Activation of coal tar derived needle coke with K2CO3 into an active carbon of low surface area and its performance as unique electrode of electric double-layer capacitor

Raw needle coke from coal tar pitch was activated with K₂CO₃ at a coke:carbonate weight ratio of 1:4, to prepare an electrode for an electric double-layer capacitor (EDLC). Although the surface area of the coke activated at 900 °C for 3 h was as small as 20 m²/g, with a very high yield, the coke achieved capacitances per weight and volume of 20 F/g and 20 F/ml, respectively, in the two-electrode system, by charging at 2.7 V. The surface area of KOH-activated coke with a similar ratio (coke:hydroxide = 1:4, wt:wt) was over 2300 m²/g, and it exhibited capacitance per weight and volume values of 42 F/g and 17 F/ml, respectively. The coke activated by K₂CO₃ was found to be further activated by the charging. This electrochemical activation, which has been reported as activation in an electric field, was investigated by cyclic voltammetry in order to clarify it. The graphitic and pore structures of the coke after the electrochemical activation were analyzed by XRD to confirm retention of the graphene structure. Xe-NMR showed that the formation of small new pores was induced in the cathode material, increasing the surface area from 6 m²/g to 18 m²/g before use, although the pore volume was around 0.015-0.017 m³/g both before and after the charging. This activation with K₂CO₃ and a deeper understanding of the activation on charging suggest future directions for the preparation of electrode carbon for EDLCs.     

Preparation of activated carbon derived from Jatropha curcas fruit shell by simple thermo-chemical activation and characterization of their physico-chemical properties

High surface area activated carbons were prepared by simple thermo-chemical activation of Jatropha curcas fruit shell with NaOH as a chemical activating agent. The effects of the preparation variables, which were impregnation ratio (NaOH:char), activation temperature and activation time, on the adsorption capacity of iodine and methylene blue solution were investigated. The activated carbon which had the highest iodine and methylene blue numbers was obtained by these conditions as follows: 4:1 (w/w) NaOH to char ratio, 800 °C activation temperature and 120 min activation time. Characterization of the activated carbon obtained was performed by using scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and nitrogen adsorption isotherm as BET. The results present that the activated carbon possesses a large apparent surface area (S_BET = 1873 m²/g) and high total pore volume (1.312 cm³/g) with average pore size diameter of 28.0 Å.     

Preparation of granular activated carbon from oil palm shell by microwave-induced chemical activation: Optimisation using surface response methodology

In this study, waste palm shell was used to produce activated carbon (AC) using microwave radiation and zinc chloride as a chemical agent. The operating parameters of the preparation process were optimised by a combination of response surface methodology (RSM) and central composite design (CCD). The influence of the four major parameters, namely, microwave power, activation time, chemical impregnation ratio and particle size, on methylene blue (MB) adsorption capacity and AC yield were investigated. Based on the analysis of variance, microwave power and microwave radiation time were identified as the most influential factors for AC yield and MB adsorption capacity, respectively. The optimum preparation conditions are a microwave power of 1200 W, an activation time of 15 min, a ZnCl₂ impregnation ratio of 1.65 (g Zn/g precursor) and a particle size of 2 mm. The prepared AC under the optimised condition had a BET surface area (S_BET) of 1253.5 m²/g with a total pore volume (V_tot) of 0.83 cm³/g, which 56% of it was contributed to the micropore volume (V_mic).     

Preparation of polystyrene-based activated carbon spheres with high surface area and their adsorption to dibenzothiophene

Polystyrene-based activated carbon spheres (PACS_K) with high surface area were prepared through KOH activation. Effects of the carbonization temperature and the ratio of KOH to carbon spheres (CS) on the textural structure, hardness and yield of the resultant PACS_K were studied, and their adsorption to dibenzothiophene (DBT) were investigated. The as-prepared PACS_K exhibited a high surface area (up to 2022 m²/g), large total pore volume (≥ 0.78 cm³/g), superior mechanical hardness and high adsorption capacity (ca. 153 mg/g). With the increase of the KOH/CS ratio from 2:1 to 4:1, the surface area, total pore volume, volume of micropores, and volume of mesopores, increase, whereas the volume of small-micropores (< 0.8 nm) decreases from 0.36 to 0.31 cm³/g. The adsorption capacity has a good linear correlation with the volume of small-micropores rather than the surface area. In addition, the large quantity of acidic oxygen-containing groups of PACS_K may also be responsible for their higher adsorption capacity and selectivity of DBT. The PACS_K saturated by DBT can be regenerated by a washing process in a shaking bath or using ultrasonic with toluene at 80 °C.     

