Carbon Nanofibers: Catalytic Synthesis and Applications

Carbon nanofibers (diameter range, 3-100 nm; length range, 0.1-1000 µm) have been known for a long time as a nuisance that often emerges during catalytic conversion of carbon-containing gases. The recent outburst of interest in these graphitic materials originates from their potential for unique applications as well as their chemical similarity to fullerenes and carbon nanotubes. In this review, we focus on the growth of nanofibers using metallic particles as a catalyst to precipitate the graphitic carbon. First, we summarize some of the earlier literature that has contributed greatly to understand the nucleation and growth of carbon nanofibers and nanotubes. Thereafter, we describe in detail recent progress to control the fiber surface structure, texture, and growth into mechanically strong agglomerates. It is argued that carbon nanofibers are unique high-surface-area materials (~200 m²/g) that can expose exclusively either basal graphite planes or edge planes. Subsequently, we will present the recently explored applications of carbon nanofibers: polymer additives, gas storage materials, and catalyst supports. The latter application is described in detail. It is shown that the graphite surface structure and the lyophilicity play a crucial role during metal emplacement and catalytic use in liquid-phase catalysis. A case in point is fiber-supported Pd catalysts for nitrobenzene hydrogenation. Finally, we summarize issues with respect to the large-scale production of carbon nanofibers, including production cost estimates and research items to be dealt with in future work.     

Synthesis of carbon nanofibers and measurements of hydrogen storage

The synthesis of carbon nanofibers was carried out by catalytic decomposition of ethylene in presence of hydrogen. Bimetallic catalysts, e.g. Fe-Cu or Ni-Cu, were synthesized by coprecipitation, reduction-precipitation and reverse microemulsion techniques and were proven to have a strong influence on the morphology of the nanofibers. The best results in terms of synthesis homogeneity were obtained by supporting the bimetallic catalyst on a high surface area silica support by the “incipient wetness” method. The hydrogen storage capacity of carbon nanofibers was tested in a custom made Sievert apparatus operating up to 160 bar and 450 °C. Several “in situ” activation procedures were experimented, however according to our data carbon nanofibers do not seem a suitable candidate for hydrogen storage. With the purpose of promoting a “spillover” function, 2 wt.% Pd-doped nanofibers were prepared. After loading at 77 bar, a hydrogen storage of 1.38 ± 0.30 wt.% was measured at room temperature.     

Catalytic growth of macroscopic carbon nanofiber bodies with high bulk density and high mechanical strength

Carbon nanofibers (CNF) are non-microporous graphitic materials with a high surface area (100-200 m²/g), high purity and tunable surface chemistry. Therefore the material has a high potential for use as catalyst support. However, in some instances it is claimed that the low density and low mechanical strength of the macroscopic particles hamper their application. In this study we show that the bulk density and mechanical strength of CNF bodies can be tuned to values comparable to that of commercial fluid-bed and fixed-bed catalysts. The fibers were prepared by the chemical decomposition of CO/H₂ over Ni/SiO₂ catalysts. The resulting fibers bodies (1.2 μm) were replicates of the Ni/SiO₂ bodies (0.5 μm) from which they were grown. The bulk density of CNF bodies crucially depended on the metal loading in the growth catalyst. Over 5 wt% Ni/SiO₂ low density bodies (0.4 g/ml) are obtained while 20 wt% Ni/SiO₂ leads to bulk densities up to 0.9 g/ml with a bulk crushing strength of 1.2 MPa. The 20 wt% catalysts grow fibers with diameters of ∼22 nm, which grow irregularly in space, resulting in a higher entanglement and a concomitant higher density and strength as compared to the thinner fibers (∼12 nm) grown from 5 wt% Ni/SiO₂.     

On the control of carbon nanostructures for hydrogen storage applications

The storage of hydrogen in different carbon nanostructures has been investigated using classical Monte-Carlo simulations techniques. Very low hydrogen uptakes (?1% wt) have been calculated for single-walled and double-walled carbon nanotubes, as well as for graphite nanofibers at 293 K and 10 MPa. The amount of hydrogen uptake strongly depends on the porosity within the nanostructure network where optimal arrangements give rise to the formation of a well-defined two-dimensional adsorbed hydrogen layer. The presence of metallic impurities within single-walled nanotube bundles was modeled by disseminating atomic particles, characterized by a highly attractive potential, throughout the nanotube network. It has been found that the presence of metallic particles significantly enhances the hydrogen uptake, but not to a point where this could be considered a promising storage solution.     

