Microporous activated carbons from ammoxidised anthracite and their capacitance behaviours

The paper presents results of a study on obtaining N-enriched active carbons from anthracite mined in Siberia, and on its use as electrode material in supercapacitors. The anthracite was carbonised, activated with KOH and ammoxidised by a mixture of ammonia and air at the ratio 1:3 at 300 or 350 °C, at each stage of the activate production. The products were microporous N-enriched active carbon samples of well-developed surface area reaching from 1255 m²/g to 2011 m²/g and containing from 0.3 to 5.4 wt% of nitrogen. Capacity curves characteristics of the ammoxidised active carbon samples were determined by the galvanostatic and potentiodynamic methods, and by impedance spectroscopy for acidic and basic electrolyte solutions. The best capacity parameters in an acidic medium were obtained for the coal samples ammoxidised at the precursor stage (191 F/g), containing about 0.4 wt% of nitrogen, while in a basic medium—for the coal samples ammoxidised at the stage of active carbon (200 F/g), containing 4.0 wt% of nitrogen.     

Carbon dioxide activated carbide-derived carbon monoliths as high performance adsorbents

Carbide-derived carbon (CDC) monoliths (DUT-38) with a distinctive macropore network are physically activated using carbon dioxide as oxidizing agent. This procedure is carried out in a temperature range between 850 and 975 °C with durations ranging from 2 to 6 h. Resulting materials show significantly increased specific surface areas as high as 3100 m²/g and total (micro/meso) pore volumes of more than 1.9 cm³/g. The methane (214 mg/g at 80 bar/25 °C), hydrogen (55.6 mg/g at 40 bar/−196 °C), and n-butane (860 mg/g at 77 vol.%/25 °C) storage capacities of the activated CDCs are significantly higher as compared to the non-activated reference material. Moreover, carbon dioxide activation is a suitable method for the removal of metal chlorides and chlorine residuals adsorbed in the pores of CDC after high temperature chlorination. The activation does not influence the hydrophobic surface properties of the CDCs as determined by water adsorption experiments. The macropore network and the monolithic shape of the starting materials can be fully preserved during the activation procedure. n-Butane breakthrough studies demonstrate the materials applicability as an efficient hydrophobic filter material by combining excellent materials transport with some of the highest capacity values that have ever been reported for CDCs.     

Relationship among the physicochemical properties,electrocatalytic performance and kinetics of carbon supported Pt catalyst for ethanol oxidation

A new carbon supported Pt (Pt/C(b)) catalyst was prepared by reducing H₂PtCl₆ in glycol solution using formic acid as a reducing agent, and has been found in this work to be highly active and stable for the electrochemical oxidation of ethanol. The preparation produces highly dispersed Pt particles, of 2.6 nm average size, and with high electrochemical surface area, 98 m²/g. The apparent activation energy of ethanol oxidation over the Pt/C(b) catalyst electrode is low, 10–14 kJ/mol, over the range of potentials from 0.3 to 0.6 V.     

Molded micro- and mesoporous carbon/silica composite from rice husk and beet sugar

A molded carbon/silica composite with high micro- and mesoporosity, as well as a high bulk density, was fabricated by activating a disk-molded precursor made from carbonized rice husk (RH) and beet sugar (BS) at 875 °C in CO₂. The pore structure of the RH- and BS-based carbon/silica composite (RBC) was analysed in relation to the bulk density. An activation time of 2.0 h provided the largest BET specific surface area (1027 m²/g) and total pore volume (0.68 cm³/g) and a low bulk density (0.54 g/cm³). An RBC that was first activated for 1 h was immersed again in BS syrup and then activated in CO₂ for 1 h. This two-step activation process provided both a high bulk density (0.69 g/cm³) and a highly textured structure (BET specific surface area, 943 m²/g; total pore volume, 0.56 cm³/g). The immersion in BS syrup was useful for improving the texture without reducing the bulk density, in comparison to one-step activation for 1.0 h. The suspension of the RBCs was basic because of the residual inorganic compounds of potassium and calcium. However, the basicity of the suspension was alleviated by washing the RBCs with water.     