Hierarchical porous carbons with controlled micropores and mesopores for supercapacitor electrode materials

Various porous carbons were prepared by CO₂ activation of ordered mesoporous carbons and used as electrode materials for supercapacitor. The structures were characterized by using X-ray diffraction, transmission electron microscopy and nitrogen sorption at 77 K. The effects of CO₂ treatment on their pore structures were discussed. Compared to the pristine mesoporous carbons, the samples subjected to CO₂ treatment exhibited remarkable improvement in textural properties. The electrochemical measurement in 6 M KOH electrolyte showed that CO₂ activation leads to better capacitive performances. The carbon CS15A6, which was obtained after CO₂ treatment for 6 h at 950 °C using CMK-3 as the precursor, showed the best electrochemical behavior with a specific gravimetric capacitance of 223 F/g and volumetric capacitance of 54 F/cm³ at a scan rate of 2 mV/s and 73% retained ratio at 50 mV/s. The good capacitive behavior of CS15A6 may be attributed to the hierarchical pore structure (abundant micropores and interconnected mesopores with the size of 3-4 nm), high surface area (2749 m²/g), large pore volume (2.09 cm³/g), as well as well-balanced microporosity and mesoporosity.     

Preparation of a highly microporous carbon from a carpet material and its application as CO2 sorbent

In order to increase the use of carpet wastes (pre- and/or post-consumer wastes), this work studies for the first time the preparation and characterisation of a microporous material from a commercial carpet (pile fiber content: 80% wool/20% nylon; primary and secondary backings: woven polypropylene; binder: polyethylene) and its application for CO₂ capture. The porous material was prepared from an entire carpet material using a standard chemical activation with KOH and then, characterised in terms of their porous structure and surface functional groups. Adsorption of CO₂ was studied using a thermogravimetric analyser at several temperatures (25-100 °C) and under different CO₂ partial pressures (i.e. pure CO₂ flow and a ternary mixture of 15% CO₂, 5% O₂ and 80% N₂). In order to examine the adsorbent regenerability, multiple CO₂ adsorption/desorption cycles were also carried out. The surface area and micropore volume of the porous adsorbent were found to be 1910.17 m² g^− 1 and 0.85 cm³ g^− 1, respectively. The CO₂ adsorption profiles illustrate that the maximum CO₂ capture on the sample was reached in less than 10 min. CO₂ adsorption capacities up to 8.41 wt.% and 3.37 wt.% were achieved at 25 and 70 °C, respectively. Thermal swing regeneration studies showed that the prepared adsorbent has good cyclic regeneration capacities.     

Microwave-hydrothermal synthesis of extremely high specific surface area anatase for decomposing NOx

Apparently C-doped and undoped or pure nanoparticles of anatase were synthesized using a microwave hydrothermal process in the temperature range of 140–180 °C for 1 h from several Ti precursors, such as Ti ethoxide, Ti isopropoxide and Ti oxysulfate. Nanoparticles of anatase samples were characterized by powder X-ray diffraction, transmission electron microscopy (TEM) and photocatalytic activity measurements. Results showed that nanoparticles in the size range of 4–17 nm of anatase were obtained in all cases with surface areas in the range of 151–267 m²/g. The photocatalytic activity of the prepared titanias was measured using methylene blue (MB) and NO_x molecules. Because MB has very strong adsorption on the samples, photocatalytic degradation under either solar light or black light irradiation was found to be very limited. However, the DeNO_x abilities of carbon-doped titanias were higher than those of Degussa P25 commercial titania sample and undoped or pure titanias especially under irradiation by long wavelength or visible light (>500 nm).     