Hydrogen storage capacity of carbon nanotubes, filaments, and vapor-grown fibers

We have studied the sorption of hydrogen by nine different carbon materials at pressures up to 11 MPa (1600 psi) and temperatures from −80 to +500°C. Our samples include graphite particles, activated carbon, graphitized PYROGRAF vapor-grown carbon fibers (VGCF), CO₂ and air-etched PYROGRAF fibers, Showa-Denko VGCF, carbon filaments grown from a FeNiCu alloy, and nanotubes from MER Corp. and Rice University. We have measured hydrogen sorption in two pieces of equipment, one up to 3.5 MPa, and one to 11 MPa. The results so far have been remarkably similar: very little hydrogen sorption. In fact, the sorption is so small that we must pay careful attention to calibration to get reliable answers. The largest sorption observed is less than 0.1 wt.% hydrogen at room temperature and 3.5 MPa. Furthermore, our efforts to activate these materials by reduction at high temperatures and pressures were also futile. These results cast serious doubts on any claims so far for room temperature hydrogen sorption in carbon materials larger than a 1 wt.%.     

Carbon nanotube synthesis upon stainless steel meshes

In this paper we report and interpret the effectiveness of different bulk metal catalyst preparations and of various components within reactive gas mixtures for carbon nanotube (CNT) synthesis. The combined catalyst precursor and supporting material is type 304 stainless steel mesh. The steel mesh keenly illustrates the net effect of different pretreatments upon the catalyst because of its resistance to oxidation. These preparative treatments include oxidation, reduction, and their combinations. Finally the utility of the different components within the reactive gas mixture are illustrated by synthesis tests in their individual absence. The effect of catalyst preparation and gas mixture on CNT synthesis is judged on the basis of the relative surface density and morphology of the CNTs (as observed via SEM) and their graphitic structure (as observed via TEM).     

An accurate volumetric differential pressure method for the determination of hydrogen storage capacity at high pressures in carbon materials

Widely different hydrogen adsorption capacities have been reported for a variety of carbon materials which have attracted attention for hydrogen storage. This has led to doubts as to the validity of some of the claims and it has been suggested that one possible reason for the disparate hydrogen sorption capacities may lie in the inaccurate measurement of the hydrogen adsorbed. The aim of the work described in this paper was to make a contribution to this debate by developing a means and method of producing repeatable, accurate measurements of hydrogen sorption capacity in carbon materials. The apparatus developed is a volumetric differential pressure set-up operating at up to 10 MPa and the method has a conservative limit of detection of 0.1 wt% and an accuracy of ±0.05 wt%, using 1.0-2.5 g samples of the carbon materials studied. These included a carbon nanofiber sample and a series of activated carbons, the latter displaying a direct correlation between the BET effective surface area and the hydrogen sorption capacity of the materials. The amount of hydrogen adsorbed was less than 1 wt% for all the carbons examined.     

Carbon nanofibers supported Pt-Ru electrocatalysts for direct methanol fuel cells

Oxidized and reduced carbon nanofibers (OCNF and RCNF) were used as supports to prepare highly dispersed PtRu catalysts for the direct methanol fuel cells (DMFC). The structural and surface features and electrocatalytic properties of bimetallic PtRu/OCNF and PtRu/RCNF were extensively investigated. FT-IR spectra show that carboxyl groups exist on the surface of the OCNF, which greatly influence the morphology and crystallinity of the electrocatalysts. Transmission electron microscopy and X-ray diffraction consistently show that PtRu/RCNF has a smaller particle size and more uniform distribution than PtRu/OCNF. However, both catalysts have very similar methanol oxidation peak current densities that are significantly lower than commercial catalyst based on current-voltage (CV) results. These two catalysts also give very similar single cell performance except for some difference in the resistance polarization region. The OCNF supported catalysts give better performance than commercial catalysts when current density is higher than 50 mA cm⁻² in spite of low methanol oxidation peak current density. These results can be ascribed to the specific surface and structural properties of carbon nanofibers.     

