Surface characteristics of Ni catalystic films on growth behavior of multi-walled carbon nanotubes

The effect of the surface characteristics of Ni catalyst films on the growth behavior of multi-walled carbon nanotubes (MWCNTs) were investigated using Ni catalyst films prepared by different physical vapor deposition methods, electron-beam evaporation and sputtering. The growth behavior of MWCNTs was dependent upon the surface roughness of the Ni films. After a pretreatment process with NH₃, the root mean squares of surface roughness of e-beam evaporated and sputtered Ni catalyst films increased to 16.6 and 3.2 nm, respectively. Curled-MWCNTs and carbon-encapsulated Ni nanoparticles were formed on the Ni film deposited by e-beam evaporation while vertically aligned-MWCNTs were grown on the sputter-deposited film. In addition, the surface roughness of the Ni films affected the field emission properties of the MWCNTs. This was considered to originate from the specific growth behavior of the MWCNTs which was primarily caused by the initial surface roughness of the Ni films.     

Synthesis of carbon nanotubes by CVD: Effect of acetylene pressure on nanotubes characteristics

The effect of acetylene partial pressure on the structural and morphological properties of multi-walled carbon nanotubes (MWCNTs) synthesized by CVD on iron nanoparticles dispersed in a SiO₂ matrix as catalyst was investigated. The general growing conditions were: 110 cm³/min flow rate, 690 °C synthesis temperature, 180 Torr over pressure and two gas compositions: 2.5% and 10% C₂H₂/N₂. The catalyst and nanotubes were characterized by HR-TEM, SEM and DRX. TGA and DTA were also carried out to study degradation stages of synthesized CNTs. MWCNTs synthesized with low acetylene concentration are more regular and with a lower amount of amorphous carbon than those synthesized with a high concentration. During the synthesis of CNTs, amorphous carbon nanoparticles nucleate on the external wall of the nanotubes. At high acetylene concentration carbon nanoparticles grow, covering all CNTs’ surface, forming a compact coating. The combination of CNTs with this coating of amorphous carbon nanoparticles lead to a material with high decomposition temperature.     

Carbon nanotubes supported Cu-Ni bimetallic catalysts and their properties for the direct synthesis of dimethyl carbonate from methanol and carbon dioxide

Multi-walled carbon nanotubes (MWCNTs) supported Cu-Ni bimetallic catalysts for the direct synthesis of dimethyl carbonate (DMC) from CH₃OH and CO₂ were synthesized and investigated. The supporting materials and the synthesized catalysts were fully characterized using FTIR, scanning electron microscopy (SEM), transmission electron microscopy (TEM), temperature-programmed reduction (TPR), X-ray diffraction (XRD) and X-ray photoelectron spectrum (XPS) techniques. The catalytic activities were investigated by performing micro-reactions. The experimental results showed that the metal phase and Cu-Ni alloy phase in the catalyst were partially formed during the calcination and activation step. Active metal particles were dispersed homogeneously on the surface of the MWCNTs. Cu-Ni/MWCNTs catalysts were efficient for the direct synthesis of DMC. The highest conversion of CH₃OH was higher than 4.3% and the selectivity of DMC was higher than 85.0% under the optimal catalytic conditions of 120 °C and around 1.2 MPa. The high catalytic activity of Cu-Ni/MWCNTs in DMC synthesis can be attributed to the synergetic effects of metal Cu, Ni and Cu-Ni alloy in the activation of CH₃OH and CO₂, the unique structure of MWCNTs and the interaction between the metal particles and the supports.     

A novel continuous process for synthesis of carbon nanotubes using iron floating catalyst and MgO particles for CVD of methane in a fluidized bed reactor

A novel continuous process is used for production of carbon nanotubes (CNTs) by catalytic chemical vapor deposition (CVD) of methane on iron floating catalyst in situ deposited on MgO in a fluidized bed reactor. In the hot zone of the reactor, sublimed ferrocene vapors were contacted with MgO powder fluidized by methane feed to produce Fe/MgO catalyst in situ. An annular tube was used to enhance the ferrocene and MgO contacting efficiency. Multi-wall as well as single-wall CNTs was grown on the Fe/MgO catalyst while falling down the reactor. The CNTs were continuously collected at the bottom of the reactor, only when MgO powder was used. The annular tube enhanced the contacting efficiency and improved both the quality and quantity of CNTs.The SEM and TEM micrographs of the products reveal that the CNTs are mostly entangled bundles with diameters of about 10-20 nm. Raman spectra show that the CNTs have low amount of amorphous/defected carbon with I_G/I_D ratios as high as 10.2 for synthesis at 900 °C. The RBM Raman peaks indicate formation of single-walled carbon nanotubes (SWNTs) of 1.0-1.2 nm diameter.     

