Easy synthesis of mesoporous carbon using nano-CaCO3 as template

Mesoporous carbon has been synthesized using nano-CaCO₃ as a template and sucrose as carbon precursor. It is shown that the CaCO₃/sucrose weight ratio has a marked effect on the porosity of the carbon. At a weight ratio of CaCO₃/sucrose of 1:1, the surface area of the carbon reaches 892 m² g⁻¹ and the pore size is around 45 nm. The carbon shows a capacitance of 155 F/g with excellent rate capability in 6 mol L⁻¹ KOH aqueous electrolytes.     

Magnetic properties of carbon nano-particles produced by a pulsed arc submerged in ethanol

Carbon powder was produced by a pulsed arc ignited between two carbon electrodes submerged in ethanol, and was comprised of both micro- and nano-particles. The measured magnetic properties of the mixed “raw” powder at 20 and 300 K were: saturation magnetization M_s ∼ 0.90-0.93 emu/g, residual magnetization M_r = 0.022 and 0.018 emu/g, and coercive force H_c = 11 and 8 Oe, respectively. The data lead to conclusion that the powder consisted of ferromagnetic particles with a critical temperature much higher than 300 K. Magnetic particles in solution were separated by means of bio-ferrography. It was found that the magnetically separated particles included chains of ∼30-50 nm diameter spheres, and nanotubes and nanorods with lengths of 50-250 nm and diameters of 20-30 nm. In contrast, the residual particles which passed through the bio-ferrograph consisted of 1 μm and larger micro-particles, and nano-particles without any definite shape.     

Cyclic CO2 capture behavior of KMnO4-doped CaO-based sorbent

This study examines the CO₂ capture behavior of KMnO₄-doped CaO-based sorbent during the multiple calcination/carbonation cycles. The cyclic carbonation behavior of CaCO₃ doped with KMnO₄ and the untreated CaCO₃ was investigated. The addition of KMnO₄ improves the cyclic carbonation rate of the sorbent above carbonation time of 257 s at each carbonation cycle. When the mass ratio of KMnO₄/CaCO₃ is about 0.5-0.8 wt.%, the sorbent can achieve an optimum carbonation conversion during the long-term cycles. The carbonation temperature of 660-710 °C is beneficial to cyclic carbonation of KMnO₄-doped CaCO₃. The addition of KMnO₄ improves the long-term performance of CaCO₃, resulting in directly measured conversion as high as 0.35 after 100 cycles, while the untreated CaCO₃ retains conversion less than 0.16 at the same reaction conditions. The addition of KMnO₄ decreases the surface area and pore volume of CaCO₃ after 1 cycle, but it maintains the surface area and pores between 26 nm and 175 nm of the sorbent during the multiple cycles. Calculation reveals that the addition of KMnO₄ improves the CO₂ capture efficiency significantly using a CaCO₃ calcination/carbonation cycle and decreases the amount of the fresh sorbent.     

Low-temperature solution synthesis of carbon nanoparticles, onions and nanoropes by the assembly of aromatic molecules

Graphitic carbon nanostructures were prepared in solution by two methods: solvothermal synthesis and hot injection. Small carbon nanoparticles with uniform diameters of 3-6 nm, carbon onion particles with larger diameters of 30-80 nm, and carbon nanoropes with a length of hundreds of nm and a width of 3-20 nm, were formed using commercial mesophase pitches as a carbon precursor through solution-phase synthesis below 200 °C. In the solvothermal synthesis, organic-organic assemblies of aromatic molecules from the pitches could be constrained into different stacking arrangements directed by varying the concentration of the block copolymer P123 template in toluene solution at 200 °C. In the hot injection method, when oleic acid was used as a solvent at 180 °C, the assemblies of the aromatic building blocks were controlled by varying the reaction time (5-30 min) or the concentration of H₂SO₄ catalyst (0.015-0.061 mol L⁻¹) in the nucleation and growth process.     

