Cuong Pham-Huu

Silicon Carbide: A Novel Catalyst Support for Heterogeneous Catalysis

Progress in developing a new class of support materials based on silicon carbide (SiC)is reviewed. Silicon carbide has superior mechanical and thermal properties which, coupled to chemical inertness,avoids several of the problems inherent in the use of commercial oxide and carbon based supports and catalysts. High surface area SiC can now be prepared easily in a commercially viable shape,with good mechanical properties,and at reasonable cost.I t can be shaped directly into monolith or honeycomb forms including some catalytically active material, rendering fabrication simple and cost effective. Furthermore, it can be modified for specific catalytic applications through the addition of metals. In many respects, it combines the best properties of oxide and carbon based supports without suffering many of their disadvantages.

Physical characterization of molybdenum oxycarbide catalyst; TEM, XRD and XPS

Abstract Controlled reduction of MoO 3 can produce different phases of catalytic interest. One of these phases has been considered as being an oxycarbide of molybdenum. Various techniques mainly TEM but also XRD and others have been extensively used to understand the mechanism of formation and the structure of this oxycarbide. Its structure is reminiscent of the MoO 3 structure as shown by XRD, but reconstructed by shear planes and the introduction of carbon atoms to fill oxygen vacancies, both blocking the formation of MoO 2 the normal product of the slow reduction of MoO 3 . The HRTEM pictures showed a ‘chevron-like’ arrangement and the electronic microdiffraction a square lattice reminiscent of the (0 k 0) planes of MoO 3 .

Selective Deposition of Metal Nanoparticles Inside or Outside Multiwalled Carbon Nanotubes

A general method is described for the deposition of metal nanoparticles selectively either inside or outside of carbon nanotubes (CNTs). The method is based on the difference in the interface energies of organic and aqueous solutions with the CNT surface. Because of their lipophilic character, the organic solvent better wets the surface of the nanotubes compared to water and penetrates into the inner volume. The precise control of the volume of each phase allows filling the CNT with the organic phase and covering its outer surface with the aqueous one. Hence, metal nanoparticles can be put with high selectivity either inside or outside the CNT, just by choosing in which solvent the metal precursor is dissolved. SEM, TEM, and 3D-TEM investigations show that a selectivity in localization close to 75% can be reached by this technique. The nanoparticles are homogeneously dispersed and present a narrow size distribution, centered on 5 nm. In this way, one can decorate either the inner or the outer surface of open CNTs, without the need of discriminating the diameter of the opening and without any further step of functionalization than a treatment with nitric acid.

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.

Electrical Transport Measured in Atomic Carbon Chains

The first electrical-transport measurements of monatomic carbon chains are reported in this study. The chains were obtained by unraveling carbon atoms from graphene ribbons while an electrical current flowed through the ribbon and, successively, through the chain. The formation of the chains was accompanied by a characteristic drop in the electrical conductivity. The conductivity of the chains was much lower than previously predicted for ideal chains. First-principles calculations using both density functional and many-body perturbation theory show that strain in the chains has an increasing effect on the conductivity as the length of the chains increases. Indeed, carbon chains are always under varying nonzero strain that transforms their atomic structure from the cumulene to the polyyne configuration, thus inducing a tunable band gap. The modified electronic structure and the characteristics of the contact to the graphitic periphery explain the low conductivity of the locally constrained carbon chain.

New catalytic phenomena on nanostructured (fibers and tubes) catalysts

The recent development of new catalytic syntheses of carbon or carbide nanostructures has enabled the production of large amounts of these materials. Consequently, it is now possible to use them as supports for active phases in novel catalytic reactions and processes. New phenomena at the surface or inside these structures open up the way to unexpected applications. We shall first present the latest methods of preparation of these nanomaterials and their characterization and then provide some examples of applications in the fields of catalysis for synthesis of chemicals and catalysis applied to environmental remediation.

Large scale synthesis of carbon nanofibers by catalytic decomposition of ethane on nickel nanoclusters decorating carbon nanotubes

A large scale synthesis of carbon nanofibers with a controlled diameter of about 50 nm has been achieved at relatively low temperatures (550–650 °C) by the decomposition of ethane on a carbon nanotube supported nickel catalyst. The carbon nanofibers can be used as a catalyst or a catalyst support without subsequent purification, due to the use of carbon nanotubes as support, the high nanofiber yields, and the purity obtained.

Graphene growth by a metal-catalyzed solid-state transformation of amorphous carbon.

Single and few-layer graphene is grown by a solid-state transformation of amorphous carbon on a catalytically active metal. The process is carried out and monitored in situ in an electron microscope. It is observed that an amorphous carbon film is taken up by Fe, Co, or Ni crystals at temperatures above 600 °C. The nucleation and growth of graphene layers on the metal surfaces happen after the amorphous carbon film has been dissolved. It is shown that the transformation of the energetically less favorable amorphous carbon to the more favorable phase of graphene occurs by diffusion of carbon atoms through the catalytically active metal.

3D analysis of the morphology and spatial distribution of nitrogen in nitrogen-doped carbon nanotubes by energy-filtered transmission electron microscopy tomography.

We present here the application of the energy-filtered transmission electron microscopy (EFTEM) in the tomographic mode to determine the precise 3D distribution of nitrogen within nitrogen-doped carbon nanotubes (N-CNTs). Several tilt series of energy-filtered images were acquired on the K ionization edges of carbon and nitrogen on a multiwalled N-CNT containing a high amount of nitrogen. Two tilt series of carbon and nitrogen 2D maps were then calculated from the corresponding energy-filtered images by using a proper extraction procedure of the chemical signals. Applying iterative reconstruction algorithms provided two spatially correlated C and N elemental-selective volumes, which were then simultaneously analyzed with the shape-sensitive reconstruction deduced from Zero-Loss recordings. With respect to the previous findings, crucial information obtained by analyzing the 3D chemical maps was that, among the two different kind of arches formed in these nanotubes (transversal or rounded ones depending on their morphology), the transversal arches contain more nitrogen than do the round ones. In addition, a detailed analysis of the shape-sensitive volume allowed the observation of an unexpected change in morphology along the tube axis: close to the round arches (with less N), the tube is roughly cylindrical, whereas near the transversal ones (with more N), its shape changes to a prism. This relatively new technique is very powerful in the material science because it combines the ability of the classical electron tomography to solve 3D structures and the chemical selectivity of the EFTEM imaging.

High specific surface area carbides of silicon and transition metals for catalysis

Abstract A new synthesis of carbides based on the concept of shape memory is summarized. High specific surface area activated carbon is reacted with a vapor of the oxide to give the corresponding high specific surface area carbide and carbon monoxide. Some catalytic applications of these new materials are presented.