Siberian anthracite as a precursor material for microporous activated carbons

The technology of obtaining active carbon from anthracite mined in Siberia is described. The effect of the activating agent, anthracite/activator ratio and activation temperature has been tested. The activation either with KOH or NaOH has been found to lead to microporous active carbon samples of well-developed surface area reaching from 588 to 2260 m²/g and pore volume from 0.29 to 1.12 m³/g. The structural properties of the active carbons obtained have been found to depend first of all on the anthracite/activating agent ratio, on the kind of activating agent and finally on the temperature of activation.     

Nitrogen-enriched bituminous coal-based active carbons as materials for supercapacitors

The paper presents the results of a study on obtaining N-enriched active carbons from bituminous coal and on testing its use as an electrode material in supercapacitors. The coal was carbonised, activated with KOH and ammoxidised by a mixture of ammonia and air at the ratio 1:3 at 300 °C or 350 °C, at different stages of the production, that is, at those of precursor, carbonisate, and active carbon. The products were microporous N-enriched active carbon samples of well-developed surface area reaching from 1577 to 2510 m²/g and containing 1.0 to 8.5 wt% of nitrogen. The XPS measurements have shown that in the active carbons enriched in nitrogen at the stage of precursor and at the stage of carbonisate, the dominant nitrogen species are the N-5 groups, while in the samples ammoxidised at the last stage of the treatment the dominant nitrogen species are the surface groups of imines and/or nitriles, probably accompanied by amines and amides. The paper reports the results of a comprehensive study of the effect of the structure and chemical composition of a series of active carbon samples of different properties on their capacity performance in water solutions of H₂SO₄ or KOH, with the behaviour of positive and negative electrodes analysed separately.     

Ultrahigh surface area carbon from carbonated beverages: Combining self-templating process and in situ activation

Ultrahigh surface area carbons (USACs, e.g., >2000 m²/g) are attracting tremendous attention due to their outstanding performance in energy-related applications. The state-of-art approaches to USACs involve templating or activation methods and all these techniques show certain drawbacks. In this work, a series of USACs with specific surface areas up to 3633 m²/g were prepared in two steps: hydrothermal carbonization (200 °C) of carbonated beverages (CBs) and further thermal treatment in nitrogen (600–1000 °C). The rich inner porosity is formed by a self-templated process during which acids and polyelectrolyte sodium salts in the beverage formulas make some contribution. This strategy covers various CBs such as Coca Cola®, Pepsi Cola®, Dr. Pepper®, and Fanta® and it enables an acceptable product yield (based on sugars), for example: 21 wt% for carbon (2940 m²/g) from Coca Cola®. Being potential electrode materials for supercapacitors, those carbon materials possessed a good specific capacitance (57.2–185.7 F g⁻¹) even at a scan rate of 1000 mV s⁻¹. Thus, a simple and efficient strategy to USACs has been presented.     

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.     

Effects of carbon surface area on performance of lithium sulfur battery cathodes

The effect of carbon surface area on capacity is investigated in cathodes for lithium sulfur batteries. Carbon additives help overcome the low electrical conductivity of sulfur. Cathodes were prepared at 30 wt% sulfur on different activated carbons having unloaded BET surface areas of 1200–3200 m²/g. Sulfur utilization ranged from 33% to 83% of the theoretical capacity (1672 mAh/g) with a strong correlation to the accessible pore volumes having pore widths between 1 and 5 nm. Additionally, cathodes prepared at 12.5–68 wt% on an activated carbon having unloaded BET surface area of 3200 m²/g showed excessive sulfur loading provided little additional capacity.     

Pressureless sintered silicon carbide tailored with aluminium nitride sintering agent

This study reports the influence of aluminium nitride on the pressureless sintering of cubic phase silicon carbide nanoparticles (β-SiC). Pressureless sintering was achieved at 2000 °C for 5 min with the additions of boron carbide together with carbon of 1 wt% and 6 wt%, respectively, and a content of aluminium nitride between 0 and 10 wt%. Sintered samples present relative densities higher than 92%. The sintered microstructure was found to be greatly modified by the introduction of aluminium nitride, which reflects the influence of nitrogen on the β-SiC to α-SiC transformation. The toughness of sintered sample was not modified by AlN incorporation and is relatively low (around 2.5 MPa m^1/2). Materials exhibited transgranular fracture mode, indicating a strong bonding between SiC grains.     