Production and adsorption characteristics of MAXSORB: High-surface-area active carbon

High-surface-area (over 3000 m² g⁻¹) active carbon has been developed with an extremely large adsorption capacity. Various kinds of petroleum coke were mixed with an excess amount of KOH and dehydrated at 400°C, followed by activation at 600–900°C in an inert atmosphere. The remaining KOH was removed by washing with water after the activation. Pore analysis indicated that this active carbon has a large portion of mesopores (1.0–1.5 ml g⁻¹) with radii between 10 and 20 Å, whereas micropores are as numerous as in conventional steam activated carbon (0.5 ml g⁻¹). Since considerable amounts of K₂CO₃ and hydrogen were formed, the majority of the carbon consumption was due to the transformation of K₂O into K₂CO₃ by CO₂. Potassium metal was also formed from the hydroxide by dehydration and reduction by hydrogen or carbon. Reversible adsorption of gasoline vapour, and isotherms of methylene blue and iodine in solution were obtained. Regardless of the kind of adsorbent tested, the adsorption capacity increased proportionally to the BET surface area. The fact that the surface area exceeds the geometric maximum was explained by introducing the concept of associated adsorption. This product is now commercially available from our company under the brand name of MAXSORB.     

Soot surface area evolution during air oxidation as evaluated by small angle X-ray scattering and CO2 adsorption

The total surface area of two diesel engine produced soots, a high volatile content NIST standard (termed NIST) and a low volatile content soot (termed NEU), were determined with CO₂ adsorption and small angle X-ray scattering (SAXS), as a function of the extent of oxidation. During initial volatilization of condensables of the NIST and NEU soots in a thermogravimetric analyzer, in helium at 1073 K, their CO₂ surface areas increased sharply from 49 m²/g to 273 m²/g and from 96 m²/g to 367 m²/g, respectively. During oxidation, the CO₂ surface area increased by an additional 100-150 m²/g, until 50% conversion was reached. Thereafter, the CO₂ surface area was relatively constant with conversion for the NIST soot, but decreased to 150 m²/g for the NEU soot. Three porosity regimes were assumed for the calculation of SAXS areas; they were based on (a) constant density (shrinking core), (b) constant diameter, and (c) an observed (with a TEM) diameter variation. The best agreement between the CO₂ and SAXS surfaces area occurred for the constant density assumption, in contrast to the actual measured diameter variation. By applying fractal surface analysis to the SAXS data, this discrepancy is ascribed to the opening up of internal volume to reaction volatilization of condensables and oxidation.     

Process optimization of K2C2O4-activated carbon from kenaf core using Box–Behnken design

Potassium oxalate was evaluated as a new activating agent for preparation of kenaf core-based activated carbons. The preparation conditions were optimized through Box–Behnken design (BBD) to maximize I₂ and methylene blue (MB) adsorption values. Two quadratic models were developed to correlate the preparation variables namely activation temperature, impregnation ratio and activation time for both responses. The activated carbon produced at the optimum combination of process parameters showed 1161 mg/g and 330 mg/g of I₂ and MB uptakes, which were in excellent agreement with the predicted values from the models. Porosity parameters and scanning electron microscopy were used to investigate the obtained optimal sample. The results reveal that K₂C₂O₄ could be recommended as a promising effective activating agent for producing activated carbons from kenaf core with high surface area and potentially desirable dye removal capacity.     

New acrylic monolithic carbon molecular sieves for O2/N2 and CO2/CH4 separations

The modification of activated carbon fibres prepared from a commercial textile acrylic fibre into materials with monolithic shape using phenolic resin as binder was studied. The molecular sieving properties for the gas separations CO₂/CH₄ and O₂/N₂ were evaluated from the gas uptake volume and selectivity at 100 s contact time taken from the kinetic adsorption curves of the individual gases. The pseudo-first order rate constant was also determined by the application of the LDF model. The samples produced show high CO₂ and O₂ rates of adsorption, in the range 3-35 × 10⁻³ s⁻¹, and in most cases null or very low adsorption of CH₄ and N₂ which make them very promising samples to use in PSA systems, or similar. Although the selectivity was very high, the adsorption capacity was low in certain cases. However, the gas uptake in two samples reached 23 cm³ g⁻¹ for CO₂ and 5 cm³ g⁻¹ for O₂, which can be considered very good. The materials were heat-treated using a microwave furnace, which is a novel and more economic method, when compared with conventional furnaces, to improve the molecular sieves properties.     