Synthesis of carbon nanotubes over gold nanoparticle supported catalysts

The synthesis of carbon nanotubes (CNTs) through the catalytic decomposition of acetylene was carried out over gold nanoparticles supported on SiO₂-Al₂O₃. Monodispersed gold nanoparticles with 1.3-1.8 nm in diameter were prepared by the liquid-phase reduction method with dodecanethiol as protective agent. The carbon products formed after acetylene decomposition consist of multi-walled carbon nanotubes with layered graphene sheets, carbon nanofilaments (CNFs), and carbon nanoparticles encapsulating gold particles. The observed CNTs have outer diameters of 13-25 nm under 850 °C. The influence of several reaction parameters, such as kind of carriers, reaction temperature, gas flow rate, was investigated to search for optimum reaction conditions. The CNTs were observed at a relatively low temperature (550 °C). The silica-alumina carrier showed higher activity for the formation of CNTs than others used in the screening test. With increasing temperature, the CNTs showed cured structures having thick diameters and inside compartments. When Au content on the support was over 5 wt.%, the gold nanoparticles coagulated to form large ones >20 nm in diameter and became encapsulated with graphene layers after decomposition of acetylene.     

Efficiency of C60 incorporation in and release from single-wall carbon nanotubes depending on their diameters

We show that the efficiency of incorporating C₆₀ in single-wall carbon nanotubes (SWCNTs) and that of the incorporated C₆₀’s release from the SWCNTs depend on the SWCNT diameter. Through transmission electron microscopy, we found that the C₆₀ incorporation efficiency reached its maximum at diameters of 1-2 nm, while the efficiency of C₆₀ release from SWCNTs in toluene was maximized at 3-5 nm. The difficulty of C₆₀ release from SWCNTs with diameters of 5-6 nm might reflect either the effective packing of C₆₀ inside SWCNTs or a flattened SWCNT structure. We occasionally observed C₆₀ molecules arranged in a line along the sidewall inside SWCNTs with large diameters/width (>7 nm), indicating that large diameter SWCNTs were sometimes flattened.     

Semi-quantitative study on the fabrication of densely packed and vertically aligned single-walled carbon nanotubes

This paper presents, for the first time, a semi-quantitative study on the production of densely packed and vertically aligned (DPVA) single-walled carbon nanotubes (SWNTs) from ultra-thin catalytic films. An up-to-date highest volume density (60-70 kg m⁻³) and the corresponding high surface density on the order of 10¹⁶ m⁻² of DPVA-SWNTs have been achieved by point-arc microwave plasma chemical vapor deposition. The precise thickness control of the sandwich-like catalytic nanostructure of 0.5 nm Al₂O₃/0.5 nm Fe/>5 nm Al₂O₃, developed by the authors, and a short-time (5 min) heat pretreatment of substrates at a temperature as low as 600 °C play the very key role in the process of fabricating DPVA-SWNTs.     

Selectively attaching Pt-nano-clusters to the open ends and defect sites on carbon nanotubes for electrochemical catalysis

Pt nano-clusters (nano-Pt) have been selectively attached to the open ends and defect sites of mildly oxidized multi-wall carbon nanotubes (MWCNTs) on a glassy carbon electrode (GCE) by a cyclic voltammetry (CV) electrodeposition method. The nano-Pt functionalized MWCNTs were characterized by XPS, XRD, FE-SEM and electrochemical techniques. The catalytic activity of the nano-Pt functionalized MWCNTs were tested by an oxygen reduction reaction (ORR) and a methanol oxidation reaction (MOR). Taking the ORR as an example, we found that the electrocatalytic activity of the nano-Pt functionalized MWCNTs can be well tuned by varying the cycle number and the PtCl₆²⁻ concentration of the deposition conditions. The average size of the nano-Pt was 123 nm, and it was constituted of nano-crystallite of an average size of 10.8 nm. Though the large nano-Pt particles (100-150 nm) were only attached on the open ends and defect sites of the MWCNTs, which were very different from the highly dispersed small Pt nanoparticles (<10 nm) on carbon nanotubes reported by other research groups. In our method, excellent electrocatalytic activity of the nano-Pt functionalized MWCNTs for ORR and MOR can be obtained. The mechanisms for nano-Pt deposition are proposed.     

