catalyst for steam-free industrial dehydrogenation applications.

Few layer graphene decorated with homogeneous magnetic Fe3O4 nanoparticles with tunable covering densities

Magnetic iron oxide nanoparticles (NPs) with narrow size distribution (8 ± 2 nm), well defined chemical composition and crystalline structure are synthesized and homogeneously dispersed onto the surface of few-layer graphene (FLG) via a solvothermal decomposition method. The iron oxide NPs are strongly anchored to the graphene surface and confer a magnetic character to the final composite. The metal oxide/support interaction is high enough to avoid the NPs coalescence and/or agglomeration and thus to preserve the NPs size and dispersion after thermal treatment up to 400 °C. The introduced iron oxide NPs on FLG also play a role of nano-spacers to prevent the re-stacking of the graphene sheets upon the drying process. It is expected that such a composite could find use in several application fields such as catalyst support for liquid-phase reactions with easy magnetic separation, in electrochemical energy storage and in waste water treatment. The ability of the synthesized iron oxide NP/FLG composite to adsorb foreign elements (organic pollutants) is demonstrated in the methylene blue (MB) adsorption and its catalytic properties are evaluated in the selective oxidation of H2S.

Synthesis of porous carbon nanotubes foam composites with a high accessible surface area and tunable porosity

The macroscopic shaping of carbon nanostructure materials with tunable porosity, morphologies, and functions, such as carbon nanotubes (CNT) or carbon nanofibers (CNF), into integrated structures is of great interest, as it allows the development of novel nanosystems with high performances in filter applications and catalysis. In the present work, we report on a low temperature chemical fusion (LTCF) method to synthesize a self-macronized carbon nanotubes foam (CNT-foam) with controlled size and shape by using CNT as a skeleton, dextrose as a carbon source, and citric acid as a carboxyl group donor reacting with the hydroxyl group present in dextrose. The obtained composite has a 3D pore structure with a high accessible surface area (>350 m2 g−1) and tunable meso- and macro-porosity formed by the addition of a variable amount of ammonium carbonate into the starting mixture followed by a direct thermal decomposition. The as-synthesized CNT-foam also exhibits a relatively high mechanical strength which facilitates its handling and transport, while the nanoscopic morphology of the CNT significantly reduces the problem of diffusion and contributes to an improvement of the effective surface area for subsequent applications. These CNT-foams are successfully employed as selective and recyclable organic absorbers with high efficiency in the field of waste water treatment.

UV-A photocatalytic treatment of Legionella pneumophila bacteria contaminated airflows through three-dimensional solid foam structured photocatalytic reactors

A 3D-structured photocatalytic media was designed for allowing a tubular reactor to work in a traversing-flow mode at low pressure drops with a strong increase in the surface area-to-volume ratio inside the reactor. A protective polysiloxane coating was performed for protecting a structured polyurethane foam and anchoring the active TiO(2) particles. Filled with the 3D-structured solid foam supporting TiO(2) photocatalyst, the reactor could thus take advantages from the static mixer effect and from the low pressure drop resulting from the reticulated foam support. Very efficient decontamination levels towards airborne Legionella pneumophila bacteria were reached in a single-pass test mode.

Electrical conductivity of anthracites as a function of heat treatment temperature

Abstract The electrical conductivity of various kinds of charred anthracites has been systematically studied as a function of their heat treatment temperature. Concurrently, volume and mass variations of several samples of these materials were measured after each calcination. From these results and based on a simplified picture of the structure of ideal anthracites, we propose to quantitatively explain the thermal variations of their conductivity. With this aim in view, we refer to a percolation of conducting pseudo-graphitic microcrystallites. Within the raw materials, these latter are initially bordered with volatilizable organic groups; as the heat treatment temperature progressively rises, a growing amount of volatile substances is removed from the material, making the conducting units to come into intimate contact with each other. The relevance of this model seems confirmed by the fact that a conductivity law quantitatively consistent with percolation theory predictions is observed in each kind of studied anthracite.

Influence of Water on the Dynamic Adsorption of Chlorinated VOCs on Active Carbon: Relative Humidity of the Gas Phase versus Pre-adsorbed Water

The present work deals with the influence of water on the adsorption of two chlorinated volatile organic compounds (VOCs) on activated carbons (ACs) having very different pore textures and surface chemistry. Two kinds of moisture were considered, viz. pre-adsorbed on the AC or present as steam in the gaseous phase, at various relative humidities ranging from 30% to 75%. It is shown that the adsorption of the VOCs depends on the kind of moisture. If the latter is pre-adsorbed, water is just displaced by the VOCs (overshoot). The adsorption capacities of the AC remain unchanged and only some minor changes in the shape of the breakthrough front, corresponding to hindered diffusion, may sometimes occur. In contrast, the simultaneous adsorption of steam and VOC leads to competition between water and the chlorinated compound, with direct consequences on the adsorption kinetics and capacities of the AC. However, the decrease of the water-induced adsorption performances depends strongly on the AC and the VOC (through different VOC/AC and water/VOC interactions), and on the concentration of the VOC.