Isotropic and anisotropic microporosity development upon chemical activation of carbon fibers, revealed by microbeam small-angle X-ray scattering

A sub-micrometer size beam (0.5 μm diameter) in a position-resolved small angle X-ray scattering set-up (μSAXS) has been used for the characterization of chemically activated carbon fibers (ACF). These materials have been prepared from isotropic carbon fibers (pitch carbon fibers) and anisotropic carbon fibers (PAN-based carbon fibers) by chemical activation with KOH and NaOH. The μSAXS experimental set-up made it possible to analyze different regions of a single fiber across its diameter and to distinguish the structural features already existing in the raw fibers or being created during the activation process. The results showed that depending on the precursor, the chemical activation process produces isotropic or anisotropic development of porosity. It was observed that chemically ACF prepared from isotropic carbon fibers present an isotropic development of the porosity and that a high micropore volume is developed not only in the external region of the fiber, but also in the core. On the other hand, in the case of anisotropic PAN-based carbon fibers the existence of two regions with different structure was detected by μSAXS measurements across the fiber diameter: an anisotropic external ring and a more isotropic fiber core. The results showed that these two regions remain after chemical activation and that the activating agents are reaching the fiber core. It seems that the more isotropic fiber core is activated easier by NaOH than KOH.     

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).     

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.     

Role of surface chemistry on electric double layer capacitance of carbon materials

A large number of porous carbon materials with different properties in terms of porosity, surface chemistry and electrical conductivity, were prepared and systematically studied as electric double layer capacitors in aqueous medium with H₂SO₄ as electrolyte. The precursors used are an anthracite, general purpose carbon fibres and high performance carbon fibres, which were activated by KOH, NaOH, CO₂ and steam at different conditions. Among all of them, an activated anthracite with a BET surface area close to 1500 m²/g, presents the best performance, reaching a value of 320 F/g, using a three-electrode system. The results obtained for all the samples, agree with the well-known relationship between capacitance and porosity, and show that the CO-type oxygen groups have a positive contribution to the capacitance. A very good correlation between the specific capacitance and this type of oxygen groups has been found.     

KOH and NaOH activation mechanisms of multiwalled carbon nanotubes with different structural organisation

New information was obtained on the mechanism of porosity development during chemical activation by KOH and NaOH using various multiwalled nanotubes (MWNTs) of different structural organization. The high purity MWNTs were prepared by acetylene decomposition on a cobalt-based catalyst at different temperatures. The obtained samples ranged from MWNTs with well organised graphitic walls to nanotubes with disorganised layers mixed with some pyrolytic carbon when decreasing synthesis temperature. The results of transmission electron microscopy (TEM) observations were linked with gas adsorption measurements and X-ray diffraction data. They show that NaOH is only effective with disordered materials whereas KOH is effective whatever the structural order. After reaction of the poorly ordered precursor with KOH, the nanotubular morphology is completely destroyed, whereas it is preserved when NaOH is used. However for the more ordered materials, the morphology remains unchanged with both reactants. Effects of activation are only seen with KOH, which generated a large concentration of defects in the nanotubes walls. The differences found between KOH and NaOH during activation are related with an additional intercalation step of metallic K or Na produced during the redox reactions. It is shown that metallic K has the ability to be intercalated in all materials in contrast with Na which can only intercalate in the very disorganised ones. The conclusions obtained from the study on ordered nanotubes were confirmed with an ordered carbon black, demonstrating that the structural organization of the carbon precursor is an important parameter which must be taken into account when alkali reactants are used for the activation.     

On the reaction mechanism of the chemical activation of Quercus Agrifolia char by alkaline hydroxides

Activation of Quercus Agrifolia char with NaOH and KOH using a rotary batch reactor is presented in this work. Several samples of activated carbon showing a very high degree of activation with predominance of microporosity were obtained. Nitrogen and argon were used as gaseous media in the activation procedure. Samples were evaluated using nitrogen adsorption applying BET and DR equation for porosity assessment. The existence of CN⁻ in activated samples suggests the occurrence of not previously reported chemical reactions in this process and could be an indication of the involvement of N₂ in the chemical reaction. Following these results, some additional chemical reactions are proposed as part of the reaction mechanism for MeOH-C-N₂ system.     

