Electrochemical catalytic modification of activated carbon fabrics by ruthenium chloride for supercapacitors

A novel method, electrochemical catalytic oxidation via a ruthenium redox couple in an aqueous RuCl₃ · xH₂O solution rather than the anodic deposition of Ru oxides, was developed to modify the microstructure and electrochemical properties of activated carbon fabrics (ACFs). The variation in microstructures (i.e., specific surface area and mean pore size) for the modified ACFs was examined by means of nitrogen gas adsorption isotherms. The distribution of oxygen-containing functional groups within the modified ACFs was identified by temperature programmed desorption (TPD) and X-ray photoelectron (XPS) spectra. Effects of the electrochemical catalytic modification on the electrochemical characteristics and reversibility of ACFs were investigated systematically by means of cyclic voltammetry (CV) and chronopotentiometry (CP) in 0.5 M H₂SO₄. The total specific capacitance of ACFs reached a maximum (ca. 180 F/g measured at 10 mA/cm²) when they were catalytically modified at 1.15 V with a passed charge density of 5 C/cm². These modified ACFs were demonstrated to be an excellent candidate for the supercapacitor application.     

Influence of HNO3 oxidation on the structure and adsorptive properties of corncob-based activated carbon

An investigation of the impact of strong oxidation with HNO₃ on the porosity and adsorption characteristics of char and activated carbons, derived from corncobs, is presented. Texture parameters, as obtained from N₂ adsorption at 77 K, showed a considerable decrease in surface area of the activated carbons with enhanced pore widening. The extent of porosity modification was found to depend on the scheme of activation of the precursor, simple carbonization, steam pyrolysis, steam gasification of the char, or chemical activation with H₃PO₄. Surface-chemical changes were detected by FTIR spectroscopy, where absorption bands assigned to carboxyl, carboxylate, carbonyl, and phenolic groups were observed. A SEM study demonstrated the erosive effect of HNO₃, detected by the presence of disintegration of the carbon grains, with the porous structure probably containing very large macropores. As a consequence of the oxidation process, elemental analysis showed high contents of O, H and N, and TG confirmed that the weight loss distribution in the thermogram becomes slower at higher temperatures. The removal of phenol decreased as a result of the formation of oxygen functionalities. Mono-nitrophenols were adsorbed in smaller amounts than phenol, and p-nitrophenol showed a relatively higher uptake than the other two mono-nitrophenols, whereas the uptake of Methylene Blue was improved. Removal of Pb²⁺ from aqueous non-buffered solution was considerably enhanced by chemical oxidation, which may be related to pore widening, increased cation-exchange capacity by oxygen groups, and the promoted hydrophilicity of the carbon surface.     

Effect of air oxidation of Rayon-based activated carbon fibers on the adsorption behavior for formaldehyde

The tailoring of pore surface chemistry of activated carbon fibers is shown to be an effective method for improving the adsorption efficiency of various volatile chemical compounds (VOCs). An oxidation treatment with air resulted in a significant increase in the adsorption capacities and breakthrough time for Rayon-based activated carbon fibers (ACFs) in removal of formaldehyde. The porous structure parameters of Rayon-based ACFs were determined with standard nitrogen adsorption analysis. The pore surface chemistry of samples under study was analyzed by Fourier Transform Infrared spectra (FTIR). Thus to some extent, the relationship between the adsorption properties, porous structure and pore surface chemistry was revealed.     

Destruction of methyl ethyl ketone vapor by ozone on activated carbon

This study attempts to combine the technologies of adsorption of volatile organic compounds (VOCs) on activated carbon and the oxidation of the VOCs by ozone (O₃). In the adsorption/oxidation process, the effects of ozone on the adsorption characteristics of methyl ethyl ketone (MEK) vapor on activated carbon are investigated. The kinetic parameters of the reaction for MEK vapor and O₃ on activated carbon are also determined. The results show that the destructive efficiencies of MEK by 1000 ppmv O₃ on activated carbon are from 12.4% to 48.5%. From the power law kinetic model, the apparent kinetic constant, k, is obtained with a value of 0.0438 h⁻¹. Moreover, from the analytical results of the Arrhenius equation, the activation energy, E_a, is found to be 5.12 kcal/mol and the value of rate constant, A, is 189.54 h⁻¹. From the Langmuir–Hishelwood model [Escobar, P., Beroy, Q., Iritia, P.P., Huerta, J.H., 2004. Kinetic Study of the Combustion of Methyl–Ethyl–Ketone over α-Hematite Catalyst. Chem. Eng. J. 102, 107] the values of the kinetics parameters k^′LH${k^{\prime }}_{\text{LH}}$ and k_LH were 0.035 and 0.6183, respectively. Finally, the modified Wheeler equation [Busmundrud, O., 1993. Vapour Breakthrough in Activated Carbon Beds. Carbon 31, 279; Wood, G., Moyer, E.S., 1989. A Review of the Wheeler Equations and Comparison of Its Applications to Organic Vapor Respirator Cartridges Breakthrough Data. Am. Ind. Hyg. Assoc. J. 50, 400; Yoon, Y.H., Nelson, J.J., 1984. Application of Gas Adsorption Kineties I. A Theoretical for Respirator Cartridge Service Life. Am. Ind. Hyg. Assoc. J. 45, 509] in combination with the power law kinetic model or Langmuir–Hishelwood is used to predict the breakthrough curves. The destruction of MEK can be effectively promoted as the bed height of activated carbon and the concentration of ozone increase. When the ozone concentration is increased to 7800 ppmv and the amount of activated carbon is increased to 5 g the destructive efficiency of MEK is still greater than 95% even after a prolonged operational time. From the results of this study, an adsorption process in combination with ozone oxidation shows potential for the control of VOCs and odor.     

