Growth of carbon nanofibers from the iron-copper catalyzed decomposition of CO/C2H4/H2 mixtures

The growth of carbon nanofibers from Fe-Cu catalyzed decomposition of CO/C₂H₄/H₂ mixtures at temperatures over the range 500-650 °C has been investigated. Based on analysis of the gas phase and solid products it is apparent that co-adsorption of CO and C₂H₄ induces major perturbations in the surfaces of the bimetallic catalyst particles. These features are reflected in an increase in the yield of solid carbon and subtle changes in the structural characteristics of the carbon nanofibers. Optimum performance with respect to the yield of carbon nanofibers is found for iron-rich particles treated in CO/C₂H₄/H₂ (1:3:1) at 600 °C. Deactivation of the catalyst is observed to occur with high Cu concentrations and at reaction temperatures in excess of 600 °C. It is suggested that under these conditions the surface of the particles in contact with the reactant gas mixture become enriched in Cu, which does not possess the ability to dissociatively chemisorb either CO or C₂H₄.     

Transmission electron microscopy characterization of nanostructured carbon derived from Cr3C2 and Cr(C5H7O2)3

The preparation, characterization and comparison of nanostructured carbons derived by direct chlorination of Cr₃C₂ and Cr(C₅H₇O₂)₃ are reported in this work. Cr₃C₂ precursor was treated at 400 and 900 °C with a reaction time of 1 h. The nanostructure of the products has been characterized in some detail by means of transmission electron microscopy and associated techniques, such as electron energy-loss and X-ray energy dispersive spectroscopies and high-angle annular dark field imaging. Remains of Cr₃C₂ encapsulated in an amorphous carbon shell were observed at 400 °C, whereas carbon with higher ordering degree was produced at 900 °C. In the latter case, the sample can be described as a continuous variation from poorly-stacked graphene-like carbon to graphitic agglomerates. Remains of the reaction by-product, CrCl₃, are detected in the carbon particles, forming monolayers intercalated inside the graphitic agglomerates and amorphous nanoparticles. As a comparison, carbon samples derived from Cr(C₅H₇O₂)₃ were prepared at 300 and 900 °C. They mainly consist of highly disordered carbon, with local graphite-like stacking in the sample prepared at 900 °C.     

Effects of hydrogen on carbon nanotube formation in CH4/H2 plasmas

Carbon nanotubes (CNTs) were synthesized using CH₄/H₂ plasmas and plasmas simulated using a one-dimensional fluid model. The thinnest and longest CNTs with the highest number density were obtained using CH₄/H₂ = 27/3 sccm at 10 Torr. These conditions allowed CNTs to grow for 90 min without any meaningful loss of catalyst activity. However, an excess H₂ supply to the CH₄/H₂ mixture plasma made the diameter distribution of the CNTs wider and the yield lower. Hydrogen concentration is considered to affect catalyst particle size and activity during the time interval before starting CNT growth (=incubation period). With CH₄/H₂ = 27/3 sccm for a growth time of 10 min efficient CNT growth was achieved because the amount of carbon atoms in the CNTs and that calculated from simulation showed good agreement. The effect of hydrogen etching on CNTs was analyzed by scanning electron microscopy and X-ray photoelectron spectroscopy by observing CNTs treated by H₂ plasma after CNT growth. It was confirmed that (a) multi-walled CNTs were not etched by the H₂ plasma, (b) the C 1s XPS spectra of the CNTs showed no chemical shift after the treatment, and (c) C-H bonds were produced in CNTs during their growth.     

Aligned carbon nanotubes fabricated by thermal CVD at atmospheric pressure using Co as catalyst with NH3 as reactive gas

Co is used as a catalyst for chemical vapor deposition (CVD) of vertically aligned multi-walled carbon nanotubes (CNTs) in a tube furnace at atmospheric pressure. C₂H₂ and NH₃ were used for the carbon feedstock and reaction control, respectively. The CVD process parameters determine the chemical properties of the Co particles and subsequently the morphologies and field emission behavior of CNTs as they strongly depend upon the catalyst condition. The flow rate ratio of NH₃ to C₂H₂ is shown to be central to the synthesis of vertically aligned CNTs. Repeatable synthesis of vertically aligned CNTs at atmospheric pressure in a tube furnace is cost effective for large area deposition of such structures which may be used, for example, in vacuum field emission devices.     

