Preparation and characterization of porous carbon beads and their application in dispersing small metal crystallites

Porous carbon beads were prepared by the pyrolysis of poly(vinylidene chloride) beads that were synthesized by suspension polymerization. After prolysis treatment at 180–300 °C under argon stream, the polymeric beads were further carbonized at 1000 °C for 3 h under argon stream to acquire porous carbon beads, of which the specific surface area was about 1000 m²/g, and pore size was mainly in the width range of 0.8–1.2 nm. The carbon structure and surface chemical composition characterized by X-ray diffraction and X-ray photoelectron spectroscopy, depended on the preparation temperature and the relations between them were examined. The characterization of the carbon beads by scanning electron microscopy, atomic force microscopy presented the morphological structure of the carbon beads surface and a global view of pores. The dispersion of nickel crystallites on the carbon beads surface was characterized by electron microprobe analysis. This study reveals that uniform surface morphological structure leads to the fine dispersion of metal crystallites.     

Carbon nanotubes prepared from three-layered copolymer microspheres of acrylonitrile and methylmethacrylate

Carbon nanotubes (CNTs) were synthesized from fine three-layered copolymer microspheres using the polymer blend technique. Diameter of PMMA core/Poly(AN-co-MMA) shell-1/PMMA shell-2 microspheres, prepared by a radical soap-free emulsion polymerization of methylmethacrylate (MMA) and acrylonitrile (AN), was between 400 nm and 500 nm. Microspheres were subjected to melt-spinning at 305 °C, stabilizing in oxygen at 220 °C for 4 h, and finally carbonizing at 1000 °C for 30 min. FE-SEM study of carbonized sample revealed the presence of CNTs arrays on carbon blocks. Similar arrays were observed in a comparative CNTs sample prepared from three-layered microspheres with the pure PAN shells-1 layers. HRTEM showed that the CNTs derived from copolymer microspheres had different structure when compared to the control sample, i.e. CNTs often adhered to each other and contained the internal compartments. The insufficient PMMA shell-2 coating of copolymer microspheres is believed to be a reason for CNTs adhesion. The possible mechanisms of the carbon block formation and the adhesion of CNTs are introduced.     

Carbon membranes from cellulose and metal loaded cellulose

The focus of this work was to find a low-cost precursor for carbon molecular sieve (CMS) membranes, and a simple way of producing them. In addition, several ways of modifying a carbon material are described. The modification method used in this study was metal doping of carbon. CMS membranes were formed by vacuum carbonization of cellulose and metal loaded cellulose. Metal additives include oxides of Ca, Mg, Fe(III) and Si, and nitrates of Ag, Cu and Fe(III).The carbon membrane containing Fe-nitrate has promising separation performance for the gas pairs O₂/N₂ and CO₂/CH₄. Carbon containing nitrates of Cu or Ag show high selectivity, but reduced O₂ and CO₂ permeability compared to carbon with Fe-nitrate. Element analysis indicates that Cu migrates to the carbon surface, creating an extra layer resistance to gas transport. A silver mirror is also seen on the surface of Ag-nitrate-containing carbon. However, the Ag- and Cu-containing membranes show a high H₂ permeability. Adding metal oxides makes the carbon membranes retard the transport of easily condensable gases (e.g. CO₂). This can be exploited for enhanced H₂/CO₂ separation efficiency.     

Microporous carbons prepared from cationic surfactant-resorcinol/formaldehyde composites

Microporous carbons have been synthesized by the carbonization of cationic surfactant-resorcinol/formaldehyde (RF) composites, which were themselves formed by electrostatic organic-organic interaction. The porous structure produced by the decomposition of the surfactant plays an important role for the gasification of the RF polymer at higher temperatures. The pore size of the carbon prepared from tetrapropylammonium bromide (TPAB)-RF, cetyltrimethylammonium bromide (C₁₆TAB)-RF and decyltrimethylammonium bromide (C₁₀TAB)-RF mixtures can be estimated as 0.53 nm from the Horvath-Kawazoe method using N₂ adsorption isotherms. Their pore size distributions were very narrow, showing that the microporous carbons derived from surfactant-RF mixture may have promise as adsorbents and membrane materials.     