Carbon nanotube supported ruthenium catalysts for the treatment of high strength wastewater with aniline using wet air oxidation

Multi-walled carbon nanotubes (MWCNT) can be efficiently used as support of ruthenium catalysts for the catalytic wet air oxidation of high strength wastewater containing aniline. Catalysts were prepared using different ruthenium precursors, Ruthenocene [Ru(η⁵-C₅H₅)₂], Ruthenium (1,5-cyclooctadiene, 1,3,5-cyclooctatriene) [Ru(cod)(cot)] and Ruthenium trichloride (RuCl₃ · xH₂O), different impregnation methods (excess solution and incipient wetness impregnation) and different MWCNT support surface chemistry (nitric acid oxidized MWCNT-COOH and Na₂CO₃ ion exchanged MWCNT-COONa). The efficiency of the aniline removal obtained with the catalysts prepared with different precursors decreases in the order [Ru(cod)(cot)] > RuCl₃ · xH₂O > [Ru(η⁵-C₅H₅)₂], 100% aniline conversion being obtained after 45 min of reaction with the catalyst prepared with [Ru(cod)(cot)]. The influence of the impregnation technique was found to be negligible, while the use of the MWCNT-COONa support led to increased catalyst performances when compared to that obtained with catalysts prepared with the MWCNT-COOH support. Leaching of ruthenium was observed in all cases, but the use of the precursor [Ru(cod)(cot)] and of the support MWCNT-COONa in the preparation of the catalysts seems to improve their stability. A direct relationship between metal load and catalyst stability was found and attributed to the strength of metal-support interactions.     

Nitrogen-doped carbon nanotubes synthesized with carbon nanotubes as catalyst

Nitrogen-doped carbon (CN_x) nanotubes were synthesized with carbon nanotubes (CNTs) as catalyst by detonation-assisted chemical vapor deposition. CN_x nanotubes exhibited compartmentalized bamboo-like structure. Electron energy loss spectroscopy and elemental mapping studies indicated that the synthesized tubes contained high concentration of nitrogen (ca. 17.3 at.%), inhomogeneously distributed with an enrichment of nitrogen within the compartments. X-ray photoelectron spectroscopy analysis revealed the presence of pyridine-like N and graphitic N incorporated into the graphitic network. The catalytic activity of CNTs for CN_x nanotube growth was ascribed to the nanocurvature and opening edges of CNT tips, which adsorbed C_n/CN species and assembled them into CN_x nanotubes.     

Two-step pyrolysis process to synthesize highly dispersed Pt-Ru/carbon nanotube catalysts for methanol electrooxidation

Highly dispersed Pt-Ru particles with different atomic ratios supported on carbon nanotubes were synthesized using an easy two-step synthesis method including adsorption and pyrolysis. In this method, the functionalized carbon nanotubes act as adsorption sites for metallic ions and subsequently act as nucleation center for catalyst deposition in the pyrolysis process. The deposited Pt-Ru nanoparticles disperse on the carbon nanotubes surface uniformly, and the bulk composition of the Pt-Ru particles can be adjusted simply by changing atomic ratios of the metallic solution for adsorption. Finally, the electrocatalytic activity of the as-prepared catalysts supported on carbon nanotubes toward oxidation of methanol was studied. Results showed that their electrocatalytic activity, having long-term stability, strongly depends on the atomic ratio of Pt to Ru. The higher the concentration of Pt in the binary system is, the greater the electrocatalytic activity will be.     

Effect of carbon black composite (CBC) support properties on hydrodesulfurization performance of sulfided Mo and Co, and carburized Mo, catalysts

Carbon black composites (CBCs) have been prepared by pyrolyzing mixture of a carbon black with polyfurfuryl alcohol and then pretreated by oxidation with nitric acid, gasification with water steam or ammoxidation. The effects of the chemical character of the carrier surface, nature of the active metal phase and pH value of the impregnation solution on the catalytic activity towards the hydrodesulfurization (HDS) of thiophene of the CBC supported Mo (Co) catalysts were determined. It was stated that the catalytic properties of the CBC supported sulfides of Mo or Co and of Mo carbides are affected by the chemical character of the carrier surface. Generally, catalysts supported over basic surface CBC exhibit higher activity than those ones supported over CBC possessing acidic surface character. Co catalysts supported on acidic surface show lower activity (per mol of active metal) than Mo based ones supported on the same carrier. In the case of catalysts supported on basic CBC, Co exhibits distinctly higher activity than Mo. At the experimental conditions adopted for this study, CBC surface properties, active phase nature, and catalyst impregnation pH were found to exert a relatively small influence on both HDS and hydrogenation activities.     