Synthesis of carbon nanowalls by plasma-enhanced chemical vapor deposition in a CO/H2 microwave discharge system

Synthesis of carbon nanowalls was performed by a plasma-enhanced chemical vapor deposition in a CO/H₂ microwave discharge system. At the optimum CO/H₂ feed ratio of 46 sccm/4 sccm, the aligned carbon nanowalls with thickness of about several tens of nanometers were able to be synthesized. The extremely high growth rate of 1 μm min^− 1 was obtained in our system with a relatively low microwave discharge power of 60 W for a growth area of 1 cm². An optical emission spectroscopy was performed to clarify the characteristics of a CO/H₂ discharge system.     

Enhancement of H2 and CH4 adsorptivities of single wall carbon nanotubes produced by mixed acid treatment

Single wall carbon nanotubes (SWCNTs) were treated with a HNO₃/H₂SO₄ mixed solution to increase the number of narrow micropores. The mixed acid treatment increased the micropore volume from 0.13 to 0.35 mL g⁻¹ as measured by N₂ adsorption at 77 K. The micropore volume evaluated with CO₂ adsorption at 273 K increased from 0.06 to 0.27 mL g⁻¹. This remarkable micropore volume increase was ascribed to the formation of a highly packed and ordered SWCNT assembly with the acid treatment, which was confirmed by field emission scanning electron microscopy. The adsorption amount of supercritical H₂ at 77 K under 5 MPa pressure increased twofold as a result of the acid treatment, while the supercritical CH₄ adsorption amount at 303 K and 5 MPa pressure increased by 40%. These remarkable increases were caused by increased amount of narrow micropores as a result of the acid treatment.     

Visible light induced photocatalytic activity of Nb2O5/carbon cluster/Cr2O3 composite materials

Nano-sized Nb₂O₅/carbon cluster/Cr₂O₃ composite material was prepared by the calcination of NbCl₅/chromium acetylacetonate/epoxy resin complex under an argon atmosphere. The Pt-loaded Nb₂O₅/carbon cluster/Cr₂O₃ composite material shows the photocatalytic activity under visible light irradiation. The composite material successfully decomposed the water into H₂ and O₂ in the [H₂]/[O₂] ratio of 2. Electron spin resonance spectral examination suggests a two-step electron transfer in the process of Nb₂O₅ → carbon cluster → Cr₂O₃ → Pt.     

Gasoline-range hydrocarbon synthesis over Co/SiO2/HZSM-5 catalyst with CO2-containing syngas

Selective synthesis of gasoline-range hydrocarbons (C₅-C₁₂) was investigated in a fixed-bed micro reactor using two series of CO₂-containing syngas with various mole CO₂/(CO + CO₂) and H₂/(CO + CO₂) ratios, where Fischer-Tropsch synthesis(FTS) and in situ hydrocracking/hydroisomerization were performed over bifunctional Co/SiO₂/HZSM-5 catalyst. CO₂ was converted at 0.15-0.55 of CO₂/(CO + CO₂) ratio under H₂-rich condition (H₂/(CO + CO₂) = 2.0), highest conversion of 20.3% at 0.42. Further increasing CO₂ content decreased CO₂ conversion and quite amount of CO₂ acted as diluting component. For the syngas with low H₂ content or H₂/(CO + CO₂) ratio(< 1.85, H₂/CO = 2.0), the competitive adsorption of CO, H₂ and CO₂ resulted in low CO, CO₂ and total carbon conversion, which was 57.9%, 12.7% and 31.4% respectively at 0.74 of H₂/(CO + CO₂) ratio(H₂/CO/CO₂/N₂ = 40.8/20.4/34.8/4). FTS results indicated that high H₂ content and proper H₂/(CO + CO₂) ratio were favorable for the conversion of CO₂-containing syngas. More than 45% selectivity to gasoline-range hydrocarbons including isoparaffins was obtained under the two series of syngas. It was also tested that the catalytic activity of Co/SiO₂/HZSM-5 kept stable under CO₂-containing syngas(< 7.5%). And the quick catalytic deactivation under high CO₂ containing syngas(H₂/CO/CO₂/N₂ = 45.3/23.2/27.1/3.06) was due to carbon deposition and pore blockage by heavy hydrocarbon, tested by thermal gravimetry, N₂ physisorption and scanning electron microscopy(SEM).     

