Selective growth of single-walled carbon nanotubes over Co–MgO catalyst by chemical vapor deposition of methane

The selective synthesis of SWCNTs with narrow chirality and diameter distribution by methane decomposition over a Co–MgO catalyst is reported. Raman spectroscopy, temperature programmed oxidation (TPO), UV–Vis–NIR absorption spectroscopy, and nitrogen physisorption were used to probe SWCNTs morphology, reaction selectivity, SWCNTs chirality and diameter distribution, and carbon yield. The catalyst was examined by nitrogen physisorption, X-ray diffraction (XRD), temperature programmed reduction (TPR), and UV–Vis-diffuse reflectance spectroscopy to elucidate the structure and chemical state of the species responsible for SWCNT growth. The results established a clear link between the degree of dispersion of Co species inside the MgO lattice and the catalyst activity and selectivity for SWCNT growth. High dispersion and stabilization of Co species influenced catalytic activity for methane decomposition and the high SWCNT selectivity. The yield of carbon and SWCNT selectivity increased with an increase in temperature, however, SWCNTs diameter distribution shifts to larger diameter tubes as synthesis temperature was increased.     

Impact of nanometal catalysts on the laser vaporization synthesis of single wall carbon nanotubes

The effects of catalyst particle size on the purity, yield, and purification efficiency of single wall carbon nanotubes (SWCNTs) synthesized via pulsed laser vaporization were investigated. The purity of as-produced SWCNT material synthesized using Ni and Co nanometal (∼13 nm diameter) catalyst particles was compared to material synthesized using conventional micronmetal (2-3 μm diameter) particles. The SWCNT material from nanometal catalysts demonstrated a 50% increase in SWCNT purity as assessed by optical absorption spectroscopy and thermogravimetric analysis (TGA). A change in the thermal oxidation properties was also observed with the nanometal-SWCNTs exhibiting a suppression of the exothermic oxidation of post-synthesis catalyst. Statistical analysis of the TGA residue yielded mean post-synthesis catalyst particle diameters of 18 ± 6 nm and 3 ± 1 nm for the micronmetal and nanometal produced material, respectively. When a thermal oxidation profile was performed, the micronmetal-produced material showed the typical decrease in SWCNT purity with increasing oxidation temperature while the nanometal-produced material showed increasing SWCNT purity with increasing temperature. Overall, the use of nanometal catalysts significantly increases synthesis yield and offers novel thermal oxidation procedures to thermally remove carbonaceous impurities without the aid of acid treatments for the development of potential large-scale purification processing.     

Fabrication of single-wall carbon nanotubes within the channels of a mesoporous material by catalyst-supported chemical vapor deposition

Diameter-controlled single-wall carbon nanotubes (SWCNTs) have been synthesized using Co, Fe/Co and Rh/Pd alloy nanoparticles trapped within the one-dimensional channels of a mesoporous materials (Folded Sheets Mesoporous material: FSM-16) by catalyst-supported chemical vapor deposition (CCVD) using ethanol as carbon source at 973-1173 K. The SWCNTs synthesized are characterized by transmission electron microscopy, Raman spectroscopy and photoluminescence spectroscopy. The yield, diameter distribution and quality of the SWCNTs strongly depend on the reaction temperature during CCVD. The product synthesized at 1173 K contains only SWCNTs, in marked contrast to those synthesized at lower temperatures. As the reaction temperature decreases, the relative abundance of multi-wall carbon nanotubes against SWCNTs significantly increases, whereas the mean diameter of SWCNTs increases as reaction temperature increases. The results show that a careful control of the reaction temperature is crucial to fabricate diameter-controlled SWCNTs from the channels of FSM-16.     

Control of the single-wall carbon nanotube mean diameter in sulphur promoted aerosol-assisted chemical vapour deposition

The influence of gas flow on nanotube diameter during the synthesis of high-purity, very long single-wall carbon nanotubes (SWCNT) via aerosol-assisted chemical vapour deposition is reported. The sample morphology, nanotube yield, defect concentration and amount of carbonaceous impurities, as well as the mean diameter and the diameter distribution of the SWCNTs were analysed by combined scanning- and transmission electron microscopy, Fourier Transform Raman spectroscopy and optical absorption spectroscopy. The results show that by using a solution of ferrocene and sulphur in m-xylene the addition of sulphur as a promoter was found to enhance the SWCNT growth and to increase the yield. A reduction of the mean diameter and a change in the diameter distribution are observed when the total gas flow is increased.     