Nitrogen in aramid-based activated carbon fibers by TPD, XPS and XANES

Activated carbon fibers were prepared from Nomex® [poly(m-phenylene isophthalamide)] by either H₃PO₄ activation, H₃PO₄-CO₂ activation, or simply CO₂ or steam activation. These treatments converted amide groups from the polymer precursor into complex and heterogeneously distributed nitrogen functionalities. TPD, XPS and XANES were used to study the effects of these treatments on the local bonding environment around nitrogen in the resulting carbons. These analytical techniques showed that nitrogen atoms are present in the 6-membered rings located at the edges of condensed polyaromatic systems as pyridine-like sp² nitrogen (N1 or N2) or in the interior, where nitrogen replaces one carbon atom and is bonded to three carbon neighbors (N3). The occurrence of a species (N2) hypothetically related to a pyridinic cycle bearing oxygen substituents or intracyclic oxygen atoms could be correlated with the degree of oxidation of the carbon surface. Assuming that a relative N3 increase is indicative of aromatization and that the reverse, correlated with a N2 increase, is indicative of surface oxidative denitrogenation, the ratio between these nitrogen species revealed that aromatization and oxidative denitrogenation processes occur sequentially or simultaneously to different extents according to the type of carbon activation and to the burn-off degree. Physical activation involves thermal aromatization reactions during the carbonization stage and the subsequent isothermal activation one. In this second activation stage, co-occurring thermal oxidation reactions lead to a less intense denitrogenation during CO₂ activation than during steam activation. H₃PO₄ activation induces the largest nitrogen retention in the final product in a double process of aromatization and “auto-activation” producing a moderate oxidative attack of nitrogen. However, an increase of the H₃PO₄ ratio fostered the oxidation of the carbon surface and consequently enhanced nitrogen gasification during the subsequent activation.     

The role of different nitrogen functional groups on the removal of SO2 from flue gases by N-doped activated carbon powders and fibres

SO₂ removal from flue gases by carbonaceous materials is determined by their behaviour as catalysts for SO₂ oxidation into SO₃ or H₂SO₄ in the presence of O₂ or O₂ and steam, respectively. Previous studies have demonstrated that nitrogen (N) functional groups are active sites for the adsorption and oxidation of SO₂, although the nature of the N groups with the higher activity had not been established yet. For this reason, in the present work a number of activated carbons (AC) and activated carbon fibres (ACF) doped with N atoms have been prepared using different methods. The number and nature of these N groups have been assessed by XPS. The materials prepared have a wide range of nitrogen content, which is distributed into different chemical species. In this way, we were able to determine the effect of the N content and the role of the different N-containing functional groups on the catalytic activity for SO₂ oxidation. The results confirm that, although the pore volume and the pore size distribution strongly influence the catalytic activity, the presence of N species at the surface increases the catalytic activity. They also demonstrate that, among the different N functional groups, pyridinic nitrogen is the most active for this reaction.     

Pore structure alteration of porous carbon by catalytic coke deposition

The feasibility of preparing Carbon Molecular Sieve (CMS) by tailoring pore structure of activated carbon under catalytic cracking of benzene has been examined. In this method, benzene vapour was cracked over metal-impregnated activated carbon particles at 523–773 K. Among the metal catalysts tested, only cobalt exhibited significant cracking activity toward benzene. In this range of temperature coke was originated on the metal surface only, therefore an excessive coke deposition as indicated in non-catalytic process was not observed. The amount of coke and the site of deposition in the pore network were determined to some extent by the metal loading as well as the rate of benzene cracking. Raman spectra indicated that the coke produced was less amorphous than those produced in non-catalytic processes. Only a small loss in micropore volume and surface area was observed after the coke deposition process. The CMS produced was tested for its adsorption characteristics of carbon dioxide and methane. The improvement in the CO₂/CH₄ kinetic selectivity was observed.     