Influence of H2/NH3 mixtures on the composition of SiCNYO and SiCNAl(O) nanopowders

We performed pyrolysis of SiCNAlH and SiCNYOH nanopowder precursors under a reactive atmosphere (Ar/NH₃/H₂) with various compositions of ammonia (NH₃) and dihydrogen (H₂) to diminish C content, which is deleterious for thermal stability and sintering of the powders. This paper continues a previous work on the fabrication of an Si₃N₄/SiC composite without free C by studying the effect of H₂ on the C/N atomic ratio of the powder. We studied the influence of the nature of the gaseous mixture (Ar/NH₃/H₂) on the powder composition. Elemental analysis showed that the introduction of H₂ in the pyrolysis atmosphere limited the decomposition of NH₃ and allowed for control of the C/N ratio. This behaviour can be explained by the structural evolution observed by ²⁹Si NMR spectrometry but also by Fourier transform infrared and Raman spectroscopy. An Si₃N₄/SiC composite, with traces of free C, was obtained after post-pyrolysis heat treatment of the powders synthesized with 10 wt.% of H₂ and 25 wt.% NH₃.     

Defect structure for the ultra-nanocrystalline diamond films synthesized in H2-containing Ar/CH4 plasma

The modification on the microstructure of diamond films due to the addition of H₂ species into the Ar/CH₄ plasma was investigated. While the Ar/CH₄ plasma produced UNCD films with equiaxed grains (about 5 nm in size), the (Ar-H₂)/CH₄ plasma produced acicular-shaped grains (about 5 × 20 nm in size). Transmission electron microscopy studies indicate that these acicular-shaped grains actually are agglomerates of diamond flakes, which contain stacking faults lying on the (111) lattice plane. Presumably, the incorporation of H₂ species in the plasma leads to partial etching of hydrocarbons adhered onto the diamond clusters, such that the C₂- (or active carbon) species contained in the plasma can attach to the diamond surface anisotropically, leading to diamond flakes. The incorporation of H₂ in Ar plasma can also suppress the formation of i-carbons, an allotropic phase of diamonds. The critical proportion of H₂ in Ar plasma for inducing the changes in the granular structure is around 0.03%. The proportion of grain boundaries was thus reduced and the electron field emission properties of the materials were thus degraded. However, the suppression of the film electrical conductivity without sacrificing the smooth surface characteristic has the applications as high-thermal-conductivity heat spreaders and substrates for surface-acoustic-wave devices.     

Control of morphology and composition of self-organized zirconium titanate nanotubes formed in (NH4)2SO4/NH4F electrolytes

We investigated the formation of self-organized zirconium titanate nanotubes by anodizing a Ti-35Zr alloy in 1 M (NH₄)₂SO₄ + 0.1-2.0 wt.% NH₄F electrolytes. The morphology and composition of the zirconium titanate nanotube are controlled by the applied electrochemical conditions. The outer diameter of nanotubes is controlled by the anodization potential in the range between 1 and 100 V (versus Ag/AgCl). Tubes with diameters from 14 to 470 nm can be grown. The nanotube length correlates with the anodic charge up to a length where significant dissolution of the nanotube layer is observed. The wall thickness, composition of the nanotubes and porosity of the nanotube layer are significantly affected by the fluoride ion concentration. The length limiting factor of the nanotube growth is found to be the diffusion of ionic species in the electrolyte.     