Selective synthesis of single-walled carbon nanotubes on Fe–MgO catalyst by chemical vapor deposition of methane

The selective synthesis of single-walled carbon nanotubes (SWCNTs) with narrow chirality and diameter distribution by methane decomposition over Fe–MgO catalyst is reported. The catalyst was examined by nitrogen physisorption, X-ray diffraction, temperature programmed reduction, X-ray photoelectron spectroscopy, and UV–Vis diffuse reflectance spectroscopy to elucidate the structure and chemical state of the species responsible for SWCNT growth. High resolution electron microscopy, Raman and optical absorption spectroscopy, temperature programmed oxidation, energy dispersive X-ray spectroscopy and nitrogen physisorption were used to probe reaction selectivity, SWCNT chirality and diameter distribution, carbon yield and effectiveness of purification protocols. The yield of carbon increased with an increase in temperature, although SWCNTs selectivity decreased above the optimum synthesis temperature. Results established a clear link between the degree of dispersion of iron oxide species inside the MgO lattice and the catalyst selectivity for SWCNT growth.     

Characterization of dispersed hydroprocessing catalysts prepared in reversed micelles

Fe, Co and Ni particles were prepared in water/polyoxyethylene-4-laurylether/n-hexane and water/polyoxyethylene-4-laurylether/decahydronaphthalene microemulsions by reduction of metal nitrates dissolved in the water pools of the reversed micelles. The particles were mostly monodispersed with average diameters in the range 8 to 23 nm, as determined by dynamic light scattering (DLS). However, significantly smaller size estimates were obtained using transmission electron microscopy (TEM). The average DLS particle diameters increased with increased average diameter of the reversed micelles, and the diameter of the reversed micelles increased with an increase in the microemulsion water: surfactant ratio and metal ion concentration. The diameter of the reversed micelles was also dependent upon the metal dissolved in the water pool, increasing in the order Ni < Co < Fe. These trends are explained in terms of changes that occur to the microemulsion hydrophilic-lipophilic balance. Preparation of nickel and cobalt sulfides by sulfidation of the metal salt with H₂S at low temperature, yielded much larger diameter particles (average diameter 75 nm). Measurement of the activity of the sulfided catalysts showed that the Co catalyst was more active than the Ni catalyst for the hydrocracking of diphenylmethane, and Co was more effective than Fe in reducing coke yield during Cold Lake residue hydroprocessing.     

On-substrate growth of single-walled carbon nanotube networks by an “all-laser” processing route

We report on the process latitude of an “all-laser” approach for the controlled growth of single-walled-carbon-nanotube (SWCNT) mats at predefined locations on silicon substrates. Unlike the conventional laser ablation methods where the SWCNTs are produced in the soot form, from the concomitant ablation of a graphite target loaded with metal catalyst, the “all-laser” process proceeds in two consecutive and independent steps. Indeed, the same KrF pulsed laser is first used to deposit at room temperature, the Co/Ni catalyst nanoparticles (NPs) onto the substrates – of which size and surface density can be controlled by adjusting the number of laser ablation pulses – and subsequently to grow SWCNTs onto the Co/Ni NPs sites, from the laser ablation of a pure graphite target. The grown SWCNT networks are shown to be fairly controllable by choosing the appropriate ratio of “graphite to Co/Ni-NPs” laser ablation pulses. The Co/Ni NPs and the grown SWCNTs were systematically characterized by atomic force microscopy, scanning/tunnelling electron microscopy, Raman spectroscopy and thermogravimetry analysis, and their potential as an active material in thin film transistor was evaluated. Obtained characterization data have led to identify key growth parameters of this novel approach, and to propose growth mechanism models that best describe our observations.     