Utilization of Crofton weed for preparation of activated carbon by microwave induced CO2 activation

Crofton weed was converted into a high-quality activated carbon (CWAC) via microwave-induced CO₂ physical activation. The operational variables including activation temperature, activation duration and CO₂ flow rate on the adsorption capability and activated carbon yield were identified. Additionally the surface characteristics of CWAC were characterized by nitrogen adsorption isotherms, FTIR and SEM. The operating variables were optimized utilizing the response surface methodology and were identified to be an activation temperature of 980 °C, an activation duration of 90 min and a CO₂ flow rate of 300 ml/min with a iodine adsorption capacity of 972 mg/g and yield of 18.03%. The key parameters that characterize quality of the porous carbon such as the BET surface area, total pore volume and average pore diameter were estimated to be 1036 m²/g, 0.71 ml/g and 2.75 nm, respectively. The findings strongly support the feasibility of microwave heating for preparation of high surface area porous carbon from Crofton weed via CO₂ activation.     

Activated carbon xerogels with a cellular morphology derived from hydrothermally carbonized glucose-graphene oxide hybrids and their performance towards CO2 and dye adsorption

We report the preparation of micro-/mesoporous carbon monolithic xerogels by means of a two-step approach that comprises (1) hydrothermal carbonization of glucose in the presence of graphene oxide (GO) sheets as morphology-directing agents and (2) chemical activation of the resulting hydrothermal carbon (HTC) xerogels with KOH. The as-prepared HTC xerogels were made up of a random assembly of thin (<30 nm) carbon platelets, which were interpreted to arise via dehydration and condensation reactions of glucose at catalytically active (acidic) sites present on the surface of GO. The chemical activation afforded xerogels with large surface areas and pore volumes (up to ∼2000 m² g⁻¹ and 1.15 cm³ g⁻¹, respectively) and a cellular morphology, which could be attributed to the combined effect of the activating agent and the unusual, compliant nature of the HTC xerogel. Additionally, the use of different activation conditions allowed fine-tuning the porous texture of the activated xerogels. Finally, the activated carbon xerogels displayed CO₂ uptake capacities up to 4.9 mmol g⁻¹ at 0 °C and 1 bar, as well as an efficient performance (between 600 and 700 mg g⁻¹) in the adsorption of bulky dyes, thus demonstrating their application potential.     

Chemically activated fungi-based porous carbons for hydrogen storage

A set of porous carbons has been prepared by chemical activation of various fungi-based chars with KOH. The resulting carbon materials have high surface areas (1600–2500 m²/g) and pore volumes (0.80–1.56 cm³/g), regardless of the char precursors. The porosities mainly derived from micropores in activated carbons strongly depend on the activation parameters (temperature and KOH amount). All activated carbons have uniform micropores with pore size of 0.8–0.9 nm, but some have a second set of micropores (1.3–1.4 nm pore size), further broadened to 1.9–2.1 nm as a result of increasing either the activation temperature to 750 °C or KOH/char mass ratio to 5/1. These fungi-based porous carbons achieve an excellent H₂ uptake of up to 2.4 wt% at 1 bar and −196 °C, being in agreement with results from other porous carbonaceous adsorbents reported in the literature. At high pressure (ca. 35 bar), the saturated H₂ uptake reaches 4.2–4.7 wt% at −196 °C for these fungi-based porous carbons. The results imply a great potential of these fungi-based porous carbons as H₂ on-board storage media.     

Preparation of carbon adsorbents from lignosulfonate by phosphoric acid activation for the adsorption of metal ions

Activated carbons were prepared from sodium lignosulfonate by phosphoric acid activation at carbonization temperatures of 400–1000 °C. The resulting materials were characterized with regard to their surface area, pore volume, pore size distribution, distribution of surface groups and ability to adsorb copper ions. Activated carbons were characterized by nitrogen adsorption, scanning electron microscopy, Fourier transform infrared spectroscopy and thermal gravimetric analyses. The results indicate that with increasing carbonization temperature, the surface area decreased from 770 m²/g at 400 °C to 180 m²/g at 700 °C and increased at higher temperatures to 1370 m²/g at 1000 °C. The phosphorus content peaked at 11% for carbon obtained by carbonization at 800 °C. Potentiometric titration revealed the acidic character of all the phosphoric acid-activated carbons, which were found to have total concentrations of surface groups of up to 3.3 mmol/g. The carbons showed a high adsorption capacity for copper ions even at pH values as low as 2.     