Encapsulation mechanism of N2 molecules into the central hollow of carbon nitride multiwalled nanofibers

Nitrogen molecules have been encapsulated into the central hollows of vertically aligned carbon nitride (CN) multiwalled nanofibers by dc plasma-enhanced chemical vapor deposition with C₂H₂, NH₃, and N₂ gases on a Ni/TiN/Si(1 0 0) substrate at 650 °C. X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectra showed the existence of nitrogen molecules in CN nanofibers. Elemental mapping images with electron energy loss spectroscopy of the CN nanofiber and catalyst metal, and optical emission spectroscopy spectra of the plasma showed the distribution of nitrogen atoms and molecules in the CN nanofiber, catalyst metal, and gaseous precursor, respectively. These studies showed that atomic nitrogen diffused into the catalytic metal particle because of the concentration gradient and then saturated at the bottom of the particle. Saturated nitrogen atom participated in the formation of the CN nanofiber wall but most of nitrogen was trapped in the central hollow of the nanofiber as molecules.     

Fixed- and fluidised-bed synthesis of coiled carbon fibres on an in situ generated H2S-modified Ni/Al2O3 catalyst from a NiSO4/Al2O3 precursor

NiSO₄/Al₂O₃ and NiO/Al₂O₃ catalyst precursors were formed by calcination of NiSO₄·6H₂O/Al₂O₃ at 500 and 800 °C, respectively. The catalyst precursor was reduced under H₂ and N₂ and then reacted under C₂H₂, H₂ and N₂ at 650 °C. Coiled carbon fibres were formed in fixed- and fluidised-bed reactors using the NiSO₄/Al₂O₃ catalyst precursor. Thermodynamic modelling using an infinite equilibrium stage construction predicted complete reduction of NiSO₄ to Ni and simultaneous H₂S formation occurs in both fixed- and fluidised-bed systems. XRD measurements confirmed that Ni was the only catalytically active crystalline species present at concentrations >0.5 wt.% (XRD detection limit) post-reduction, however XRF and XPS measurements additionally detected the presence of small quantities (<0.9 wt.% S) of S species. S is adsorbed onto the Ni surfaces during reduction when H₂S is released and dissociates on the Ni surface. Non-coiled carbon fibres produced on the Ni/Al₂O₃ catalyst formed from the NiO/Al₂O₃ precursor demonstrated that modification of Ni/Al₂O₃ with S is required for coiled carbon fibre synthesis.     

Electrochemical performance of the carbon coated Li3V2(PO4)3 cathode material synthesized by a sol-gel method

A carbon coated Li₃V₂(PO₄)₃ cathode material for lithium ion batteries was synthesized by a sol-gel method using V₂O₅, H₂O₂, NH₄H₂PO₄, LiOH and citric acid as starting materials, and its physicochemical properties were investigated using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), energy dispersive analysis of X-ray (EDAX), transmission electron microscope (TEM), and electrochemical methods. The sample prepared displays a monoclinic structure with a space group of P2₁/n, and its surface is covered with a rough and porous carbon layer. In the voltage range of 3.0-4.3 V, the Li₃V₂(PO₄)₃ electrode displays a large reversible capacity, good rate capability and excellent cyclic stability at both 25 and 55 °C. The largest reversible capacity of 130 mAh g⁻¹ was obtained at 0.1C and 55 °C, nearly equivalent to the reversible cycling of two lithium ions per Li₃V₂(PO₄)₃ formula unit (133 mAh g⁻¹). It was found that the increase in total carbon content can improve the discharge performance of the Li₃V₂(PO₄)₃ electrode. In the voltage range of 3.0-4.8 V, the extraction and reinsertion of the third lithium ion in the carbon coated Li₃V₂(PO₄)₃ host are almost reversible, exhibiting a reversible capacity of 177 mAh g⁻¹ and good cyclic performance. The reasons for the excellent electrochemical performance of the carbon coated Li₃V₂(PO₄)₃ cathode material were also discussed.     