Multiple “optimum” conditions for Co-Mo catalyzed growth of vertically aligned single-walled carbon nanotube forests

Carbon nanotubes (CNTs) were grown directly on substrates by alcohol catalytic chemical vapor deposition using a Co-Mo binary catalyst. Optimum catalytic and reaction conditions were investigated using a combinatorial catalyst library. High catalytic activity areas on the substrate were identified by mapping the CNT yield against the orthogonal gradient thickness profiles of Co and Mo. The location of these areas shifted with changes in reaction temperature, ethanol pressure and ethanol flow rate. Vertically aligned single-walled CNT (SWCNT) forests grew in several areas to a maximum height of ca. 30 μm in 10 min. A pure Co catalyst yielded a vertically aligned SWCNT forest with a bimodal diameter distribution. The effects of Mo on the formation of catalyst nanoparticles and on the diameter distribution of SWCNTs are discussed and Mo as thin as a monolayer or thinner was found to suppress the broadening of SWCNT diameter distributions.     

LaCoO3 ceramics obtained from reactive powders

The aim of the present study was to establishing the correlation between the structure and properties of the LaCoO₃ powders obtained by aqueous sol–gel method with citric acid and their sintering behavior in order to obtain fully densified ceramics with perovskite structure. Two types of cobalt and lanthanum reagents were used in synthesis, namely nitrates and acetates. The sintering was realized at temperatures ranging between 800 and 1200 °C for 2 h. The sintered samples were investigated by classical ceramic methods (shrinkage, density, porosity) and by structural and morphological investigations: XRD, SEM, AFM and XPS. The electrical properties of the samples were determined by impedance spectroscopy. The ceramics obtained with powders starting with acetates have presented a lower sintering ability as compared with the samples obtained from powders starting with nitrates. LaCoO₃ ceramics with best properties was obtained from powders starting with nitrates sintered at 1100 °C.     

Growth of single-walled carbon nanotubes with controlled diameters and lengths by an aerosol method

On the basis of combined study of the transmission electron microscopy, scanning electron microscopy, Raman spectroscopy and ultraviolet–visible–near infrared absorption spectroscopy, the properties of the single-walled carbon nanotubes (SWCNTs), synthesized by aerosol (floating catalyst) chemical vapor deposition method by ferrocene vapor decomposition in the presence of carbon monoxide, are studied in details. The results show that increasing the temperature gives rise to the formation of high quality and large diameter SWCNTs. By monitoring the water-cooled probe position, both the bundle length and the diameter of the SWCNTs are effectively tuned due to the variation of the residence time and temperature profile in the reactor. An introduction of a small amount of CO₂ suppresses the growth of small diameter nanotubes and enlarges the mean diameter of SWCNT samples. The mean diameter of SWCNTs could be easily altered in a broad range from 1.1 to 1.9 nm during growth, which is essential for the SWCNT applications in optical and electronic devices.     

The electrochemical behaviour of cobalt in alkaline nitrate melts at different temperatures

The electrochemical behaviour of cobalt in molten alkali nitrates in the temperature range from 141 to 321°C has been investigated. At lower temperatures the metal dissolves as Co(II); the oxidation product at higher temperatures is Co₃O₄. Nitrogen oxides are also formed. Passivation and localized corrosion occur under definite anode potential, Co(II) concentration and temperature conditions. These effects have been studied by non-stationary measurements. Co(II) dissolved in the melt can be electrodeposited either on cobalt or platinum cathodes.     

Decomposition of metal carbides as an elementary step of carbon nanotube synthesis

The role of catalyst components in catalysts containing molybdenum, Mo/M/MgO (MNi, Co, and Fe), as well as Mo-free catalysts, M/MgO (MNi, Co, and Fe), for carbon nanotube (CNT) synthesis have been investigated by TEM, XRD, and Raman spectroscopy. CNT synthesis by the catalytic decomposition of CH₄ over M/MgO catalysts can proceed at reaction temperatures higher than the decomposition temperature of the metal carbides (Ni₃C, Co₂C, and Fe₃C), which indicates that carbon in the CNT originates from the graphitic carbon formed on the catalyst surface by the decomposition of metal carbides. For all catalysts containing Mo, thin CNT formation starts at an identical temperature of 923 K, corresponding to the decomposition temperature of MoC_1−x into Mo₂C. The significant effect of the addition of Mo is concerned with the formation of Mo₂C in a catalyst particle during CNT synthesis at high reaction temperatures. The presence of a stable Mo₂C phase leads to the formation of thin CNT with better crystallinity at high reaction temperatures. The role of Ni, Co, and Fe in the Mo/M/MgO catalysts is ascribed to the dissociation of CH₄.     