Temperature stability and high-Qf of low temperature firing Mg2SiO4–Li2TiO3 microwave dielectric ceramics

In this work, a series of low-temperature-firing (1−x)Mg₂SiO₄–xLi₂TiO₃–8 wt% LiF (x = 35–85 wt%) microwave dielectric ceramics was prepared through conventional solid state reaction. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses showed that the Li₂TiO₃ phase was transformed into cubic phase LiTiO₂ phase and secondary phase Li₂TiSiO₅. Partial substitution of Mg²⁺ ions for Ti³⁺ ions or Li⁺Ti³⁺ ions increased the cell volume of the LiTiO₂ phase. The dense microstructures were obtained in low Li₂TiO₃ content (x ≤ 65 wt%) samples sintered at 900 °C, whereas the small quantity of pores presented in high Li₂TiO₃ content (x ≥ 75 wt%) samples sintered at 900 °C and low Li₂TiO₃ content (x = 45 wt%) sintered at 850 and 950 °C. Samples at x = 45 wt% under sintering at 900 °C for 4 h showed excellent microwave dielectric properties of ε_r = 10.7, high Q × f = 237,400 GHz and near-zero τ_f = − 3.0 ppm/°C. The ceramic also exhibited excellent chemical compatibility with Ag. Thus, the fabricated material could be a possible candidate for low temperature co-fired ceramic (LTCC) applications.     

Preparation and characterization of BaCe0.95Tb0.05O3−α hollow fibre membranes for hydrogen permeation

BaCe_0.95Tb_0.05O_3?α (BCTb) perovskite hollow fibre membranes were fabricated by spinning the slurry mixture containing 66.67 wt% BCTb powder, 6.67 wt% polyethersulphone (PESf) and 26.67 wt% N-methyl-2-pyrrolidone (NMP) followed by sintering at elevated temperatures. The influence of sintering temperature on the membrane properties was investigated in terms of crystal phase, morphology, porosity and mechanical strength. In order to obtain gas-tight hollow fibres with sufficient mechanical strength, the sintering temperature should be controlled between 1350 and 1450 °C. Hydrogen permeation through the BCTb hollow fibre membranes was carried out between 700 and 1000 °C using 50% H₂–He mixture as feed on the shell side and N₂ as sweep gas in the fibre lumen. The measured hydrogen permeation flux through the BCTb hollow fibre membranes reached up to 0.422 μmol cm^?2 s^?1 at 1000 °C when the flow rates of the H₂–He feed and the nitrogen sweep were 40 mL min^?1 and 30 mL min^?1, respectively.     

The production of ultra clean coal by sequential leaching with HF followed by HNO3

A UK bituminous coal with particle size <62 μm and containing 5.0 wt% ash and 2.4 wt% S was treated with a two-stage leaching sequence of aqueous HF followed by aqueous HNO₃. The ash and S contents reduced to 0.2 wt% and 1.3 wt%, respectively. In addition, the calorific value (CV) dropped from 31.5 to 29.5 MJ/kg, and the N content increased from 2.0 to 2.8 wt%, due to attack on the carbonaceous matrix during the HNO₃ leach. Interestingly, this attack only occurs when HNO₃ reacts with and dissolves pyrite, suggesting that it is the products of reaction between HNO₃ and pyrite which react with the coal. It is proposed here that localised concentrations of sulphuric and nitric acids at the pyrite site may react to form the powerful nitrating agent NO₂⁺ which then reacts with the carbonaceous coal matrix. The fluoride content of the coal increases from 80 to 3240 ppm after the HF leach, yet drops to 130 ppm following the HNO₃ leach. The mineral matter remaining in the coal after the leaching sequence consists largely of Fe, which is most likely present as finely disseminated unreacted pyrite.     