Preparation of porous carbon nanofibers derived from graphene oxide/polyacrylonitrile composites as electrochemical electrode materials

Porous carbon nanofibers (CNFs) derived from graphene oxide (GO) were prepared from the carbonization of electrospun polyacrylonitrile nanofibers with up to 15 wt.% GO at 1200 °C, followed by a low-temperature activation. The activated CNFs with reduced GOs (r-GO) revealed a specific surface area and adsorption capacity of 631 m²/g and 191.2 F/g, respectively, which are significantly higher than those of pure CNFs (16 m²/g and 3.1 F/g). It is believed that rough interfaces between r-GO and CNFs introduce oxygen pathways during activation, help to produce large amounts of all types of pores compared to pure activated CNFs.     

Nitrogen-doped porous carbons through KOH activation with superior performance in supercapacitors

A series of nitrogen-doped porous carbons are prepared through KOH activation of a nonporous nitrogen-enriched carbon which is synthesized by pyrolysis of the polymerized ethylenediamine and carbon tetrachloride. The porosity and nitrogen content of the nitrogen-doped porous carbons depend strongly on the weight ratio of KOH/carbon. As the weight ratio of KOH/carbon increases from 0.5 to 2, the specific surface area increases from 521 to 1913 m² g⁻¹, while the nitrogen content decreases from 10.8 to 1.1 wt.%. The nitrogen-doped porous carbon prepared with a moderate KOH/carbon weight ratio of 1, which possesses a balanced specific surface area (1463 m² g⁻¹) and nitrogen content (3.3 wt.%), exhibits the largest specific capacitance of 363 F g⁻¹ at a current density of 0.1 A g⁻¹ in 1 M H₂SO₄ aqueous electrolyte, attributed to the co-contribution of double-layer capacitance and pseudocapacitance. Moreover, it shows excellent rate capability (182 F g⁻¹ remained at 20 A g⁻¹) and good cycling stability (97% capacitance retention over 5000 cycles), making it a promising electrode material for supercapacitors.     

Preparation and characterization of activated carbon from oil sands coke

Several million tonnes of oil sands coke are generated each year in Alberta, Canada as a by-product of bitumen upgrading. Due to its high carbon content, oil sands coke can be a suitable precursor for the preparation of activated carbon. In this study, delayed and fluid oil sands coke were physically activated in a muffle furnace under select conditions of activation time (2–6 h), temperature (800–900 °C), steam rate (0.3–0.5 mL/min), and activation atmosphere (CO₂, CO₂ + steam, and N₂ + steam). The activated products were characterized using thermogravimetric analysis, X-ray diffraction, scanning electron microscopy, nitrogen adsorption, iodine and methylene blue tests. An increase in activation time and temperature resulted in higher surface areas in both delayed and fluid coke due to an enhanced etching of pores. An increase in steam rate led to the production of the highest specific surface area (577 m²/g) and iodine number (670 mg/g) within delayed coke; whereas, a lower steam rate resulted in the production of the highest specific surface area (533 m²/g) and iodine number (530 mg/g) in activated fluid coke samples.     

The effect of wetting on pore texture and methane storage ability of NaOH activated anthracite

The present work deals with the role of water commonly present in carbonaceous materials, or added to them, on the NaOH activation process. The preliminary wetting of an anthracite subsequently activated with NaOH in definite conditions (1 h at 730 °C, mass ratio NaOH/carbon = 3) and its consequence on the pore texture and resulting methane adsorption capacities are discussed. Water was added to a powder of anthracite according to wetting ratios water/carbon ranging from 0% to 30%. Significant effects on BET surface area, pore texture, packing density and corresponding methane storage capacity were evidenced. Among the investigated wetting ratios, an optimum of 20–25 wt.% of water added to the anthracite was found to lead to the highest adsorption properties for methane. An additional densification finally allowed reaching deliverable methane capacities higher than 150 V/V.     