Growth of conformal single-walled carbon nanotube films from Mo/Fe/Al2O3 deposited by electron beam evaporation

We discuss growth of high-quality carbon nanotube (CNT) films on bare and microstructured silicon substrates by atmospheric pressure thermal chemical vapor deposition (CVD), from a Mo/Fe/Al₂O₃ catalyst film deposited by entirely electron beam evaporation. High-density films having a tangled morphology and a Raman G/D ratio of at least 20 are grown over a temperature range of 750-900 °C. H₂ is necessary for CNT growth from this catalyst in a CH₄ environment, and at 875 °C the highest yield is obtained from a mixture of 10%/90% H₂/CH₄. We demonstrate for the first time that physical deposition of the catalyst film enables growth of uniform and conformal CNT films on a variety of silicon microstructures, including vertical sidewalls fabricated by reactive ion etching and angled surfaces fabricated by anisotropic wet etching. Our results confirm that adding Mo to Fe promotes high-yield SWNT growth in H₂/CH₄; however, Mo/Fe/Al₂O₃ gives poor-quality multi-walled CNTs (MWNTs) in H₂/C₂H₄. An exceptional yield of vertically-aligned MWNTs grows from only Fe/Al₂O₃ in H₂/C₂H₄. These results emphasize the synergy between the catalyst and gas activity in determining the morphology, yield, and quality of CNTs grown by CVD, and enable direct growth of CNT films in micromachined systems for a variety of applications.     

Microstructural and electrochemical characterization of RuO2/CNT composites synthesized in supercritical diethyl amine

A simple and efficient route to decorate carbon nanotubes (CNTs) with nanocrystalline RuO₂ has been developed. In this method, RuCl₃ · 3H₂O was oxidized into RuO₂ by oxygen in supercritical diethyl amine, and the produced RuO₂ deposited on CNTs, resulting in RuO₂/CNT nanocomposites. The as-prepared composites were structurally and morphologically characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy (TEM). TEM images showed that RuO₂ nanoparticles attached on CNTs had uniform shape and a narrow particle size distribution. The loading content and the size of RuO₂ particles on CNTs could be tuned by changing the mass ratio of RuCl₃ · 3H₂O/CNT. Electrochemical measurements by cyclic voltammetry demonstrated a substantial increment of the specific capacitance of CNTs due to a pseudocapacitance originated from the deposited RuO₂ nanoparticles.     

Steam reforming of LPG over Ni and Rh supported on Gd-CeO2 and Al2O3: Effect of support and feed composition

The steam reforming of liquefied petroleum gas (LPG) over Ni- and Rh-based catalysts supported on Gd-CeO₂ (CGO) and Al₂O₃ was studied at 750-900 °C. The order of activity was found to be Rh/CGO > Ni/CGO ∼ Rh/Al₂O₃ > Ni/Al₂O₃; we indicated that the comparable activity of Ni/CGO to precious metal Rh/Al₂O₃ is due to the occurring of gas-solid reactions between hydrocarbons and lattice oxygen () on CGO surface along with the reaction taking place on the active site of Ni, which helps preventing the carbon deposition and promoting the steam reforming of LPG.The effects of O₂ (as oxidative steam reforming) and H₂ adding were further studied over Ni/CGO and Ni/Al₂O₃. It was found that the additional of these compounds significantly reduced the amount of carbon deposition and promoted the conversion of hydrocarbons (i.e., LPG as well as CH₄, C₂H₄ and C₂H₆ occurred from the thermal decomposition of LPG) to CO and H₂. Nevertheless, the addition of too high O₂ oppositely decreased H₂ yield due to the oxidizing of Ni particle and the possible combusting of H₂ generated from the reaction, while the addition of too high H₂ also negatively affect the catalyst activity due to the occurring of catalyst active site competition and the inhibition of gas-solid reactions between the gaseous hydrocarbon compounds and on the surface of CGO (for the case of Ni/CGO).     