Effective synthesis of carbon nanotubes via catalytic decomposition of methane: Influence of calcination temperature on metal–support interaction of Co–Mo/MgO catalyst

The present work investigated the influence of calcination temperature for bimetallic Co–Mo/MgO catalyst on the synthesis of carbon nanotubes (CNTs) via catalytic chemical vapor deposition (CCVD) of methane. The experimental results showed that variation in the catalyst calcination temperature affected carbon yield, diameter distribution and quality of the CNTs. Increasing the catalyst calcination temperature enabled Co–Mo/MgO catalysts in growing CNTs at higher yield, narrower diameter distribution and better degree of graphitization, credited to the strong metal–support interaction (MSI) formed between CoO species and MgO support. We also discovered that the catalysts of weak MSI were beneficial to the nucleation and growth of CNTs, meanwhile the catalysts with strong MSI provoked the growth of CNTs with narrow diameter distribution. The catalyst calcined at 700 °C, possessing moderate MSI, was found to be the most suitable catalyst for the growth of high quality CNTs with the diameter of 7.70±0.77 nm and the carbon yield of as high as 647.4%.     

Short time synthesis of high quality carbon nanotubes with high rates by CVD of methane on continuously emerged iron nanoparticles

We report the variation of yield and quality of carbon nanotubes (CNTs) grown by chemical vapor deposition (CVD) of methane on iron oxide-MgO at 900-1000 °C for 1-60 min. The catalyst was prepared by impregnation of MgO powder with iron nitrate, dried, and calcined at 300 °C. As calcined and unreduced catalyst in quartz reactor was brought to the synthesis temperature in helium flow in a few minutes, and then the flow was switched to methane. The iron oxide was reduced to iron nanoparticles in methane, while the CNTs were growing.TEM micrographs, in accordance with Raman RBM peaks, indicate the formation of mostly single wall carbon nanotubes of about 1.0 nm size. High quality CNTs with I_G/I_D Raman peak ratio of 14.5 are formed in the first minute of CNTs synthesis with the highest rate. Both the rate and quality of CNTs degrades with increasing CNTs synthesis time. Also CNTs quality sharply declines with temperature in the range of 900-1000 °C, while the CNTs yield passes through a maximum at 950 °C. About the same CNTs lengths are formed for the whole range of the synthesis times. A model of continuous emergence of iron nanoparticle seeds for CNTs synthesis may explain the data. The data can also provide information for continuous production of CNTs in a fluidized bed reactor.     

EPMA-EDS surface measurements of interdiffusion coefficients between miscible metals in thin films

A new technique is developed to study interdiffusion between two miscible metals. The technique is applied to the Ni-Pd system. It consists in measuring the change of apparent surface composition of a Pd substrate coated with an 800 nm Ni thin film during annealing at a given temperature. The measurement is carried out in-situ inside the chamber of a SEM (scanning electron microscope) by EPMA-EDS (electron probe microanalysis-energy dispersive X-ray spectroscopy). The experimental data are processed using a model that mixes the Fick's diffusion equations and the electron probe microanalysis equation. This process allows the determination of the mean interdiffusion coefficient at a given annealing temperature. The main advantages of the technique are the possible determination of interdiffusion coefficients in thin films and at very low temperature (down to 430 °C, i.e. ∼0.4 T_m), which is not achievable with other techniques conventionally used for the study of interdiffusion. The Ni-Pd mean interdiffusion coefficient is shown to follow an Arrhenius law between 430 °C and 900 °C, in relatively good agreement with previous interdiffusion measurements made on the Ni-Pd system at higher temperature.     