Formation of carbon nanotubes through ethylene decomposition over supported Pt catalysts and silica-coated Pt catalysts

Ethylene decomposition was performed over supported Pt catalysts to fabricate composites of Pt metal nanoparticles and carbon nanotubes (CNTs). All supported Pt catalysts (Pt/carbon black, Pt/CNT, Pt/MgO, Pt/Al₂O₃ and Pt/SiO₂) showed catalytic activity for ethylene decomposition at 973 K to form CNTs. Pt metal particles were found at tips of CNTs. These results indicate that Pt metal particles have catalytic activity for growth of CNTs through hydrocarbon decomposition. A broad range (5-50 nm) of CNT diameters were formed from the use of supported Pt metal catalysts although Pt metal particles in the catalysts before ethylene decomposition were relatively uniform in size (2-5 nm). These results imply that Pt metal particles in the catalysts aggregated during ethylene decomposition at 973 K. Aggregation of Pt metal particles in catalysts during ethylene decomposition could be suppressed by covering catalysts with silica layers that were a few nanometers thick. Silica-coated Pt catalysts showed high activity for ethylene decomposition to form CNTs with uniform diameters (8-10 nm) despite the uniform coverage of Pt metal particles with silica layers.     

Growth and characteristics of carbon nanotubes obtained under different C2H2/H2/NH3 concentrations

Aligned carbon nanotubes were synthesized under a combination of 20 different C₂H₂/H₂/NH₃ compositions at 700 °C using a thermal chemical vapor deposition method. Thin film Fe was used as the catalyst, which was pretreated with H₂ or NH₃ prior to the growth of carbon nanotubes. The use of different pretreatment gases results in little difference in the growth and characteristics of the carbon nanotubes except that the carbon nanotubes grown on H₂ treated catalysts have smaller diameters. The growth rate of the CNTs does not depend on the NH₃ concentration but on the ratio of NH₃/C₂H₂. There is a critical NH₃/C₂H₂ ratio that is independent of the C₂H₂ concentration and at which the peak growth rate occurs. The critical value was found to be 4.7 ± 1.2. Microstructural analysis indicates that the carbon nanotubes obtained at higher NH₃ concentrations contain defects and disorder. Field emission tests show that the carbon nanotubes exhibit a turn-on field of 2.36 V/μm and a maximum current density of 1.91 mA/cm². The field emission properties were found to be stable after 15 test cycles.     

Combined catalyst system for preferential growth of few-walled carbon nanotubes

The effect of a combined catalyst system on the synthesis of carbon nanotubes (CNTs) from methane (CH₄) was investigated using molybdenum trioxide (MoO₃) as a conditioning catalyst and molybdenum-doped iron supported on magnesia as the main catalysts. Without the conditioning catalyst, only single-walled CNTs with diameters smaller than 2 nm were formed on the main catalyst. With the conditioning catalyst, double-walled CNTs and few-walled CNTs with larger hollow diameters than 2 nm were produced with much higher yields. The combination of the two kinds of Mo-containing catalyst would more effectively transform CH₄ into reactive species related to the early stage of nanotube formation on the main catalyst, resulting in the increase of the yield, diameter and layer number of the CNTs.     