Nitrogen/sulfur dual-doped mesoporous carbon with controllable morphology as a catalyst support for the methanol oxidation reaction

Ordered mesoporous carbon (OMC) was synthesized by nano-casting method using novel fluidic precursor – acrylonitrile telomer (ANT). By the penetration of mesoporous silica template with pure ANT, followed by the stabilization, carbonization and removal of the template, we obtained highly ordered mesoporous carbon rods (specific area 408 m² g⁻¹). When an acetone solution of ANT (66 and 33 wt.%) was used instead of pure ANT, carbon materials with mesopore ranging from 2 to 7 nm were obtained (specific area 843 and 1012 m² g⁻¹ respectively). Both nitrogen and sulfur atoms were doped into mesoporous carbon with 4 and 0.6 at.% using nitrogen containing monomer and sulfur containing chain transfer agent, without involving complicated synthetic technique and poisonous gaseous compounds. This method was proved to be a facile way to synthesize nitrogen and sulfur containing OMC with partially controllable pore distribution and morphology. More importantly, due to unique mesopore structure and heteroatom doping, Pt nano-particles deposited on the OMCs showed electrocatalytic activity as high as 508 mA mg⁻¹ Pt in methanol oxidation which is 1.7-fold of activity of Pt deposited on commercial Vulcan carbon black.     

Nitrogen-doped ordered mesoporous carbons based on cyanamide as the dopant for supercapacitor

Nitrogen-doped ordered mesoporous carbons (N-doped OMCs) with a high surface area of 1741 m²/g and nitrogen content up to 15 wt.% have been synthesized by nanocasting approach by using SBA-15 as a hard template, phenolic resin (resol) as a carbon source and high nitrogen-containing cyanamide as the nitrogen dopant. The introduction of cyanamide not only incorporates high-content nitrogen into the carbon matrix in the primary forms of pyridinic and quaternary species, but also greatly increases the surface area of materials. The obtained N-doped OMCs have large surface area with mesoporosity up to 92%, uniform and appropriate pore size (3.6–4.1 nm), large pore volume (1.2–1.81 cm³/g). These merits together with high nitrogen enrichment lead to a specific capacitance (230 F/g at 0.5 A/g) and good rate capability (175 F/g at 20 A/g with capacitance retention of 77.4%) in 6 M KOH aqueous electrolytes.     

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.     

Oxidation of arsenite in aqueous solutions by redox copolymer with N-bromosulfonamide functional groups

Macromolecular oxidant [P]-SO₂NBrNa (a macroporous styrene/divinylbenzene copolymer containing N-bromosulfonamide functional groups in the sodium form) was synthesized and used to oxidize arsenites to arsenates in dilute aqueous solutions. The oxidant, containing active bromine (1.65 mmol/g) in its functional groups, was obtained through the transformation of Amberlyst 15 (Rohm and Haas) commercial cation exchanger’s sulfonic functional groups. The batchwise method and the column method and NaAsO₂ solutions (375, 93 and 10 mg As(III)/dm³) in water alone and in 0.01 M NaOH were used in the investigations. Special potentiometric, reductometric measurements showed that the investigated oxidation reaction was favoured by a weak acidic to weak alkaline medium. The determined redox potential of the resin was 440 mV at pH = 6.3 and 130 mV at pH = 11.01. In the column process experiments, conducted using NaAsO₂ solutions with a concentration of 10 mg As(III)/dm³ at a flow rate of 6 BV/h, a breakthrough (defined as the exceedance of 0.01 mg As(III)/dm³ in the effluent) would occur after the solutions amounting to about 1700 bed volumes were passed though the column.     