Adsorption of p-nitrophenol on an activated carbon with different oxidations

An activated carbon prepared from olive stones has been modified through oxidation by nitric acid or sodium hypochlorite. These treatments introduced large amounts of oxygen groups, which were characterized by mass-spectrometry, temperature-programmed desorption (DTP-MS). Both CO₂- and CO-evolving groups were created by these oxidation treatments. A part of these oxidized samples was then outgassed under vacuum up to 823 K in order to remove most of the CO₂-evolving groups from their surface. Oxidized samples have a smaller surface area than the original sample. The subsequent partial outgassing increases the surface area which, however, does not reach the value it had before oxidation. p-Nitrophenol (PNP) adsorption isotherms from aqueous solutions were determined at 298 K for the original, oxidized, and partly outgassed samples. The results confirm the presence of an intermediate plateau at low equilibrium PNP concentration (at about 10 mg/l). The relative effects of textural versus surface chemistry on PNP uptakes are then discussed. The presence of CO-evolving groups showed no influence on PNP uptakes. The conclusion is that models in which carbonylic groups are basic adsorption sites for substituted phenols can be ruled out for the entire isotherm of PNP obtained with the original carbon. These models are also unlikely for PNP adsorption on oxidized and partly outgassed samples.     

Removal of ionic substances from dilute solution using activated carbon electrodes

Removal of various electrolytes from aqueous solution and a recycling operation were carried out using a flow-through capacitor. The amount of ions removed corresponds to the surface area and especially the micropore volume of the activated carbon electrode. Introduction of acidic functional groups on the surface of the carbon promoted ion removal (i.e. increase in rate and capacity), but there is a limit to the amount of functional groups that can be introduced with good effect. The adsorption-desorption properties of various alkali, alkaline earth and heavy metal sulfates were investigated. It was found that removal characteristics were different for the different types of ions. Depletion of the electrode also differed depending on the electrolyte that was removed. When copper and zinc ions were removed, the surface area of the cathode was reduced by a small amount.     

Phenol wastewater treatment by a two-step adsorption-oxidation process on activated carbon

The interest of a two-step adsorption-oxidation process for treatment of aqueous phenolic effluents has been investigated. This process is based on the use of activated carbon as adsorbent in the first step and as oxidation catalyst in the second step, in a single bi-functional reactor. The main advantage of this process concerns the regeneration-oxidation step, for which only a small quantity of liquid has to be heated and pressurised, reducing then the heat consumption. Calculations and design were performed based on the experimental results obtained separately for the adsorption and the oxidation steps. This two-step adsorption-oxidation process appears to offer good potentialities for treating moderate flow rates of wastewater, especially when the effluent is dilute.     

Pore structure of activated carbons prepared by carbon dioxide and steam activation at different temperatures from extracted rockrose

The influence of the activation temperature on the pore structure of granular activated carbons prepared from rockrose (Cistus ladaniferus L.), extracted previously into petroleum ether, is comparatively studied. The preparation was carried out by pyrolysis of a char in nitrogen and its subsequent activation by carbon dioxide and steam (flow of water controlled to generate the same mol number per minute of water as well as carbon dioxide/nitrogen) at 700-950°C to 40% burn-off. The techniques applied to study the pore structure were: pycnometry (mercury, helium), adsorption (carbon dioxide, 298 K; nitrogen, 77 K), mercury porosimetry and scanning electron microscopy. The preparation by steam activation, especially at 700°C, yields activated carbons showing a total pore volume larger than those prepared by carbon dioxide activation. The pore structures present the greatest differences when the activations are carried out between 700 and 850°C and closer at higher temperatures. At high temperatures, the decrease of differences in pore development caused by carbon dioxide or steam is attributed to an external burn-off. The micropore structure of each activated carbon is mainly formed by wide micropores. At the lowest activation temperatures, especially at 700°C, steam develops the mesoporosity much more than carbon dioxide. At 950°C, a similar reduction of pore volume in the macropore range occurs.     