KOH activation of ordered mesoporous carbons prepared by a soft-templating method and their enhanced electrochemical properties

Ordered mesoporous carbon (COU-2) was synthesized by a soft-templating method. The COU-2 mesoporous carbon was activated by using KOH to improve its porosity. The mesopore size of COU-2 was 5.5 nm and did not change by the KOH activation. But, the BET surface area of COU-2 largely increased from 694 to 1685 m²/g and total pore volume was increased from 0.54 to 0.94 cm³/g after the KOH activation. The large increase of micropore volume is due to the increase of the surface area. Electrochemical cyclic voltammetry measurements were conducted in aqueous (1 M sulfuric acid) and organic (1 M tetraethyl ammonium tetrafluoroborate/polypropylene carbonate) electrolyte solutions. The KOH-activated COU-2 carbon shows superior capacitances over the COU-2 carbon and a commercial microporous carbon both in aqueous and organic electrolyte solutions. These results suggest that the carbons having regularly-interconnected uniform mesopores and micropores in thin pore walls are desirable for the electrodes in electrochemical double-layer capacitors.     

Effect of activation on the carbon fibers from phenol–formaldehyde resins for electrochemical supercapacitors

Activated carbon fibers (ACF) are prepared from phenol–formaldehyde resin fibers through chemical activation and physical activation methods. The chemical activation process consisted of KOH, whereas the physical activation was performed by activation in CO₂. The characteristics of the electrochemical supercapacitors with carbon fibers without activation (CF), carbon fibers activated by CO₂ (ACF-CO₂), and carbon fibers activated by KOH (ACF-KOH) have been compared. The activated carbon fibers from phenol–formaldehyde resins present a broader potential range in aqueous electrolytes than activated carbon and other carbon fibers. Activation does not produce any important change in the shape of starting fibers. However, activation leads to surface roughness and larger surface areas as well as an adapted pore size distribution. The higher surface areas of fibers treated by KOH exhibited higher specific capacitances (214 and 116 F g⁻¹ in aqueous and organic electrolytes, respectively) and good rate capability. Results of this study suggest that the activated carbon fiber prepared by chemical activation is a suitable electrode material for high performance electrochemical supercapacitors.     

Preparation of porous carbons from petroleum coke by different activation methods

Porous carbons were prepared from Shengli petroleum coke (SPC) and Minxi petroleum coke (MPC) by different activation methods with H₂O, KOH and/or KOH+H₂O as active agents. The porous carbons were characterized by nitrogen adsorption at 77 K. It has been found that activation method and component of petroleum coke, of which different kinds of transitional metals on petroleum coke are crucial for preparing high quality porous carbons. Under the identical experimental conditions, the co-activation with KOH and H₂O as active agents in the same activation process, which has been rarely reported in literature, is the easiest method for the preparation of porous carbons with high surface area. The sequence of active agents in terms of difficulty in the preparation of porous carbons with high surface area is as follows: KOH+H₂O>KOH>H₂O. A drawback of KOH+H₂O activation in the preparation of porous carbon in this work is found to be its low carbon yield in comparison to KOH activation. Compared with the SPC coke, the MPC coke with higher contents of transitional metal and carbon and lower content of nitrogen is more suitable for making high surface area porous carbons, which is believed to be mainly due to the difference in the contents of transitional metals. Porous carbon with surface area around 2500–3000 m²/g and carbon yield about 25–30% has been obtained from MPC coke by KOH+H₂O activation with less KOH and shorter activation time in comparison to the traditional methods.     

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.     