Synthesis, characterization and performance of CuO/La2O3 composite catalyst for ammonia catalytic oxidation

This work considers the oxidation of ammonia (NH₃) by selective catalytic oxidation (SCO) over a CuO/La₂O₃ composite catalyst at temperatures between 150 and 400 °C. A CuO/La₂O₃ composite catalyst was prepared by co-precipitation of copper nitrate and lanthanum nitrate at various molar concentrations. This study also considers how the concentration of influent NH₃ (C₀ = 1000 ppm), the space velocity (GHSV = 92,000 l/h), the relative humidity (RH = 12%) and the concentration of oxygen (O₂ = 4%) affect the operational stability and the capacity for removing NH₃. The catalysts that were characterized using FTIR, XRD, UV-Vis, BET and PSA, have shown that the catalytic behavior is related to the copper (II) oxide, while lanthanum (III) oxide may serve only to provide active sites for the reaction during a catalyzed oxidation run. The experimental results show that the extent of conversion of ammonia by SCO in the presence of the CuO/La₂O₃ composite catalyst was a function of the molar ratio. The ammonia was removed by oxidation in the absence of CuO/La₂O₃ composite catalyst, and around 93.0% NH₃ reduction was achieved during catalytic oxidation over the CuO/La₂O₃ (8:2, molar/molar) catalyst at 400 °C with an oxygen content of 4.0%. Moreover, the effect of the reaction temperature on the removal of NH₃ in the gaseous phase was also monitored at a gas hourly space velocity of under 92,000 h^− 1.     

Electrocatalyst materials for fuel cells based on the polyoxometalates—K7 or H7[(P2W17O61)Fe(H2O)] and Na12 or H12[(P2W15O56)2Fe4(H2O)2]

Free acids of the iron substituted heteropoly acids (HPA), H₇[(P₂W₁₇O₆₁)Fe^III(H₂O)] (HFe1) and H₁₈[(P₂W₁₅O₅₆)₂Fe^III₂(H₂O)₂] (HFe2) were prepared from the salts K₇[(P₂W₁₇O₆₁)Fe^III(H₂O)] (KFe1) and Na₁₂[(P₂W₁₅O₅₆)₂Fe^III₄(H₂O)₂] (NaFe4), respectively. The iron-substituted HPA were adsorbed on to XC-72 carbon based GDLs to form HPA doped GDEs after water washing with HPA loadings of ca. 1 μmol. The HPA was detected throughout the GDL by EDX. Solution electrochemistry of the free acids are reported for the first time in sulfate buffer, pH 1-3. The hydrogen oxidation reaction was catalyzed by KFe1 at 0.33 V, with an exchange current density of 38 mA/cm². Moderate activity for the oxygen reduction reaction was observed for the iron substituted HPA, which was dramatically improved by selectively removing oxygen atoms from the HPA by cycling the fuel cell cathode under N₂ followed by reoxidation to give a restructured oxide catalyst. The nanostructured oxide achieved an OCV of 0.7 V with a Tafel slope of 115 mV/decade. Cycling the same catalysts in oxygen resulted in an improved catalyst/ionomer/carbon configuration with a slightly higher Tafel slope, 128 mV/decade but a respectable current density of 100 mA/cm² at 0.2 V.     

In situ diagnosis of chemical species for the growth of carbon nanotubes in microwave plasma-enhanced chemical vapor deposition

A synthesis of multi-wall carbon nanotubes (MWNTs) by microwave plasma-enhanced chemical vapor deposition using CH₄/H₂/NH₃ gases on Ni/Cr-coated glass at low temperature, was investigated by optical emission spectroscopy (OES) and quadrupole mass spectroscopy (MS). It was observed that the MWNTs were grown within a very restrictive range of the gas compositions. Optical emission lines were observed primarily from atomic hydrogen H_α, molecular hydrogen, and CN radicals. The quadrupole mass spectrum also showed the formation of C₂H₂ and HCN. An addition of a small amount of NH₃ resulted in a decrease of C₂H₂, which could be used to estimate amounts of carbon sources present in the plasma for the growth of MWNTs, and increases of CN and H_α radicals acting as etching species of amorphous carbon. These results show that the etching species of amorphous carbon as well as the growth species are necessary and the ratio between two species have to be in appropriate condition for the synthesis of carbon nanotubes at low temperature. The optimum C₂H₂/H_α ratio in the gas mixture for the growth of MWNTs at low temperature was found to be 1:5 in this study.