Physical and chemical characteristics of polymer-based spherical activated carbon and its ability to adsorb organics

The characterization of a polymeric spherical activated carbon (PAC) was performed by comparing its adsorption, porosity, functional groups and some of the physical properties with a commercial spherical activated carbon (CAC). The PAC was about 4 times superior to the CAC with respect to the mechanical strength. The micropore volume of the PAC was about 5% smaller than that of the CAC. The maximum methylene blue adsorption values of the PAC and the CAC were 32 and 14 mg g⁻¹, respectively, which indicated low mesopore volumes as consistent with the values of BJH volume. This resulted in the low butane working capacity values for both activated carbons. Adsorption parameters for the Langmuir and the Freundlich isotherm models were determined for all organic substances tested. Both isotherms were suitable models to analyze the equilibrium data for the removal of all organics. However, the Langmuir model fitted better than the Freundlich model and the adsorption capacities of the PAC were somewhat higher than those of the CAC. The chemical properties of the activated carbons, the pH of solutions and the substituents on absorbates have an effect on adsorption of the organics tested.     

Modified activated carbons for catalytic wet air oxidation of phenol

This study aims at testing several activated carbons for the catalytic wet air oxidation (CWAO) of phenol solutions. Two commercial activated carbons were used both as received and modified by treatment with either HNO₃, (NH₄)₂S₂O₈, or H₂O₂ and by demineralisation with HCl. The activated carbons were characterised by measuring their surface area, distribution of surface functional groups and phenol adsorption capacity. The parent and treated activated carbons were then checked for CWAO using a trickle bed at 140 °C and 2 bar of oxygen partial pressure. The treatments increase the acidic sites, mostly creating lactones and carboxyls though some phenolic and carbonyl groups were also generated. Only (NH₄)₂S₂O₈ treatment yields a significant decrease in surface area. CWAO tests show that catalytic activity mainly depends on the origin of the activated carbon. The modifications generally had a low impact on phenol conversion, which correlates somewhat with the increase in the acidity of the carbons. Characterisation of the used activated carbon evidences that chemisorbed phenolic polymers formed through oxidative coupling and oxygen radicals play a major role in the CWAO over activated carbon.     

Competitive adsorption of a benzene-toluene mixture on activated carbons at low concentration

Previous studies of the adsorption of benzene and toluene at low concentration showed that both porosity and surface chemistry of the activated carbon play an important role. This paper analyses the adsorption behaviour of a mixture of VOCs (benzene-toluene) on AC, due to the lack of information regarding the adsorption of mixtures. Thus, the performance of chemically activated carbons, physically activated carbon with steam and commercial samples is studied. This study shows that chemically activated carbons have better performance than the other samples, showing much higher adsorption capacities, breakthrough times and separation times. Porosity is a key factor and those activated carbons with higher volumes of micropores exhibit higher adsorption capacities and breakthrough times. This work also analyses the state of the adsorbed phase resulting from the mixture adsorption and comparison of the composition of the adsorbed hydrocarbons with that predicted by the ideal adsorption solution theory (IAST), shows good agreement.     

Influence of oxidation process on the adsorption capacity of activated carbons from lignocellulosic precursors

A set of activated carbon materials non-oxidised and oxidised, were successfully prepared from two different lignocellulosic precursors, almond shell and vine shoot, by physical activation with carbon dioxide and posterior oxidation with nitric acid. All samples were characterised in relation to their structural properties and chemical composition, by different techniques, namely nitrogen adsorption at 77 K, elemental analysis (C, H, N, O and S), point of zero charge (PZC) and FTIR. A judicious choice was made to obtain carbon materials with similar structural properties (apparent BET surface area ∼ 850-950 m²g⁻¹, micropore volume ∼ 0.4 cm³g⁻¹, mean pore width ∼ 1.2 nm and external surface area ∼ 14-26 m²g⁻¹). After their characterisation, these microporous activated carbons were also tested for the adsorption of phenolic compounds (p-nitrophenol and phenol) in the liquid phase at room temperature. The performance in liquid phase was correlated with their structural and chemical properties. The oxidation had a major impact at a chemical level but only a moderate modification of the porous structure of the samples. The Langmuir and Freundlich equations were applied to the experimental adsorption isotherms of phenolic compounds with good agreement for the different estimated parameters.     

Adsorption of cadmium ions from aqueous solutions by activated carbon with oxygen-containing functional groups

The adsorption of aqueous cadmium ions (Cd(II)) have been investigated for modified activated carbon (AC-T) with oxygen-containing functional groups. The oxygen-containing groups of AC-T play an important role in Cd(II) ion adsorption onto AC-T. The modified activated carbon is characterized by scanning electron microscopy, Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The results of batch experiments indicate that the maximal adsorption could be achieved over the broad pH range of 4.5 to 6.5. Adsorption isotherms and kinetic study suggest that the sorption of Cd(II) onto AC-T produces monolayer coverage and that adsorption is controlled by chemical adsorption. And the adsorbent has a good reusability. According to the FT-IR and XPS analyses, electrostatic attraction and cation exchange between Cd(II) and oxygen-containing functional groups on AC-T are dominant mechanisms for Cd(II) adsorption.