Housseinou Ba

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.

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.

Silicon carbide foam as a porous support platform for catalytic applications

This review provides an overview of the use of foam-structured SiC as a porous support platform in some typical catalytic processes both for gas-phase and liquid-phase reactions, such as H2S selective oxidation, Friedel–Crafts benzoylation and Fischer–Tropsch synthesis, where traditional catalysts have shown their weaknesses. The macroscopic thermally conductive SiC material could be efficiently employed as a support for controlling the active phase, i.e. metal and zeolite, and anchoring the powder-foam nanocarbons in the field of catalysis. In light of the results, one can state that silicon carbide foam could be regarded as an ideal alternative support, which provides a great enhancement of both the catalytic performance and the catalytic stability compared to that of the traditional catalysts, in several gas- and liquid-phase catalytic processes.

Nitrogen-doped carbon nanotubes on silicon carbide as a metal-free catalyst

Abstract A hierarchical metal-free catalyst consisting of nitrogen-doped carbon nanotubes decorated onto a silicon carbide (N-CNTs/SiC) macroscopic host structure was prepared. The influence of N-CNTs incorporation on the physical properties of the support was evaluated using different characterization techniques. The catalyst was tested as a metal-free catalyst in the selective oxidation of H 2 S and steam-free dehydrogenation of ethylbenzene. The N-CNTs/SiC catalyst exhibited extremely good desulfurization performance compared to a Fe 2 O 3 /SiC catalyst under less conducive reaction conditions such as low temperature, high space velocity, and a low O 2 -to-H 2 S molar ratio. For the dehydrogenation of ethylbenzene, a higher dehydrogenation activity was obtained with the N-CNTs/SiC catalyst compared to a commercial K-Fe/Al 2 O 3 catalyst. The N-CNTs/SiC catalyst also displayed good stability as a function of time on stream for both reactions, which was attributed to the strong anchoring of the nitrogen dopant in the carbon matrix. The extrudate shape of the SiC support allowed the direct macroscopic shaping of the catalyst for use in a conventional fixed-bed reactor without the problems of catalyst handling, transportation, and pressure drop across the catalyst bed that are encountered with nanoscopic carbon-based catalysts.

Hierarchical porous carbon fibers/carbon nanofibers monolith from electrospinning/CVD processes as a high effective surface area support platform

Nanocarbons with unique physicochemical properties have been considered typical sustainable materials for use as catalyst supports and directly as catalysts. Unfortunately, the powder form of nanocarbons renders them difficult to use in industrial processes due to the high pressure drop, their difficulty of handling as well as health injuries caused to human beings. Herein, hierarchical carbon fibers/carbon nanofibers (CF/CNF) composites, with high effective surface areas and controlled macroscopic shapes, were successfully synthesized through a combination of electrospinning (ES) and chemical vapour deposition (CVD). A web of poly(acrylonitrile)/poly(vinyl pyrrolidone) (PAN/PVP) composite fibers embedding a nickel salt was firstly produced by electrospinning. After a carbonization step, the polymeric material was converted into porous carbon embedding nickel nanoparticles, available on the fiber surface. Then, the catalytic growth of the CNFs was carried out from the nickel nanoparticles by CVD leading finally to the formation of a hierarchical carbon web of hairy fibers with a high effective surface area. The density, diameters and lengths of the CNFs attached on the surface of the CFs could be finely tuned by adjusting the CVD conditions. The specific surface area of the CF/CNF monolith amounted to more than 200 m2 g−1 along with high accessibility due to the small dimensions. The hierarchical CF/CNF composite has been used as a metal-free catalyst for the steam- and oxygen-free catalytic dehydrogenation of ethylbenzene to styrene. The catalytic results have pointed out that such a monolith can be efficiently used as a material platform for different applications , going from catalysis to wastewater treatment, thanks to the high effective surface area and reactivity of the CNF with prismatic planes.

Activation of few layer graphene by μW-assisted oxidation in water via formation of nanoballs - Support for platinum nanoparticles.