Synthesis of mesoporous carbons for supercapacitors from coal tar pitch by coupling microwave-assisted KOH activation with a MgO template

Mesoporous carbons (MCs) for supercapacitors were prepared from coal tar pitch by a microwave-assisted one-step process coupling the potassium hydroxide (KOH) activation and magnesium oxide (MgO) template. MCs were characterized by scanning electron microscope and X-ray diffraction. The results show that the specific surface area (S_BET), micropore volume and specific capacitance of MCs made by microwave heating as well as the energy density of MC capacitors pass through a maximum with increasing mass of MgO and the relative mass ratio of KOH/pitch. The S_BET of MCs varies from 1003 to 1394 m²/g. The S_BET and total pore volume of MC and microporous carbon made by microwave heating are bigger than that made by conventional heating. Under optimum conditions with the masses of coal tar pitch, MgO, KOH at 9 g, 12 g, 6 g, and the microwave power at 600 W, MC (MC_9-12-6) made at 30 min heating time shows a high specific capacitance of 224 F/g in 6 M KOH aqueous electrolyte after 1000 cycles. The results have shown that microwave-assisted rapid KOH activation coupled with the MgO template is an efficient one-step approach to the preparation of low cost yet high performance MCs for supercapacitors.     

Extraction of low-molar-mass phenolics and lipophilic compounds from Pinus pinaster wood with compressed CO2

Near-supercritical and supercritical CO₂ was used to extract low-molar-mass phenolics and lipophilic compounds from Pinus pinaster wood. Extraction of samples containing sapwood and knotwood was carried out at 10⿿25 MPa and 30⿿50 °C to assess the influence of the operational conditions on the yields of total extracts and phenolics, as well as on the radical scavenging capacity of extracts. The use of ethanol as a co-solvent increased both the extraction yields and the concentration of phenolics in extracts. Operating under selected conditions (25 MPa, 50 °C, 10% ethanol), the extraction yield accounted for 4.1 wt% of the oven-dry wood. The extracts contained up to 7.6 g of phenolic compounds (measured as gallic acid equivalents) per 100 g extract, and showed one third of the radical scavenging capacity of Trolox. Native resin acids accounted for about 24 g per 100 g extracts, whereas flavonoids, lignans, stilbenes and juvabiones were found at lower proportions.     

Hydrothermal synthesis and activation of graphene-incorporated nitrogen-rich carbon composite for high-performance supercapacitors

Graphene-incorporated nitrogen-rich carbon composite with nitrogen content of ca. 10 wt.% has been synthesized by an effective yet simple hydrothermal reaction of glucosamine in the presence of graphene oxide (GO). The nitrogen content of carbon composite is nearly twice as high as that of hydrothermal carbon without graphene. GO is favorable for the high nitrogen doping in the carbon composite by the reaction between the glucosamine-released ammonia and GO. The hydrothermal carbon composite is further activated by KOH, and graphene in the activated carbon composite demonstrates a positive effect of increasing specific surface area, pore volume and electrical conductivity, resulting in superior electrochemical performance. The activated carbon composite with higher specific surface area and micropore volume possesses higher specific capacitance with a value of 300 F g⁻¹ at 0.1 A g⁻¹ in 6 M KOH aqueous solution in the two electrode cell. Larger mesopore volume and higher conductivity of the activated carbon composite will provide fast ion and electron transfer, thus leading to higher rate capacity with a capacitance retention of 76% at 8 A g⁻¹ in comparison to the activated hydrothermal carbon without graphene.     

Effects of adding different morphological carbon nanomaterials on supercapacitive performance of sol–gel manganese oxide films