Effects of different carbon precursors on synthesis of multiwall carbon nanotubes: Purification and Functionalization

Cyclohexanol and xylene were used as carbon precursors, for synthesis of multiwall carbon nanotubes (MWCNTs) arrays in a CVD system at temperature of 750 °C, using nitrogen as carrier gas and ferrocene as catalyst. Different characterization methods were employed to compare the MWCNTs structure synthesized by these two precursors. All scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA) and Raman spectroscopy results illustrated that using cyclohexanol could significantly reduce formation of amorphous carbon and catalyst particles in the as-grown CNTs. The less amorphous carbon can be attributed to in situ oxidation in presence of oxygen atom of cyclohexanol. Characterizations showed that MWCNTs with high purity could be obtained using cyclohexanol as carbon precursor. The as-grown MWCNTs were purified by oxidation and acid treatment. Characterization of the purified MWCNTs using HNO₃/H₂SO₄ (1/3 or 1/1), 8 M HCl or 8 M HNO₃ was carried out. The results showed that 8 M HNO₃ could be considered as the best chemical to obtain more pure MWCNTs, less amorphous and metal particles and less damaged MWCNTs. The Raman spectroscopy results demonstrated that HNO₃/H₂SO₄ (1/3) treatment could more disorder the MWCNTs structure and this was attributed to the bigger destroying effect of this acid treatment. Furthermore, the TEM analysis of MWCNTs before and after acid treatment revealed that acid treatment could remove encapsulated catalyst particles. The FTIR analysis illustrated that purification of the MWCNTs with nitric acid could connect the functional groups onto the outer surface of MWCNTs and this resulted in more dispersion of the MWCNTs in water.     

Direct writing of carbon nanotube patterns by laser-induced chemical vapor deposition on a transparent substrate

Dot array and line patterns of multi-walled carbon nanotubes (MWCNTs) were successfully grown by laser-induced chemical vapor deposition (LCVD) on a transparent substrate at room temperature. In the proposed technique, a Nd:YVO₄ laser with a wavelength of 532 nm irradiates the backside of multiple catalyst layers (Ni/Al/Cr) through a transparent substrate to induce a local temperature rise, thereby allowing the direct writing of dense dot and line patterns of MWCNTs below 10 μm in size to be produced with uniform density on the controlled positions. In this LCVD method, a multiple-catalyst-layer with a Cr thermal layer is the central component for enabling the growth of dense MWCNTs with good spatial resolution.     

Reactively sputtered Ni, Ni(N) and Ni3N films: Structural, electrical and magnetic properties

Nickel thin films were deposited on glass substrates at different N₂ gas contents using a dc triode sputtering deposition system. Triode configuration was used to deposit nanostructured thin films with preferred orientation at lower gas pressure and at lower substrate temperature compared to the dc diode sputtering system. A gradual evolution in the composition of the films from Ni, Ni(N), to Ni₃N was found by X-ray diffraction analysis. The preferred growth orientation of the nanostructured Ni films changed from (1 1 1) to (1 0 0) for 9% N₂ at 100 °C. Ni₃N films were formed at 23% N₂ with a particle size of about 65 nm, while for 0% and 9% of nitrogen, the particles sizes were 60 nm, and 37 nm, respectively, as obtained by atomic force microscopy. Magnetic force microscopy imaging showed that the local magnetic structure changed from disordered stripe domains of about 200 nm for Ni and Ni(N) to a structure without a magnetic contrast, indicating the paramagnetic state of this material, which confirmed the structural transformation from Ni to Ni₃N.     

Preparation, magnetic and electromagnetic properties of polyaniline/strontium ferrite/multiwalled carbon nanotubes composite

Strontium ferrite particles were firstly prepared by sol-gel method and self-propagating synthesis, and then the polyaniline/strontium ferrite/multiwalled carbon nanotubes composites were synthesized through in situ polymerization approach. Structure, morphology and properties of the composite were characterized by various instruments. XRD analysis shows that the output of PANI increases with the increase of the content of MWCNTs, due to the large surface area of MWCNTs. Because of the coating of PANI, the outer diameter of MWCNTs increases from 10 nm to 20-40 nm. The electrical conductivity of the composites increases with the amount increase of MWCNTs and reaches 7.2196 S/cm in the presence of 2 g MWCNTs. The coercive force of the composites prepared with 2 g MWCNTs is 7457.17 Oe, which is much bigger than that of SrFe₁₂O₁₉ particles 6145.6 Oe, however, both the saturation magnetization and the remanent magnetization of the composite become much smaller than those of SrFe₁₂O₁₉ particles. The electromagnetic properties of the composite are excellent in the frequency range of 2-18 GHz, which mainly depend on the dielectric loss in the range of 2-9 GHz, and mainly on the magnetic loss in the range of 9-18 GHz.     