Spherical carbons: Synthesis,characterization and activation processes

Spherical carbons have been prepared through hydrothermal treatment of three carbohydrates (glucose, saccharose and cellulose). Preparation variables such as treatment time, treatment temperature and concentration of carbohydrate have been analyzed to obtain spherical carbons. These spherical carbons can be prepared with particle sizes larger than 10 μm, especially from saccharose, and have subsequently been activated using different activation processes (H₃PO₄, NaOH, KOH or physical activation with CO₂) to develop their textural properties. All these spherical carbons maintained their spherical morphology after the activation process, except when KOH/carbon ratios higher than 4/1 were used, which caused partial destruction of the spheres. The spherical activated carbons develop interesting textural properties with the four activating agents employed, reaching surface areas up to 3100 m²/g. Comparison of spherical activated carbons obtained with the different activating agents, taking into account the yields obtained after the activation process, shows that phosphoric acid activation produces spherical activated carbons with higher developed surface areas. Also, the spherical activated carbons present different oxygen groups’ content depending on the activating agent employed (higher surface oxygen groups content for chemical activation than for physical activation).     

Synthesis of nanostructured carbons by the microwave plasma cracking of methane

One of the attractive methods of producing hydrogen and high value-added carbon is plasma-reforming of hydrocarbons. Here, nanostructured carbon was produced by methane cracking in a relatively low-energy cold plasma reactor designed in-house specifically for such purpose. Carbon samples collected at different positions in the reactor show similar structural morphologies, indicating extensive structural uniformity of the carbon during processing. Surface area and microstructure of the materials were characterized by BET surface area analysis, X-ray diffraction and transmission electron microscopy (TEM). The effects of flow rate, temperature and power were evaluated for the formation of the carbon structures. The results show that the BET surface area and pore volume of the carbon materials vary from 74 to 125 m²/g and from 0.12 to 0.20 cm³/g, respectively. Such variations are closely associated with the magnitude of temperature drop at the sample collection position in the cold-plasma chamber before and after methane loading. The highest BET surface area of 125 m²/g is obtained at a power of 2000 W. TEM shows that the carbon consists of spherical particles of 40.8 ± 8.7 nm in diameter and graphene sheets.     

Synthesis of nanosheet-structured Na3V2(PO4)3/C as high-performance cathode material for sodium ion batteries using anthracite as carbon source

Recently, Na₃V₂(PO₄)₃ has shown great promise as cathode material for sodium-ion batteries. In this study, a series of carbon-modified Na₃V₂(PO₄)₃ (NVP/C) composites have been synthesized using anthracite as the carbon source. The NVP/C composite shows a nanosheet shape with a 3D continuously conductive network composed of carbon layer and carbon bump. The effect of anthracite dosage on the electrochemical performance of NVP/C has also been investigated. The results show that the NVP/C composite prepared with 10 wt% anthracite (NVP/C-10) exhibits the highest rate capability and a great cycle stability. Especially the NVP/C-10 electrode behaves an average capacity as high as 97 mAh g⁻¹ at a high current rate of 10 C. Moreover, NVP/C-10 still delivers a high specific capacity of 97.5 mAh g⁻¹ even after 800 cycles at 5 C, showing a very low capacity fading ratio of 0.012% per cycle. The excellent rate capability and cycle stability of NVP/C-10 can be ascribed to the synergistic effects of the nanosheet structure and the 3D continuously conductive network. Our results demonstrate that anthracite can be a promising carbon source for the preparation of NVP/C and other polyanion cathode materials as well.     

Synthesis and characterization of mesoporous carbon through inexpensive mesoporous silica as template

Mesoporous silica materials have been synthesized through sol–gel reaction using inexpensive sodium silicate as source of silica and low cost hydroxy carboxylic acid compounds as templates/pore forming agents. The material measured surface area of 1014 m²/g, pore diameter of 65 Å and pore volume of 1.4 cc/g when parameters like time and temperature of synthesis along with mole ratio of TA/SiO₂ were optimized. Here TA stands for tartaric acid. Carbonization of sucrose inside the pores of above silica material at 900 °C followed by removal of silica framework using aqueous ethanoic solution of NaOH gave rise to mesoporous carbon material. The resulting materials were characterized by N₂-sorption, FTIR spectroscopy, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, thermal analysis and cyclic voltammetry. Three dimensional interconnecting wormhole channel arrangement of mesoporous silica template leads to mesoporous carbon replica with surface area of 1200 m²/g. X-ray photoelectron spectroscopic study (XPS) of the mesoporous carbon material shows the concentration of carbon atom in the range of 97–98% with 1–2% oxygen and negligible amount of silica. The electrochemical double layer capacitance behavior of carbon material with the specific capacitance value of 88.0 F/g at the scan rate of 1 mV/s appears to be promising.     