In this study, the supercapacitive performances of manganese oxide films were investigated by adding different carbon nanomaterials, including carbon nanocapsules (CNC), multiwalled carbon nanotubes (MWCNTs) and multi-layered graphene. The manganese oxide films were prepared with manganese acetate precursor by sol–gel method, and the post-treatment effects were also examined. With a heat-treatment above 300 °C, the as-prepared amorphous films transformed to a compound of Mn₃O₄ and Mn₂O₃ phases, and the smooth surface became rough as well. Cyclic voltammogram (CV) tests showed that the manganese oxide film, which was mixed with 0.05 wt% MWCNTs and annealed at 350 °C for 1 h, exhibited the optimized specific capacitance, 339.1 F/g. During 1000CV cycles, the specific capacitances of original manganese oxide film decreased gradually from 198.7 to 149.1 (75%) F/g. After same number of cycle tests, the modified films containing 0.025 wt% CNC, 0.05 wt% MWCNTs and 0.1 wt% graphene retained 201.8 (64.2%), 267.4 (78.9%) and 193.1 (57.4%) F/g respectively. The results indicates that the supercapacitive performance of manganese oxide films were significantly modified by carbon nanomaterials; in addition, the MWCNTs additive could also reduce the decay rate.     

Fabrication of carbon fiber reinforced ceramic matrix composites with improved oxidation resistance using boron as active filler

Boron was introduced into C_f/SiC composites as active filler to shorten the processing time of PIP process and improve the oxidation resistance of composites. When heat-treated at 1800 °C in N₂ for 1 h, the density of composites with boron (C_f/SiC-BN) increased from 1.71 to 1.78 g/cm³, while that of composites without boron (C_f/SiC) decreased from 1.92 to 1.77 g/cm³. So when boron was used, two cycles of polymer impregnation and pyrolysis (PIP) could be reduced. Meanwhile, the oxidation resistance of composites was greatly improved with the incorporation of boron-bearing species. Most carbon fiber reinforcements in C_f/SiC composite were burnt off when they were oxidized at 800 °C for 10 h. By contrast, only a small amount of carbon fibers in C_f/SiC-BN composite were burnt off. Weight losses for C_f/SiC composite and C_f/SiC-BN composite were about 36 and 16 wt%, respectively.     

Structural study of mullite based ceramics derived from a mica-rich kaolin waste

Mullite-based ceramics have been synthesized by reactive sintering of a mixture containing kaolin and a mica-rich kaolin waste. Samples fired in the temperature range from 1300 to 1500 °C were characterized by X-ray diffraction (XRD). The quantitative phase analysis and unit cell parameters of the mullite were determined by Rietveld refinement analysis of the XRD data. Mullite-based ceramics with 1.2 wt% quartz, 56.3 wt% glass (amorphous phase), 2.64 g/cm³ of apparent density, and 35±1.2 MPa of flexural strength were obtained after firing at 1500 °C. A liquid phase sintering mechanism activated by a total mica content of 13.3 wt% allowed to increase the mullite content to 47.6 wt% (2.3 wt% quartz and 50.1 wt% glass phase) and improve the flexural strength (70±3.9 MPa) after firing at 1400 °C.     

Ordered mesoporous carbon–TiO2 materials for improved electrochemical performance of lithium ion battery

A series of ordered mesoporous carbon–TiO₂ (OMCT) materials with various weight percentages of TiO₂ (50–75 wt%) were synthesized by evaporation-induced self-assembly and in-situ crystallization at various calcination temperatures (600–1200 °C) to evaluate the Li-ion storage performance. The OMCT has ordered 2D hexagonal mesoporous structures and the TiO₂ nanocrystals with different phases are embedded into the frameworks of carbonaceous matrix. The reversible capacity of OMCT is highly dependent on the phase and content of TiO₂, and the anatase TiO₂ is a superior crystalline phase to rutile and TiN for Li-ion insertion. The OMCT₆₅ which contains 35 wt% carbon and 65 wt% TiO₂ shows a high capacity of 500 mAh g^?1 at 0.1C after 80 cycles. In addition, OMCT₆₅ exhibits a good cyclability and rate capability. The reversible capacity remains at 98 mAh g^?1 at a high rate of 5C, and then recoveries to 520 mAh g^?1 at 0.1C after 105 cycles. The excellent reversible capacity and rate capability of OMCT₆₅ are attributed to the embedment of well-dispersed anatase TiO₂ nanocrystals into the specific porous structure of OMCT, which can not only facilitate the fast Li-ion charge transport but can also strengthen the carbon–TiO₂ co-constructing channels for lithiated reactions.