Aniline hydrogenolysis on nickel: effects of surface hydrogen and surface structure

Fluorescence yield near-edge spectroscopy (FYNES) above the carbon K edge and temperature programmed reaction spectroscopy (TPRS) have been used as the methods for characterizing the reactivity and structure of adsorbed aniline and aniline derived species on the Ni(100) and Ni(111) surfaces over an extended range of temperatures and hydrogen pressures. The Ni(100) surface shows appreciably higher hydrogenolysis activity towards adsorbed aniline than the Ni(111) surface. Hydrogenolysis of aniline on the Ni(100) surface results in benzene formation at 470 K, both in reactive hydrogen atmospheres and in vacuum. External hydrogen significantly enhances the hydrogenolysis activity for aniline on the Ni(100) surface. Based on spectroscopic evidence, we believe that the dominant aniline hydrogenolysis reaction is preceded by partial hydrogenation of the aromatic ring of aniline in the presence of 0.001 Torr of external hydrogen on the (100) surface. In contrast, very little adsorbed aniline undergoes hydrogen induced C-N bond activation on the Ni(111) surface for hydrogen pressures as high as 10^–7 Torr below 500 K. Thermal dehydrogenation of aniline dominates with increasing temperature on the Ni(111) surface, resulting in the formation of a previously observed polymeric layer which is stable up to 820 K. Aniline is adsorbed at a smaller angle relative to the Ni(111) surface than the Ni(100) surface at temperatures below the hydrogenolysis temperature. We believe that the proximity and strong -interaction between the aromatic ring of the aniline and the surface is one major factor which controls the competition between dehydrogenation and hydrogen addition. In this case the result is a substantial enhancement of aniline dehydrogenation relative to hydrogenation on the Ni(111) surface.     

Spray coating as a simple method to prepare catalyst for growth of diameter-tunable single-walled carbon nanotubes

Spray coating is proposed as an optional wet method for preparing nano-sized particles suitable for the growth of single-walled carbon nanotubes (SWCNTs). The obtained SWCNT films are characterized by Raman spectroscopy and electron microscopy, and are confirmed to be comparable to SWCNTs produced by the conventional dip-coating process in terms of crystallinity, tube diameter and carbon yield. The mean diameter of SWCNTs can be effectively reduced from 1.85 to 1.35 nm by prolonging the deposition of Mo. In addition, spray coating allows catalyst preparation on supports other than flat wafers, as demonstrated by the synthesis of high-quality SWCNTs on Al₂O₃ fiber and quartz wool supports.     

Optical absorption response of chemically modified single-walled carbon nanotubes upon ultracentrifugation in various dispersants

Arc discharge single-walled carbon nanotubes (SWCNTs) were modified through different oxidative treatments and functionalization reactions. The modified SWCNT powders were dispersed in four different aqueous media and purified by ultracentrifugation. Extinction coefficients of the modified SWCNTs depended on the SWCNT type but did not depend on the dispersion medium. According to visible/near infrared spectroscopy, the purity of all the modified SWCNT dispersions substantially improved after ultracentrifugation; however, the spectrum profile, the degree of purity and the centrifugation yield were influenced by the SWCNT type, the surface functional groups and the dispersion medium. Semi-quantitative purity indexes calculated from optical absorption spectra were supported by transmission electron microscopy observations. Contents in metal impurities were analyzed by energy dispersive X-ray spectroscopy. SWCNT samples processed by oxidative acid treatments and ultracentrifugation showed metal contents of lower than 0.5 wt%.     