The functionalization of carbon nanomaterials in controlled and selective manner and in order to stabilize small metal nanoparticles is of high interest particularly in the catalysis field. We present the μ-waves assisted few layer graphene (FLG) oxidation in water, which results in a partial sheets exfoliation and formation of oxygen functionalized carbon nanoballs, supported on highly graphitized graphene sheets. This double morphology material allows homogenous anchoring of Pt nanoparticles, while the advantages of planar and highly crystallized FLG are preserved. For comparison, acid treated FLG (conventional heating) exhibits highly hydrophobic and inert surface with carboxylic groups as anchoring sides localized at the FLG edges. Despite similar oxygen content, the performed physicochemical analyses depict different nature and localization of the oxygen/defects functionalities introduced in water (in μ-waves) and acid treated FLGs. Finally, the addition of FLG during the preparation of Pt particles-carried out by μ-wave assisted polyol method yields small nanoparticles with average size of 1nm.

Design and Fabrication of Highly Reducible PtCo Particles Supported on Graphene-Coated ZnO

Cobalt particles dispersed on an oxide support form the basis of many important heterogeneous catalysts. Strong interactions between cobalt and the support may lead to irreducible cobalt oxide formation, which is detrimental for the catalytic performance. Therefore, several strategies have been proposed to enhance cobalt reducibility, such as alloying with Pt or utilization of nonoxide supports. In this work, we fabricate bimetallic PtCo supported on graphene-coated ZnO with enhanced cobalt reducibility. By employing a model/planar catalyst formulation, we show that the surface reduction of cobalt oxide is substantially enhanced by the presence of the graphene support as compared to bare ZnO. Stimulated by these findings, we synthesized a realistic powder catalyst consisting of PtCo particles grafted on graphene-coated ZnO support. We found that the addition of graphene coating enhances the surface reducibility of cobalt, fully supporting the results obtained on the model system. Our study demonstrates that realistic catalysts with designed properties can be developed on the basis of insights gained from model catalytic formulation.

Pyridine-decorated carbon nanotubes as a metal-free heterogeneous catalyst for mild CO2 reduction to methanol with hydroboranes

Pyridine decorated multi-walled carbon nanotubes (NPy-MW) have been successfully employed as a catalyst for the reduction of carbon dioxide to methyl borinate (R2BO–CH3) in the presence of 9-borabicyclo[3.3.1]nonane. NPy-MW represents the first example of a heterogeneous, metal-free and durable catalyst for CO2 hydroboration to methanol. A mechanistic cycle has been proposed on the basis of targeted blank experiments and a quantum chemical study, highlighting the non-innocent role played by the nanotube carrier in the final NPy-MW catalytic performance.

Colloid Approach to the Sustainable Top-Down Synthesis of Layered Materials

The successful future of 2D materials, which are crucial for accelerating technology development and societal requirements, depends on their efficient preparation in an economical and ecological way. Herein, we present a significant advance in the top-down exfoliation and dispersion method via an aqua colloid approach. We demonstrate that a broad family of natural oil-in-water emulsification agents with an elevated hydrophilic/lipophilic balance acts in the exfoliation of layered materials and the formation of their concentrated colloids. The concentration exceeds 45 g/L for exfoliated few-layered graphene sheets possessing a micrometer size. The exfoliation of carbon nanofibers provides one of the best known unsupported and N-undoped metal-free catalysts to date in the selective dehydrogenation of ethylbenzene to styrene. Other examples include aqua colloids of exfoliated/dispersed nitrides, carbides, or nanodiamonds.

How to teach an old dog new (electrochemical) tricks: aziridine-functionalized CNTs as efficient electrocatalysts for the selective CO2 reduction to CO

The electrocatalytic conversion of CO2 to energy-rich chemicals or energy vectors is a highly challenging approach to cope with an ever increasing demand for energy storage and valorization of renewable resources. Herein we report on the electrocatalytic reduction of CO2 to CO using covalently N-decorated carbon nanotubes as highly efficient and chemoselective metal-free electrocatalysts. At odds with more conventional synthetic methods for the production of N-doped nanocarbons, chemical functionalization warrants a unique control of “surface N-defects” available for the process, ruling out any synergistic contribution to electrocatalysis coming from other surface or bulk N-containing groups. With a CO faradaic efficiency (FECO) close to 90% and productivity as high as 48 NLCO gN−1 h−1, NH-aziridine functionalized MWCNTs have shown CO2RR performance that is among the highest reported so far for related metal-free systems. At the same time, it has offered a unique view-point for the comprehension of the underlying structure–reactivity relationship.