The effect of heat treatment on the performance of the Ni/(Zr-Sm oxide) catalysts for carbon dioxide methanation

The active catalysts for methane formation from the gas mixture of CO₂ + 4H₂ with almost 100% methane selectivity were prepared by reduction of the oxide mixture of NiO and ZrO₂ prepared by calcination of aqueous ZrO₂ sol with Sm(NO₃)₃ and Ni(NO₃)₂. The 50 at%Ni-50 at%(Zr-Sm oxide) catalyst consisting of 50 at%Ni-50 at%(Zr + Sm) with Zr/Sm = 5 calcined at 650 or 800 °C showed the highest activity for methanation. The active catalysts were Ni supported on tetragonal ZrO₂, and the activity for methanation increased by an increase in inclusion of Sm³⁺ ions substituting Zr⁴⁺ ions in the tetragonal ZrO₂ lattice as a result of an increase in calcination temperature. However, the increase in calcination temperature decreased BET surface area, metal dispersion and hydrogen uptake due to grain growth. Thus, the optimum calcination temperature existed.     

Formation,structure, and magnetic changes at annealing of films deposited by laser sputtering of Ni and Pd

The electron microscopy investigations of Pd, Ni, and Ni-Pd alloy films are carried out. The films were produced by laser sputtering of one- and two-element targets. It is shown that, in the case of alternate deposition of nickel and palladium, polycrystalline films with a metastable hcp lattice are formed. The hcp lattice parameters increase monotonically with increasing palladium content in the film. As a result of the annealing, Ni and Ni-Pd alloy films acquire an equilibrium fcc structure. A positive deviation from Vegard’s law occurs for the dependence of the lattice parameter of the solid solution on the Pd concentration. The as-prepared Ni and Ni-Pd alloy films with the hcp structure are characterized by the absence of a magnetic moment. The transition into the ferromagnetic state occurs after annealing, and hysteresis is observed upon magnetization reversal.     

The effect of Fe and Ni catalysts on the growth of multiwalled carbon nanotubes using chemical vapor deposition

The effect of Fe and Ni catalysts on the synthesis of carbon nanotubes (CNTs) using atmospheric pressure chemical vapor deposition (APCVD) was investigated. Field emission scanning electron microscopy (FESEM) analysis suggests that the samples grow through a tip growth mechanism. High-resolution transmission electron microscopy (HRTEM) measurements show multiwalled carbon nanotubes (MWCNTs) with bamboo structure for Ni catalyst while iron filled straight tubes were obtained with the Fe catalyst. The X-ray diffraction (XRD) pattern indicates that nanotubes are graphitic in nature and there is no trace of carbide phases in both the cases. Low frequency Raman analysis of the bamboo-like and filled CNTs confirms the presence of radial breathing modes (RBM). The degree of graphitization of CNTs synthesized from Fe catalyst is higher than that from Ni catalyst as demonstrated by the high frequency Raman analysis. Simple models for the growth of bamboo-like and tubular catalyst filled nanotubes are proposed.     

Synthesis and characterization of the Pd/InVO4-TiO2 co-doped thin films with visible light photocatalytic activities

Novel Pd/InVO₄-TiO₂ thin films with visible light photocatalytic activity were synthesized from the Pd and InVO₂ co-doped TiO₂ sol via sol-gel method. The photocatalytic activities of Pd/InVO₄-TiO₂ thin films were investigated based on the oxidative decomposition of methyl orange in aqueous solution. The as-prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and UV-vis absorption spectroscopy (UV-vis). The results indicate that the Pd/InVO₄-TiO₂ thin films are compact, uniform and consist of sphere nanoparticles with diameters about 80-100 nm. The UV-vis spectra show that the Pd/InVO₄-TiO₂ thin films extend the light absorption spectrum toward the visible region. XPS results reveal that doped Pd exist in the form of metallic palladium. The photocatalytic experiments demonstrate that Pd doping can effectively enhance the photocatalytic activities of InVO₄-TiO₂ thin films in decomposition of aqueous methyl orange under visible light irradiation. It has been confirmed that Pd/InVO₄-TiO₂ thin films could be excited by visible light (E < 3.2 eV) due to the existence of the Pd and InVO₄ doped in the films.     