Methylene blue adsorption by chemically activated waste pork bones

Bone is an inorganic template containing organic material inside which can be converted into hydroxyapatite‐rich material by pyrolysis. Nowadays, there is a growing research interest in the use of hydroxyapatite, the chemical formula of which is Ca₁₀(PO₄)₆(OH)₂. In the present work, pork bone, an abundant biomass source and food waste, has been converted into structured porous hydroxyapatite by a three‐step process including precharring under mild conditions, chemical activation, and thermal activation. The investigated activating agents were NaOH, KOH, K₂CO₃, H₂SO₄, and H₃PO₄. A thorough investigation of the influence of different activating protocols on the chemical and textural properties of the produced material was carried out by nitrogen adsorption–desorption at 77 K, potentiometric titrations, Fourier transform infrared, and X‐ray diffraction techniques. Chemical activation with NaOH, K₂CO₃, and H₂SO₄ increased the specific surface area up to 53%. H₃PO₄ reduced both surface area and pore volume, and KOH showed little influence on the pore structure. The produced materials were evaluated by methylene blue adsorption tests and showed significant improvement as a result of chemical activation. As a main effect, acid treatment increased methylene blue adsorption kinetics, probably owing to an increase in micropororosity, whereas alkali activation enhanced the adsorption capacity of the resultant biochar.     

Pore structures of multi-walled carbon nanotubes activated by air, CO2 and KOH

Multi-walled carbon nanotubes (MWNTs) synthesized by the catalytic decomposition of benzene were activated by KOH, CO₂ or air. The adsorption isotherms of the activated MWNTs were analyzed and their pore size distributions were obtained. The results showed that the specific surface areas of the MWNTs activated by KOH, CO₂ and air were increased to 785 m²/g, 429 m²/g and 270 m²/g, respectively. The MWNTs activated by KOH were rich in micropores and mesopores, especially high mesopores having volumes up to 1.04 cm³/g. The CO₂-activated MWNTs also had many micropores while the air-activated MWNTs had a much smaller micropore volume. The morphologies of the activated MWNTs were examined by transmission electron microscopy and high resolution transmission electron microscopy, and the activation mechanisms were discussed.     

Production and characterization of activated carbon derived from brewer’s yeast

Activated carbon (AC) was produced from brewer’s yeast with K₂CO₃ activation. The effects of K₂CO₃/yeast ratio and activation temperature on the yield and adsorption properties of the AC were investigated. The results indicate that the optimum conditions were as follows: ratio of K₂CO₃/yeast=2 and activation temperature 800 °C. The AC produced under the optimum conditions has BET surface area of 1,603 m²/g, pore volume of 1.43 cm²/g and average pore diameter of 3.5 nm. Adsorption of phenol onto the AC was determined by batch test at solution pH of 7. The effects of contact time and initial phenol concentration were investigated. The adsorption process was found to follow pseudo-second-order kinetics. The rate of phenol adsorption onto the AC produced was rapid with the adsorption equilibrium reached within 5 min. The experimental data fitted well with the Langmuir isotherm model. The maximum phenol uptake by the AC was estimated to be 513.5 mg/g.     

The performances of higher alcohol synthesis over nickel modified K2CO3/MoS2 catalyst

Ni modified K₂CO₃/MoS₂ catalyst was prepared and the performance of higher alcohol synthesis catalyst was investigated under the conditions: T = 280–340 °C, H₂/CO (molar radio) = 2.0, GHSV = 3000 h^− 1, and P = 10.0 MPa. Compared with conventional K₂CO₃/MoS₂ catalyst, Ni/K₂CO₃/MoS₂ catalyst showed higher activity and higher selectivity to C₂⁺OH. The optimum temperature range was 320–340 °C and the maximum space-time yield (STY) of alcohol 0.30 g/ml h was obtained at 320 °C. The selectivity to hydrocarbons over Ni/K₂CO₃/MoS₂ was higher, however, it was close to that of K₂CO₃/MoS₂ catalyst as the temperature increased. The results indicated that nickel was an efficient promoter to improve the activity and selectivity of K₂CO₃/MoS₂ catalyst.     