Avoiding structure degradation during activation of ordered mesoporous carbons

Hierarchical micro–mesoporous carbons with high porosity development and ordered structure were prepared. The innovative proposal consists in developing microporosity in ordered mesoporous carbon by chemical activation in template presence in order to minimize the structural damage. Thus, we have directly carried out the chemical activation of a mesoporous carbon/silica composite with KOH. The effect on mesoporous ordered structure of both KOH/carbon ratio and activation temperature has been studied. Following chemical activation the specific surface area is increased from 341 to 1757 m²/g and the micropore volume becomes almost six times larger than initial value. Although a slight widening of the mesopore distribution and an increase in the mesopore volume has been observed during activation, TEM and XRD results reveal an excellent conservation of the ordered mesoporous structure during activation even at conditions well above the limits that a CMK-3 type carbon can resist.     

Mechanism of decomposition of aromatics over charcoal and necessary condition for maintaining its activity

Decomposition of mono- to tetra-aromatics over charcoal was investigated under conditions such as temperature; 700–900 °C, inlet concentrations of aromatics, steam and H₂; 7.5–15 g/Nm³, 0–15.5 vol% and 0–15.5 vol%, respectively, gas residence time within charcoal bed; 0.2 s, particle size of charcoal; 1.3–2.4 mm. The charcoal, with an initial surface area of 740 m²/g, was active enough to decompose naphthalene completely even at 750 °C. Aromatics with more rings per molecule were decomposed more rapidly. The aromatics were decomposed over the charcoal by coking rather than direct steam reforming irrespective of temperature and steam/H₂ concentrations. The coking, i.e., carbon deposition from the aromatics, caused loss of micropores and thereby activity of the charcoal, while steam gasification of the charcoal/coke formed or regenerated micropores. Relationship between the overall rate of carbon deposition by the coking and gas formation by the gasification within the charcoal bed showed that progress of the gasification at a rate equivalent with or greater than that of the carbon deposition was necessary for maintaining the activity of the charcoal.     

Transition metal loaded silicon carbide-derived carbons with enhanced catalytic properties

Carbide-derived carbons (CDC) with incorporated transition metal nanoparticles (～2.5 nm) were prepared using a microemulsion approach. Time-consuming post synthesis functionalization of the carbon support material can thus be avoided and nanoparticle sizes can be controlled by changing the microemulsion composition. This synthesis strategy is a technique for the preparation of highly porous carbon materials with a catalytically active component. In particular we investigated the integration of ruthenium, palladium, and platinum in a concentration ranging from 4.45 to 12 wt.%. It was found that the transition metal has a considerable influence on sorption properties of resulting nanoparticle-CDC composite materials. Depending on the used metal salt additive the surface area and the pore volume ranges from 1480 m²/g and 1.25 cm³/g for Pt to 2480 m²/g and 2.0 cm³/g for Ru doped carbons. Moreover, members of this material class show impressive properties as heterogeneous catalysts. The liquid phase oxidation of tetralin and the partial oxidation of methane were studied, and electrochemical applications were also investigated. Primarily Pt doped CDCs are highly active in the oxygen reduction reaction, which is of great importance in present day fuel cell research.     

Rhodium complexes supported on nanoporous activated carbon for selective hydroformylation of olefins

Activated carbon with nanoporous structure, high surface area (2500 m²/g) and total pore volume (2.35 cm³/g) was prepared from Mango seed shell (Mangifera indica L.) via chemical activation method and used as support to impregnate active hydroformylation rhodium complexes HRhCO(PPh₃)₃ and Rh(acac)(CO)₂. The prepared catalysts were characterized by XRD, SEM, TEM, NMR, IR, TGA, and N₂ adsorption/desorption techniques. The supported catalysts have shown excellent selectivity for aldehydes (~ 99%) in the hydroformylation of olefins with good stability and recyclability up to 4 cycles.