Carbon nanotubes supported Pt-Ni catalysts and their properties for the liquid phase hydrogenation of cinnamaldehyde to hydrocinnamaldehyde

The Pt-Ni catalysts supported on CNTs have been prepared by wet impregnation and the selective hydrogenation of cinnamaldehyde (CMA) to the corresponding hydrocinnamaldehyde (HCMA) over the catalysts has been studied in ethanol at different reaction conditions. The results show that Pt-0.34 wt% Ni/CNTs catalyst exhibits the highest activity and selectivity at a reaction temperature of 70 °C under a pressure of around 2.0 MPa, and 98.6% for the conversion of CMA and 88.2% for the selectivity of CMA to HCMA, respectively. The selective hydrogenation for the CC bond in CMA would be improved as increasing the reaction temperature, and the hydrogenation for the CO bond in CMA is enhanced as increasing the H₂ pressure. In addition, these catalysts have also been characterized using TEM-EDS, XPS, H₂-TPR and H₂-TPD techniques. The results show that Pt particles are dispersed more homogeneously on the outer surface of the nanotubes, while the strong interaction between Pt and Ni would improve the increasing of activated hydrogen number because of the hydrogen spillover from reduced Pt⁰ onto CNTs and increase the catalytic activity and selectivity of CMA to HCMA.     

Field emission properties of carbon nanotubes film grown on NiCr alloy films

Carbon nanotubes (CNTs) are prepared on NiCr alloy films by low pressure thermal chemical vapor deposition at 600 °C. NiCr alloy films are deposited by magnetic co-sputtering method, and the various thickness and Ni/NiCr ratios are controlled by sputtering power. The diameter and length of CNTs, as well as the roughness of the CNTs films, mainly depend on the Ni/NiCr ratio. The field emission current density of the CNTs film increases with the increasing Ni/NiCr ratio from 65 wt% to 83 wt%, and decreases when the Ni/NiCr ratio is more than 87 wt% in the alloy film.     

Influence of transition metals (Cr, Mn, Fe, Co and Ni) on the methane combustion over Pd/Ce-Zr/Al2O3 catalyst

The effects of transition metals (Cr, Mn, Fe, Co and Ni) on the catalytic properties of Pd/Ce-Zr/Al₂O₃ catalyst for methane combustion have been investigated. The supported Pd catalysts are characterized by BET, XRD, TEM, TPR, TPO and TPSR measurements. Activity tests in methane combustion show that Pd/Ce-Zr-Ni/Al₂O₃ has the highest catalytic activity and thermal stability among all catalysts. The results of TEM show that the addition of Ni to Pd/Ce-Zr/Al₂O₃ increases the dispersion of Pd component and inhibits the site growth. The results of TPO and TPSR show that the addition of Ni inhibits the decomposition of PdO particles and improves the reduction-reoxidation properties of the active PdO species, which increases the catalytic activity and thermal stability of the Pd/Ce-Zr/Al₂O₃ catalyst.     

Preparation and characterization of novel Pd/SiO2 and Ca-Pd/SiO2 egg-shell catalysts with porous hollow silica

Novel egg-shell structured monometallic Pd/SiO₂ and bimetallic Ca-Pd/SiO₂ catalysts were prepared by an impregnation method using porous hollow silica (PHS) as the support and PdCl₂ and Ca(NO₃)₂·4H₂O as the precursors. It was found from transmission electron microscope (TEM), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) that Pd was loaded on PHS with a particle size of 5-12 nm in Pd/SiO₂ samples and the Pd particle size in Ca-Pd/SiO₂ was smaller than that in Pd/SiO₂ since Ca could prevent Pd particles from aggregating. X-ray photoelectron spectroscopy (XPS) analyses exhibited that Pd 3d_5/2 binding energies of Pd/SiO₂ and Ca-Pd/SiO₂ were 0.2 and 0.9 eV lower than that of bulk Pd, respectively, as a result of the shift of the electron cloud from Pd to oxygen in Pd/SiO₂ and to both oxygen and Ca in Ca-Pd/SiO₂. The activity of Ca-Pd/SiO₂ egg-shell catalyst for CO hydrogenation and the selectivity to methanol, with a value of 36.50 mmol_CO mol⁻¹_Pd s⁻¹ and 100%, respectively, were much higher than those of the catalysts prepared with traditional silica gel as the support, owing to the porous core-shell structure of the PHS support.