Carbothermal synthesis of zirconium diboride (ZrB2) whiskers

Abstract

In the present investigation, carbothermal synthesis technique is used for the production of ZrB₂ whiskers. The synthesis is carried out by heating the mixture of ZrB₂, H₃BO₃ and carbon black over the temperature range of 1300 to 1700°C in argon atmosphere. Different elements such as Ni, Co and Fe are tested for their role as catalysts. The synthesised powder contains ZrB₂ as the major phase with minor phases of ZrC and B₄C. Whisker yield is found to be low at lower temperatures (<1500°C) and then increases with the pyrolysis temperature. The Ni addition seems more effective as a catalyst than Co or Fe. Shorter length whiskers are found in the case of Co catalyst, whereas use of Fe catalyst shows whisker with rod shape and a special bird's nest type whiskers. The electron microscope study of whisker reveals the presence of various defects.     

Aluminum nitride‐single walled carbon nanotube nanocomposite with superior electrical and thermal conductivities

Development of aluminum nitride (AlN)‐single walled carbon nanotube (SWCNT) ceramic‐matrix composite containing 1‐6 vol% SWCNT by hot pressing has been reported in this article. The composites containing 6 vol% SWCNT are dense (~99% relative density) and show high dc electrical conductivity (200 Sm^?1) and thermal conductivity (62 Wm^?1K^?1) at room temperature. SWCNTs contain mostly metallic variety tubes obtained by controlled processing of the pristine tubes before incorporation into the ceramic matrix. Raman spectroscopy and field emission scanning electron microscopy (FESEM) of the fracture surface of the samples show the excellent survivability of the SWCNTs even after high‐temperature hot pressing. The results indicate the possibility of preparation of AlN nanocomposite for use in plasma devices and electromagnetic shielding.     

Catalytic synthesis of carbon nanotubes using Ni- and Co-doped calcium tartrates

Calcium tartrate doped with Ni and/or Co has been used as a catalyst source in the chemical vapor deposition synthesis of carbon nanotubes (CNTs). Thermolysis of doped calcium tartrate in an inert atmosphere was shown to yield Ni, Co or Ni-Co nanoparticles ∼6 nm in diameter dispersed in a calcium oxide matrix. The CNT synthesis was carried out by ethanol vapor decomposition at 800 °C. The structure of the products was characterized by transmission electron microscopy and Raman spectroscopy. It was found that Ni nanoparticles embedded in CaO provide the narrowest diameter distribution of CNTs, while the bimetallic Ni-Co catalyst allows the formation of the thinnest CNTs with the outer diameter of ∼2 nm. This type of CNT is more likely to be responsible for the lowest value of the turn-on field (∼1.8 V/μm) for the emission current detected for the latter sample.     

Parametric study of synthesis conditions in plasma-enhanced CVD of high-quality single-walled carbon nanotubes

High-quality single-walled carbon nanotubes (SWCNTs) have been synthesized from H₂-CH₄ mixtures on a MgO-supported bimetallic Mo/Co catalyst using microwave plasma-enhanced chemical vapor deposition (PECVD). Reaction parameters including temperature, H₂:CH₄ ratio, plasma power, and synthesis time have been examined to assess their influence on SWCNT synthesis. Raman spectroscopy and high-resolution field emission scanning electron microscopy reveal that the quality, selectivity, density and predominant diameter of SWCNTs depend on the varied synthesis parameters. Results of this study can be used to optimize SWCNT synthesis conditions and products and to improve understanding of the growth of SWCNTs by PECVD.     

Design of deicing reagents based on alkali and alkaline-earth metals and ammonium formates, acetates, and nitrates

Phase equilibria in binary, ternary, and quaternary water-salt systems containing sodium, potassium, magnesium, calcium, and ammonium nitrates, formates, and acetates have been studied in the temperature range of 0 to ?70°C, and polytherms of the fusion of ice have been plotted. A series of binary and ternary salt compositions that form low-temperature eutectics with ice, which are promising as deicing reagents, has been determined. The corrosion activity of the most promising compositions relative to metals and alloys, as well as cement concrete pavements, has been determined. Corrosion inhibitors have been chosen.