Distribution of potassium during chemical activation of petroleum coke: Electron microscopy evidence and links to phase behaviour

In this study, direct evidence for chemical penetration into petroleum coke particles during activation is presented. In addition, the porosity development was directly related to the sulphur loss and phase behaviour of the species present. Petroleum coke (petcoke, 6 wt.% sulphur) was activated with KOH and NaOH at temperatures between 400 and 800°C. The C S bonds were broken before 400°C in the presence of KOH and before 500°C in the presence of NaOH. Electron microscopy analysis of cross-sectioned and ultramicrotomed samples revealed that sulphur was still present within the particles and that the hydroxide activation agents had penetrated to the centre of the particles (90–150 μm). After heating to 800°C and washing with a weak acid aqueous solution, essentially all the sulphur was removed, as was any remaining chemical agent. The characterization results, phase diagrams, and complementary experiments with carbonate chemical agents or steam suggest that, during heating, a molten phase formed around the petcoke particles. The composition of this molten phase changed as activation proceeded and both sulphur and ash components were liberated from the petcoke. This better understanding of the activation process will improve the efficiency of preparing activated carbon.     

Comparison of the effects of different chemical activation methods on properties of carbonaceous adsorbents obtained from cherry stones

A method for obtaining activated carbons from cherry stones by chemical activation with NaOH is described. Carbonaceous adsorbents were obtained by two methods of activation (physical mixing and impregnation) and two variants of thermal treatment (at a constant or increasing temperature). Cherry stones were proved to be effective cheap precursors of carbon adsorbents, characterised by large pore volume (ranging from 0.22 to 0.47 cm³/g) and good sorption abilities (iodine number from 343 to 996 mg/g). The activated carbons obtained usually have strongly microporous structure and acidic surface character. The best physicochemical properties and adsorption properties towards iodine were found to be shown by the carbon samples obtained by physical mixing of the precursor or char with the activating agent followed by activation at 600 °C.     

Nanoporosity development in the thermal-shock KOH activation of brown coal

Thermal-shock KOH activation of brown coal (800 °C, KOH/coal ratio 1 g/g) was shown to produce nanoporous activated carbon with more developed surface area than thermally-programmed heating (S_BET up to 1700 vs 1000 m²/g). Increasing the KOH/coal ratio (up to 1 g/g) in the activated mixture increases the total pore volume (0.14–1.0 cm³/g), the micropore volume (0.03–0.71 cm³/g), and also the volume of subnanometer pores (0.01–0.40 cm³/g). Thermal shock produces nanoporosity at lower KOH/coal ratios (0.5-1.0 g/g) than respective low-rate heating KOH activation.     

A comparison of physical activation of carbon xerogels with carbon dioxide with chemical activation using hydroxides

Carbon xerogels synthesized with a fixed resorcinol/sodium carbonate molar ratio (R/C) were physically activated using CO₂. The effect of activation temperature and activation time on the final properties of the activated carbon xerogels was evaluated. The specific surface area increases from ∼600 m² g⁻¹ to 2000 m² g⁻¹ and more by increasing the temperature and duration of the activation step. A comparison between physical activation with CO₂ and chemical activation with hydroxides was also performed: it was found that both processes produce an increase of the micropore volume and specific surface area without altering the mesoporosity developed during the synthesis. However, chemical activation can lead to the development of the narrow microporosity mainly whereas, in physical activation, the widening of the narrow micropores takes place whatever the process conditions.     

Hierarchically porous phenolic resin-based carbons obtained by block copolymer-colloidal silica templating and post-synthesis activation with carbon dioxide and water vapor

A series of hierarchically porous carbons was synthesized by self-assembly of polymeric carbon precursors and block copolymer template in the presence of tetraethyl orthosilicate (TEOS) and colloidal silica under acidic conditions. Resorcinol and formaldehyde were used as carbon precursors, poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) triblock copolymer was employed as a soft template, and TEOS-generated silica and colloidal silica were used as hard templates. The carbon precursors were polymerized in hydrophilic domains of block copolymer, followed by carbonization and silica dissolution. This resulted in carbons possessing cylindrical (∼12 nm) and spherical (20 or 50 nm) mesopores created by thermal decomposition of the soft template and by the dissolution of colloidal silica, respectively; fine pores were also formed by the dissolution of the TEOS-generated silica (∼2 nm). A further increase in fine porosity was achieved by post-synthesis activation of the carbons with carbon dioxide and/or water vapor, which resulted in hierarchical carbons with a surface area and pore volume approaching 2800 m²/g and 6.0 cm³/g, respectively.     