Field emission properties of carbon nanotubes synthesized by capillary type atmospheric pressure plasma enhanced chemical vapor deposition at low temperature

Carbon nanotubes (CNTs) were grown using a modified atmospheric pressure plasma with NH₃(210 sccm)/N₂(100 sccm)/C₂H₂(150 sccm)/He(8 slm) at low substrate temperatures (?500 °C) and their physical and electrical characteristics were investigated as the application to field emission devices. The grown CNTs were multi-wall CNTs (at 450 °C, 15-25 layers of carbon sheets, inner diameter: 10-15 nm, outer diameter: 30-50 nm) and the increase of substrate temperature increased the CNT length and decreased the CNT diameter. The length and diameter of the CNTs grown for 8 min at 500 °C were 8 μm and 40 ± 5 nm, respectively. Also, the defects in the grown CNTs were also decreased with increasing the substrate temperature (The ratio of defect to graphite (I_D/I_G) measured by FT-Raman at 500 °C was 0.882). The turn-on electric field of the CNTs grown at 450 °C was 2.6 V/μm and the electric field at 1 mA/cm² was 3.5 V/μm.     

Synthesis and structural characterization of thin multi-walled carbon nanotubes with a partially facetted cross section by a floating reactant method

Here we describe synthesis of very unusual multi-walled carbon nanotubes through a catalytic chemical vapor deposition method using a floating reactant method and subsequent thermal treatment up to 2600 °C in a large quantity. Main characteristics of these nanotubes are (1) relatively wide distribution of diameters ranging from 20 to 70 nm and linear, long macro-morphology (aspect ratio >100), (2) highly straight and crystalline layers, (3) high purity through removal of metallic impurity, (4) very low interlayer spacing (0.3385 nm) and low R value (I_D/I_G = 0.0717), (5) high G′ intensity over intensity of G band (G′/G = 0.85) and strongly negative magnetoresistance value of −1.08% at 77 K and 1 T. The unusual microstructure of thin multi-walled carbon nanotubes with a partially facetted cross-sectional shape caused by thermal treatment is mainly ascribed to abrupt density changes (from 1.89 to 2.1 g/cm³) within a confined nanosized space, accompanying with the phase separation.     

Electrochemical synthesis of self-organized TiO2 nanotubular structures using an ionic liquid (BMIM-BF4)

We show that an ionic liquid consisting of imidazolium salt with a BF₄ counter ion (BMIM-BF₄) can directly be used to grow well-defined layers of self-organized TiO₂ nanotubes. For this a Ti metal substrate is anodized in this electrolyte for potential range between 3 V_Ag/AgCl and 10 V_Ag/AgCl without addition of free fluoride species (fluorides are used in all previous tube growth procedures). Key factors that influence the morphology and geometry of the resulting nanotubular layer are the anodic potential, the anodization time and particularly the water content in the ionic liquid. The resulting nanotubes layers have thickness in the range of approximately 300-650 nm; with individual tubes that have diameters between 27 nm and 43 nm.     

Efficient production of hydrogen and multi-walled carbon nanotubes from ethanol over Fe/Al2O3 catalysts

Fe/Al₂O₃ catalysts with different Fe loadings (10-90 mol%) were prepared by hydrothermal method. Ethanol decomposition was studied over these Fe/Al₂O₃ catalysts at temperatures between 500 and 800 °C to produce hydrogen and multi-walled carbon nanotubes (MWCNTs) at the same time. The results showed that the catalytic activity and stability of Fe/Al₂O₃ depended strongly on the Fe loading and reaction temperature. The Fe(30 mol%)/Al₂O₃ and Fe(40 mol%)/Al₂O₃ were both the effective catalyst for ethanol decomposition into hydrogen and MWCNTs at 600 °C. Several reaction pathways were proposed to explain ethanol decomposition to produce hydrogen and carbon (including nanotube) at the same time.     

Structural, electrical and magnetic properties of carbon-nickel composite thin films