Density control of carbon nanotubes and filaments films by wet etching of catalyst particles and effects on field emission properties

Carbon nanotubes and filaments (CNT&F) films with controlled density were grown by low pressure thermal chemical vapour deposition from acetylene on nickel nanoparticles. Density control was achieved by wet etching of the catalyst particles before carbon growth. Field emission measurements were carried out on several films with different CNT&F densities obtained with this method. Despite strong morphological changes, only slight differences in the field emission characteristics between the highest and the lowest density films were detected, suggesting that almost none of the CNT&F suppressed by the etching step took part to the field emission. However, a maximum field amplification factor was reached for the medium density film. Taking into account the field amplification factor distribution, a model is proposed to link the particles diameter distribution, the CNT&F film morphology and the field emission properties.     

Structure, composition, and chemical reactivity of carbon nanotubes by selective nitrogen doping

Carbon nanotubes (CNTs) doped with a range of nitrogen contents (0-10 at.%) were prepared via a floating catalyst CVD method using ferrocene, NH₃, and xylene or pyridine. XPS and Raman microscopy were used to assess quantitatively the compositional and structural properties of the nitrogen-doped carbon nanotubes (N-CNTs). XPS analysis indicates a shift in and broadening of the C 1s spectra track with increasing disorder induced by selective nitrogen doping. N 1s XPS spectra show three principle types of nitrogen coordination (pyridinic, pyrolic, and quaternary), with the pyridinic-like fraction selectively increased from 0.0 to 4.5 at.%. First-order Raman spectra were fit with five peaks that vary in intensity and width with nitrogen content. The ratio of the D and G bands’ integrated intensities scaled linearly with nitrogen content. Iodimetric titrations were used to gauge the number of reducing sites on as-prepared N-CNTs, representing the first report of nitrogen doping as a means to deterministically effect the chemical reactivities of carbon nanotubes. The reported methodology for the regulated growth and selective nitrogen doping of CNTs presents new ways to study systematically the influence of nanocarbon composition and structure on chemical and electrochemical reactivity for a host of applications.     

Synthesis of carbon nanotubes on carbon fibers by means of two-step thermochemical vapor deposition

The present study aimed at development of a method for synthesizing multi-walled carbon nanotubes (CNTs) on carbon paper substrates (CP) at densities as high as those so far reported for CNTs formed on quartz substrates. Applying conditions optimized for CNTs synthesis on quartz substrates, in which CP was heated at 1073 K, being placed parallel to the flow of m-xylene/ferrocene vapor, resulted in formation of extremely few deposits on CP. Forced vapor flow through the CP greatly improved the frequency and homogeneity of deposition of the Fe-bearing nanoparticles, but these became encapsulated by carbon and deactivated. The addition of H₂S to the vapor further enhanced nanoparticle deposition. Moreover, it enabled the subsequent formation of CNTs at densities as high as 2-6 × 10⁹ cm⁻². In order to realize such high population densities, it was found essential to perform CVD in a two-stage sequence commencing with nanoparticles deposition at 1073 K followed by the formation and growth of CNTs at 1273 K, with the H₂S concentration in the vapor phase optimized throughout within a range of 0.014-0.034 vol%.     

Electrochemical stability of carbon nanofibers in proton exchange membrane fuel cells

This fundamental study deals with the electrochemical stability of several non-conventional carbon based catalyst supports, intended for low temperature proton exchange membrane fuel cell (PEMFC) cathodes. Electrochemical surface oxidation of raw and functionalized carbon nanofibers, and carbon black for comparison, was studied following a potential step treatment at 25.0 °C in acid electrolyte, which mimics the operating conditions of low temperature PEMFCs. Surface oxidation was characterized using cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and contact angle measurements. Cyclic voltammograms clearly showed the presence of the hydroquinone/quinone couple. Furthermore, identification of carbonyl, ether, hydroxyl and carboxyl surface functional groups were made by deconvolution of the XPS spectra. The relative increase in surface oxides on carbon nanofibers during the electrochemical oxidation treatment is significantly smaller than that on carbon black. This suggests that carbon nanofibers are more resistant to the electrochemical corrosion than carbon black under the experimental conditions used in this work. This behaviour could be attributed to the differences found in the microstructure of both kinds of carbons. According to these results, carbon nanofibers possess a high potential as catalyst support to increase the durability of catalysts used in low temperature PEMFC applications.