KOH activated lignin based nanostructured carbon exhibiting high hydrogen electrosorption

Carbon materials capable of efficient hydrogen electrosorption at ambient conditions can be used for negative electrode material in chemical power sources, competitive for metallic hydride alloys. This paper describes physical, chemical and electrochemical properties of active carbon (LAC) produced from lignin processed by standard carbonization and KOH activation at temperature of 950 °C. Microporous carbon with BET surface of 1946 m²/g obtained in such conditions has a complex porous structure with a considerable number of supermicropores and small mesopores (ca. 50%). As a result, efficient hydrogen electrosorption of 510 mA h/g (1.89 wt% in meaning of energy storage) is obtained and favorable discharge characteristics at current densities up to 1 A/g.     

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.     

Isotropic petroleum pitch as a carbon precursor for the preparation of activated carbons by KOH activation

Results show that it is possible to activate a low softening point isotropic petroleum pitch, without intermediate pre-treatments, by chemical activation with KOH. The chemical activation is carried out by direct heat treatment of a mixture of the isotropic pitch and KOH. It produces activated carbons (ACs) with micropore volumes as high as 1.12 cm³/g, and BET surface areas around 3000 m²/g. The activating agent/precursor ratios studied (from 1/1 to 4/1; wt./wt.) show, as expected, that increasing the ratio enhances the adsorption characteristics of the resulting AC.     

Understanding chemical reactions between carbons and NaOH and KOH: An insight into the chemical activation mechanism

Direct mixing of an anthracite with hydroxides (KOH or NaOH) and heat treatment up to 730 °C has shown to be a very good activation procedure to obtain activated carbons with very high surface areas and high micropore volumes. The reactions involved during the heat treatment of these hydroxide/anthracite mixtures have been analysed to deep into the fundamental of the knowledge of this chemical activation process, that has not been studied before. For this purpose, the present paper analyses the drying process, the atmosphere during the carbonisation, the chemical state of the activating agents (NaOH, KOH and Na₂CO₃) and the chemical reactions occurring during the heat treatment which have been followed by FTIR and TPD. The analysis of our results allows us to conclude that steam is a good atmosphere for the carbonisation process, alone or joined with nitrogen, but not as good as pure nitrogen. On the other hand, during the activation process, the presence of CO₂ should be avoided because it does not develop porosity. The reactions, and chemical changes, involved during this chemical process are discussed both from a thermodynamical point of view as well as identifying the reaction products (H₂ by TPD and Na₂CO₃ by FTIR). As a result, this paper helps to cover the present lack of understanding of the fundamentals of the reactions of an anthracite with hydroxides which are necessary to understand the activation of the material.     

Porous carbon materials produced by the chemical activation of birch wood

It was established that the main factors responsible for the yield and specific surface area of porous carbon materials obtained by the chemical activation of the wood of birch are the nature of a modifying agent and the temperature of pyrolysis. The additional opening of the porous structure of the product of the chemical activation of wood occurs at the stage of its water treatment as a result of the removal of water-soluble compounds. The conditions of the carbonization of birch wood modified with H₃PO₄, KOH, and ZnCl₂ were chosen in order to provide the significant development of the porous structure of carbon materials. The porous carbon material with the highest specific surface area (more than 2560 m²/g) was obtained by the water washing of the product of the carbonization of birch wood modified H₃PO₄ at 400°C.