Carbon-nickel composite thin films (600 nm thick) were prepared by dc magnetron sputtering of Ni and C at several temperatures (25-800 °C) on oxidized silicon substrates. By transmission electron microscopy it was found that the composite consisted of Ni (or Ni₃C) nanoparticles embedded in a carbon matrix. The metallic nanoparticles were shaped in the form of globular grains or nanowires (of the aspect ratio as high as 1:60 in the sample prepared at 200 °C). The carbon matrix was amorphous, or graphite-like depending on deposition temperature. At low deposition temperatures T_S (25-400 °C) the Ni₃C nanoparticles were of hcp phase. Samples prepared at T_S ? 600 °C contained ferromagnetic fcc Ni nanoparticles. A correlation was found between the structural, electrical and magnetic properties of the composites. To characterise the films, dependences, such as resistivity vs. temperature, current vs. voltage, differential conductivity vs. bias voltage, and magnetoresistivity, were determined. For example, the tunneling effect was found in samples in which the metallic nanoparticles were separated by 2-3 nm thick amorphous carbon. When the metallic nanoparticles were connected by graphite-like carbon regions (having a metallic conductivity, in contrast to a-C), the temperature coefficient of the resistivity became slightly positive. An anisotropic magnetoresistivity of ∼0.1% was found in the sample that contained ferromagnetic columnar fcc Ni. Zero magnetoresistivity was found in the sample in which the metallic nanoparticles were of non-magnetic hcp phase.     

Ruthenium oxide/carbon composites with microporous or mesoporous carbon as support and prepared by two procedures. A comparative study as supercapacitor electrodes

Composites are prepared by deposition of nanoparticles of RuO₂·xH₂O (1-4 nm) on two carbons: microporous carbon (1.3 nm of average micropore size) and mesoporous carbon (11 nm of average mesopore size). Two-preparation procedures are used: (i) procedure A consisting of repetitive impregnations of the carbons with RuCl₃·0.5H₂O solutions, and (ii) procedure B based on impregnation of the carbons with Ru(acac)₃ vapour. The procedure B leads to supported RuO₂·xH₂O particles that appear more crystalline than those obtained by the procedure A. Specific capacitance and specific surface area of the composites are discussed as functions of the RuO₂ content, and different dependences for the composites derived from the two carbons are found. Mesoporous carbon is better support than microporous carbon. Procedure A leads to supported RuO₂·xH₂O particles with higher specific capacitance than the particles deposited by procedure B.     

Synthesis of self-organized mixed oxide nanotubes by sonoelectrochemical anodization of Ti-8Mn alloy

Self ordered arrays of titanium manganese mixed oxide nanotubes were prepared by anodization of Ti8Mn alloy (UNS R56080) under ultrasonication in diluted ethylene glycol containing fluoride. The dimensions of the nanotubes (diameter: 20-100 nm and length: 0.5-2.0 μm) could be tuned by changing the synthesis parameters. The as-anodized nanotubes showed a stoichiometry of (Ti,Mn)O₂. Upon annealing at 500 °C in oxygen atmosphere, the nanotubes contained a mixture of anatase + rutile phases of TiO₂ and Mn₂O₃. The composition of the oxide nanotubes was influenced by the chemistry of the phases present in the alloy. More manganese content was observed in the oxide formed on the β-phase than in the oxide layer of α-phase. Anodization in the ultrasonic field increased the kinetics of nanotubular oxide formation and resulted in homogeneous ordering of the nanotubular arrays as compared to the anodization by conventional stirring in the fluoride containing ethylene glycol solution. Whereas, anodization in aqueous acidified fluoride solutions resulted in severe attack of the β-phase and did not show presence of nanotubular oxide structure.     

Controlled synthesis of carbon nanocables and branched-nanobelts

Two kinds of new morphology of carbon nanomaterials, carbon nanocables and branched-nanobelts can been produced by pyrolyzing ethylene glycol monvethyl ether (CH₃CH₂OCH₂CH₂OH) with Fe as catalyst at 650-700 °C. The carbon nanocables are made of two parts, the interior carbon nanowires encapsulated in the outer carbon nanotubes. For the nanocables, HRTEM images reveal that the crystallinity of the outer carbon nanotubes is better than that of the interior carbon nanowires. HRTEM image shows that the junctions of the branched-nanobelts are composed of graphitic layers that are almost perpendicular to the respective axis of the branched-nanobelts. The catalysts, temperature and reaction time were investigated. The possible growth mechanism for the as-synthesized carbon structures is discussed.