Carbon nanofibers grown on metallic filters as novel catalytic materials

Lioubov Kiwi, Pascal Tribolet
2005
Article

Résumé

Carbon nanofibers (CNF) were synthesized on sintered metal fibers (SMF) filters of nickel and Ni-containing alloys (Inconel, stainless steel (SS)) by thermal chemical vapor deposition of ethane in the presence of hydrogen at not, vert, similar660 °C. The CNFs were formed directly over the SMF filters without deposition of metal particles. The catalytic active sites leading to the CNF formation were attained by oxidation–reduction of the SMF filter. The CNFs present platelet morphology as determined by X-ray diffraction and transmission electron microscopy. The CNF/SMF composites have thin carbon layer in the microns range strongly anchored to the metal surface. The initial open structure of SMF filters is preserved. Scanning electron microscopy together with temperature programmed oxidation suggests the formation of uniform CNFs deposits on SMFInconel with fiber's diameters in the range of 70 nm. Carbon deposits with a different nature were observed over SMFNi and SMFss. The CNF/SMFInconel composites have high specific surface area due to mesopores of CNFs, high thermo-conductivity and open 3D macrostructure. This is advantageous for catalytic applications, especially during the catalysis of highly exo/endothermic reactions in reactors with structured catalytic bed.

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The main objectives of this work are 2-fold : The development of a novel type of composite material based on carbon nanofibers supported on sintered metal fibers filters (CNF/SMF) and to explore the use of this material as a catalytic support for a model reaction: selective hydrogenation of acetylene. The advantages of this novel support are: Due to carbon nanofibers, it combines a graphitic structure with a high specific surface area without microporosity. Supported carbon nanofibers can be used in a fixed bed reactor without very high pressure drop. Combination of two materials with high thermal conductivity gives a composite which keeps this property. It is suitable for highly exo/endothermic reactions, diminishing temperature gradients in the catalytic bed. The synthesis of carbon nanofibers on SMF filters was carried out by ethane catalytic decomposition at 655°C directly on metallic filters. An oxidation of SMF followed by a reduction in H2 create surface roughness, leading to a larger area for CNF nucleation. The CNF formation mechanism includes several steps: it starts with carbon deposition on metallic surface followed by its diffusion into the metal leading to carbides formation. When the limit of carbon solubility is attained, a layer of carbon is formed on the surface of metallic fibers. High tension within the bulk metal leads to carbide dissociation and by phase separation to graphite formation, which pushes the metallic particles through the carbon layer. Nickel, stainless steel an Inconel (an alloy of mainly nickel, iron and chromium) filters were used. The latter gave the highest uniformity of the carbon nanofibers layer showing an excellent mechanical stability. In order to control carbon deposition on the filters, a formal kinetic analysis of the decomposition reaction was undertaken. Partial orders of 1 for ethane, -2 for hydrogen and an apparent activation energy of 235 kJ/mol were obtained. The observed kinetics suggests strongly that the C – C bond scission is the rate determining step and not carbon diffusion into the metal which is often reported in the literature. The synthesis procedures like time on stream and reaction temperature were optimized: 1 hour of a mixture C2H6:H2:Ar (3:17:80) decomposition over SMFInconel at 655°C lead to ∼6% of carbon, leading to a CNF layer of 1 µm thickness covering the metallic fibers entirely. This material presents a high specific surface area (22.2 m2/g) and a low pressure drop for the gas flowing through. The carbon nanofibers have a diameter between 20 and 50 nm and a crystalline structure with platelets morphology where the graphene layers are stacked one above the other. Their surface is composed almost exclusively of carbon and hydrogen. Amongst the multiple possible applications of this novel composite material, its use as a catalyst support was assessed. Selective hydrogenation of acetylene was carried out over palladium supported on CNF/SMF and compared with commercial supports (ACF, EGF and AGF). The activated carbon fibers cloth (ACF) led to a Pd activity at least twice as E-type glass fibers tissue (EGF) or EGF covered by an alumina layer (AGF). Reaction kinetics was studied for Pd/ACF, leading to acetylene and hydrogen partial orders of -0.5 and 2.4, respectively and apparent activation energy of 50 kJ/mol. The negative partial order for C2H2 suggests high adsorption strength of this compound compared to other reagents on palladium. This particularity allows Pd to be selective. Hydrogenations are known to be structure sensitive. Therefore the catalyst activity for the model reaction depends on Pd particle size. It increases for large particle sizes. The control of this parameter was a priority. Variations of the palladium precursor, of the support and catalyst treatment were carried out. Micro-wave plasma was used since it is fast and has low energy consumption allowing chemically modifying the carbon support surface and activating catalyst after impregnation. This controls not only palladium sintering, but also decomposes tetraaminopalladate more efficiently, resulting in a catalyst activity of one order of magnitude higher. In order to control the palladium deposition on CNF/SMFInconel composite, it is important to have surface functional groups. The activation of carbon nanofibers was carried out with a 4 hours treatment in a boiling aqueous solution of hydrogen peroxide. This led to an amount on surface oxygen containing groups, per mass of carbon, higher than in ACF. Palladium particle size on the composite was controlled by support activation, the use of several metal precursors or different loadings or by a thermal treatment in argon at 500°C. Optimisation of the procedure allowed to obtain in a controlled way an average palladium particle sizes between 3.6 and 25 nm. The activity and selectivity towards ethylene of Pd/CNF/SMFInconel were observed to be higher compared to palladium supported on activated carbon, alumina or barite. Graphitic nature of carbon nanofibers, leading to strong metal-support interaction, was accounted as responsible for these improvements. The high thermal conductivity of the composite CNF/SMF ensured good heat transfer released due to the exothermicity of the reaction and allowed to work close to isothermal conditions in the catalytic bed. Finally it can be concluded, that for the first time carbon nanofibers synthesis was carried out in one step on sintered metal fibers filters, resulting in a novel structured composite material combining different specific properties and having promising potential applications.

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Palladium on carbon nanofibers grown on metallic filters as novel catalytic materials

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A novel composite material based on carbon nanofibers (CNF) grown on sintered metal fibers (SMFInconel) filter was investigated for its favorable properties as catalytic support. The CNF were formed directly over the SMFInconel by thermal (650 degrees C) chemical vapor deposition of ethane-hydrogen mixture. The CNF/SMFInconel composite consists of metal fibers entangled by CNF network of microns thickness and strongly anchored to the metal surface. The properties of the CNF/SMFInconel were controlled by the synthesis conditions. The CNF coating reduced the filter porosity and decreased the material permeability, but the pressure drop during the gas passage through the reactor remained low for CNF fraction < 10 %. Palladium was deposited on CNF previously activated by boiling in hydrogen peroxide. The activity and selectivity of Pd degrees/CNF/SMFInconel catalysts were tested in the selective hydrogenation of acetylene and compared with Pd supported on activated carbon fibers (Pd degrees/ACF). The TOF was one order of magnitude higher for Pd degrees/CNF/SMFInconel as compared to Pd degrees/ACF. This effect was attributed to a strong metal-support interaction of Pd degrees-nanoparticles with the graphitized CNF. The reaction was found to be structure sensitive leading to a decrease of TOF for the Pd degrees-particles < 3 nm.

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