Changes in pore properties of phenol formaldehyde-based carbon with carbonization and oxidation conditions

Porous carbon beads were prepared by carbonizing at 700 and 1000 °C under N₂ (NN-series) or CO₂ atmospheres (CO-series) and a subsequent oxidization with boiling nitric acid solution (13%, v/v) for 3 h (ANN- and ACO-series). BET surface area of both CO- and NN-series samples tends to increase with increasing carbonization temperature, but CO-series samples show higher BET surface areas (700 °C: 610 m²/g, 1000 °C: 780 m²/g) compared with those of NN-series samples (700 °C: 380 m²/g, 1000 °C: 580 m²/g). After acid oxidation, BET surface areas of NN-series samples increased from 580 to 650 m²/g, whereas those of CO-series samples decreased from 780 to 600 m²/g. On subsequent acid oxidation, acidic surface functional groups increased in both CO- and NN-series samples, but the CO-series samples tend to have much more acidic surface functional groups. Adsorption of halogenated methanes, such as tetra-, tri- and dichloromethanes, onto the samples of CO-, NN-, ACO- and ANN-series was thought to be driven initially by the basicity, but the acidic functional groups that could attract adsorbates via dipole-dipole interaction might hinder the adsorption of subsequently incoming adsorbates.     

Evolution of chemistry and morphology during the carbonization and combustion of rice husk

Both fine carbon/silica and pure silica powders can be obtained by carbonization and combustion of rice husk under non-isothermal conditions, and the products can be used for preparation of high-quality ceramic materials. Studies on the morphology, chemical and physical characteristics of products were carried out by N₂-adsorptionmeter, SEM, XRD, FTIR, ICP-MS and EA. Results indicate that decreasing the heating rate increased the specific surface area, pore volume and pore diameter. At a heating rate of 5 °C/min, the specific surface areas of both the carbon/silica and pure silica powders were 261 and 235 m²/g, and the average pore diameters were 2.2 and 5.4 nm, respectively. The products obtained from various heating rates were all amorphous. Thermogravimetric analysis was employed to study the reaction characteristics during carbonization or combustion, indicating that decomposition process of rice husk could be divided into three temperature zones. This results of the study can also provide the important information on the recovery of biomass material from rice husk.     

Carbonization and graphitization

A review is made of recent electron microscope observations relating to the carbonization and graphitization of a variety of carbonaceous precursors. The different behaviors of graphitizing and non-graphitizing carbons are elucidated, and the effect of sulphur as a cross-linker is determined. The resulting processes are shown to apply to a wide variety of materials ranging from cokes to carbon fibers.     

Preparation of porous carbons from thermoplastic precursors and their performance for electric double layer capacitors

Porous carbons with high surface area were successfully prepared from thermoplastic precursors, such as poly(vinyl alcohol) (PVA), hydroxyl propyl cellulose and poly(ethylene terephthalate), by the carbonization of a mixture with MgO at 900 °C in an inert atmosphere. After carbonization the MgO was dissolved out using a diluted sulfuric acid and the carbons formed were isolated. The mixing of the PVA carbon precursor with the MgO precursors (reagent grade MgO, magnesium acetate or citrate) was done either in powder form or in an aqueous solution. The BET surface area of the carbons obtained via solution mixing could reach a very high value, such as 2000 m²/g, without any activation process. The pore structure of the resultant carbons was found to depend strongly on the mixing method; the carbons prepared via solution mixing were rich in mesopores, but those produced via powder mixing were rich in micropores. The size of mesopores was found to be almost the same as that of the MgO particles, suggesting a way of controlling the mesopore size in the resultant carbons. Measurement of capacitance was carried out in 1 mol/L H₂SO₄ electrolyte. The porous carbon with a BET surface area of 1900 m²/g prepared at 900 °C through solution mixing of Mg acetate with PVA showed a fairly high EDLC capacitance, about 250 F/g with a current density of 20 mA/g and 210 F/g with 1000 mA/g. The rate performance was closely related to the mesoporous surface area.