Synthesis, microstructure, and photocatalysis of In2O3 hollow particles

Indium oxide (In₂O₃) microspheres with hollow interiors have been prepared by a facile implantation route which enables indium ions released from indium-chloride precursors to implant into nonporous polymeric templates in C₂Cl₄ solvent. The templates are then removed upon calcination at 500 °C in air atmosphere, forming hollow In₂O₃ particles. Specific surface area (0.5-260 m² g⁻¹) and differential pore volume (7 × 10⁻⁹ to 3.8 × 10⁻⁴ m³ g⁻¹ Å⁻¹) of the hollow particles can be tailored by adjusting the precursor concentration. For the hollow In₂O₃ particles with high surface area (260 m² g⁻¹), an enhanced photocatalytic efficiency (up to ∼one-fold increase) against methylene blue (MB) dye is obtained under UV exposure for the aqueous In₂O₃ colloids with a dilute solids concentration of 0.02 wt.%.     

Porous structure and liquid‐phase adsorption properties of activated carbon aerogels

In this article, activated carbon aerogels (ACAs) were prepared by CO₂ activation. Their pore structures were investigated by N₂ adsorption–desorption analysis. ACAs have excellent microporosity (e.g. 0.36 cm³/g) and mesoporosity (e.g. 1.72 cm³/g). Adsorption characteristics of phenol, methylene blue, I₂, and VB₁₂ on ACAs in the liquid phase were studied by static adsorption experiments. Results showed that CO₂ activation process is an effective way to introduce micropores in carbon aerogels, which is enhanced with the increase of activation time. As a result, the adsorption capacities of the four mentioned adsorbates on ACAs were improved gradually with the increase of activation time. However, mesopore volume is also a factor on improving adsorption properties for the relatively giant molecules methylene blue and VB₁₂. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Structure of K2Co3-loaded activated carbon fiber and its deodorization ability against H2S gas

Coal tar pitch containing finely dispersed KOH was spun centrifugally, followed by stabilization through heating to 330°C under a (1:1) mixture of air and CO₂ and carbonization/activation by heating to 850°C under CO₂. The activated carbon fiber obtained possessed of a specific surface area of 491 m²g⁻¹ and contained ca. 2% of K as K₂CO₃ over the peripheral region of fiber. The fiber showed high deodorization ability against 30 ppm of H₂S gas in air at ambient temperature. H₂S gas did not diffuse to the most interior parts of the fiber and was oxidized around outer regions of the fiber. Elemental sulphur was deposited in the fiber after H₂S absorption. The deodorization mechanism was discussed. The role and action of the K₂CO₃ supported was explained.     

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.     

Synthesizing activated carbons from resins by chemical activation with K2CO3

We prepared activated carbons from phenol-formaldehyde (PF) and urea-formaldehyde (UF) resins by chemical activation with K₂CO₃ with impregnation during the synthesis of the resins. The influence of carbonization temperature (773-1173 K) on the pore structure (specific surface area and pore volume) and the temperature range at which K₂CO₃ worked effectively as an activation reagent, were investigated. The specific surface area and micropore volume of PF-AC and UF-AC increased with an increase of carbonization temperature in the range of 773-1173 K. We prepared activated carbon with well-developed micropores from PF, and activated carbon with high specific surface area (>3000 m²/g) and large meso-pore volume from UF. We deduced the activation mechanism with thermogravimetry and X-ray diffraction. In preparing activated carbon from PF, K₂CO₃ was reduced by carbon in the PF char. The carbon was removed as CO gas resulting in increased specific surface area and pore volume above 1000 K. In preparing AC from UF, above 900 K the carbon in UF char was consumed during the K₂CO₃ reduction step.