Textural characteristics,surface chemistry and oxidation of activated carbon

Numerous researches were reviewed and interpreted to depict a comprehensive illustration of activated carbon and its behavior towards oxidation.Activated carbon as one of the most important adsorbents is tried to be described in this review paper by terms of its"Textural Characteristics"and"Surface Chemistry".These two terms,coupled with each other,are responsible for behavior of activated carbon in adsorption processes and in catalytic applications.Although as-prepared activated carbons are usually nonselective and their surfaces suffer from lack of enough reactive groups,their different aspects may be improved and developed by diverse types of modifications.Oxidation is one of the most conventional modifications used for activated carbons.It may be used as a final modification or as a pre-modification followed by further treatment.In this paper,methods of oxidation of activated carbon and other graphene-layer carbon materials are introduced and wet oxidation as an extensively-used category of oxidation is discussed in more detail.     

电化学双电层电容器用新型炭材料及其应用前景

活性炭是目前使用最为广泛的一种电化学双电层电容器（EDLC）的电极材料,但其固有的缺点制约了EDLC性能的进一步提高。用新型高性能炭电极材料可使EDLC比能量和比功率性能进一步提高。这些新型炭材料包括基于石墨层状结构的纳米门炭,基于碳纳米管阵列结构的毛皮炭,通过高温置换反应制备的骨架炭以及电极可整体成型的纳米孔玻态炭。本文介绍了这些炭材料的电化学特性及其在电化学双电层电容器中的应用,指出用这4种新型炭材料制备EDLC的比能量或比功率性能远高于目前活性炭基EDLC,具有良好的应用前景。     

Influence of organics on the structure of water adsorbed on activated carbons

The influence of organics on the structure of water adsorbed on activated carbons was studied using adsorption of nitrogen, benzene, and water, and by (1)H NMR spectroscopy with freezing out of bulk water with the presence of benzene-d(6) or chloroform-d. It was found that interactions of water with the activated carbon surface depend on both structural characteristics (contributions of micro- and mesopores, pore size distributions) of adsorbents and chemical properties (changed by oxidation or reduction) of the adsorbents. Moreover, the interfacial behavior of water is affected by water-insoluble organics such as benzene and chloroform. Changes in the Gibbs free energy of water adsorbed on carbons exposed to air, water, chloroform-d, or benzene-d(6) are related to textural properties of adsorbents and the degree of their oxidation. Since chloroform-d and benzene-d(6) are strongly adsorbed on activated carbons and immiscible with water they replace a significant portion of adsorbed water in micropores, on the walls of mesopores, and in the transport pores of carbons causing changes in the Gibbs free energy and other characteristics of water.     

Study of chromium(VI) adsorption onto modified activated carbons with respect to analytical application

Two different types of modification of activated carbon, by treatment with concentrated solution of HNO₃ and outgassing treatment at high temperature, were studied in order to obtain the most effective adsorption of chromium(VI) ions from water solution. The basic parameters affecting the adsorption capacity of Cr(VI) ions on modified activated carbons were studied in details and the effect of modifications of activated carbons has been determined by studying the initial runs of adsorption isotherms. The obtained Cr(VI) adsorption isotherms were well fitted in the Freundlich equation. The reduction of Cr(VI) to Cr(III) and further ion exchange mechanism of adsorption onto oxidizing activated carbon and surface precipitation to Cr(OH)₃ in case of outgassing activated carbon were found as the main adsorption mechanisms of Cr(VI) ions onto modified activated carbons. Presence of chlorides and nitrates in studied adsorption system strongly decreased the adsorption ability of Cr(VI) onto outgassing activated carbon and mechanism of this behavior is proposed.     

The dependence of the electronic conductivity of carbon molecular sieve electrodes on their charging states

The dependence of the electronic conductivity of activated carbon electrodes on their potential in electrolyte solutions was examined. Kapton polymer films underwent carbonization (1000 degrees C), followed by a mild oxidation process (CO(2) at 900 degrees C) for various periods of time, to obtain carbons of different pore structures. A specially designed cell was assembled in order to measure the conductivity of carbon electrodes at different potentials in solutions. When the carbon electrodes possessed molecular sieving properties, a remarkable dependence of their conductivity on their charging state was observed. Aqueous electrolyte solutions containing ions of different sizes were used in order to demonstrate this phenomenon. As the average pore size of the activated carbons was larger, their molecular sieving ability was lower, and the dependence of their conductivity on their charging state regained its classical form. This behavior is discussed herein.     

Reactive adsorption of penicillin on activated carbons

A series of activated carbons with varied surface chemistry, obtained by wet oxidation and thermal treatment, was used for the removal of penicillin from low concentration aqueous solution. It was found that the carbon surface chemistry favors the degradation of the antibiotic, giving rise to various intermediates detected both in solution and in the adsorbed phase (deposited with the pore structure of the activated carbons). The confinement of penicillin molecules entrapped in the nanopores of activated carbons of acidic nature accelerates their degradation compared to that one in the bulk solution, which can be linked the strong local pH fall inside the pores. Degradation also takes place in activated carbons of basic pH, although the nature and partition of the intermediates formed differ from those in the acidic carbons. In both cases most of the breakdown products do not present therapeutic activity.     

Ozonation of naphthalenesulphonic acid in the aqueous phase in the presence of basic activated carbons

The present study aimed to explore the possibility of increasing the purification efficacy of ozone in the removal of high-toxicity contaminants by using carbons of basic character and to analyze the mechanism involved in this process. These carbons were prepared by treating a commercial activated carbon (Witco, W) with ammonia (W-A), ammonium carbonate (W-C), or urea (W-U), under high pressure and temperature. The ammonia and carbonate treatments slightly increased the mesoporosity and, to a greater degree, the macroporosity of carbon W, whereas the urea treatment produced an increase in the porosity across the whole range of pore sizes. In addition, treatment of the activated carbon with these nitrogenating agents produced a marked change in the chemical nature of its surface. Thus, according to the pH of the point of zero charge (pHPZC) values obtained for each sample, carbon W was neutral (pHPZC = 7.12), but the treated carbons were basic, especially carbon W-U (pHPZC = 8.85). This basicity results from an increased concentration of basic oxygenated and nitrogenated surface functional groups, as confirmed by the results of elemental and XPS analyses. An increase in the degradation of 1,3,6-naphthalenetrisulfonic acid was observed when the activated carbon samples were added to the system. This degradation was especially enhanced in the presence of carbon W-U. The increased NTS degradation rate in the presence of the activated carbon is due to an increased concentration of highly reactive radicals in the system. When the catalytic activity of the activated carbon samples was related to their chemical and textural characteristics, it was found that: (i) The catalytic activity increased with an increase in the surface basicity. Interestingly, in the sample with greatest catalytic activity in NTS ozonation, carbon W-U, most of the nitrogenated surface groups introduced were pyrrol groups. These groups increase the electronic density of the basal plane of the activated carbon, thereby enhancing the reduction of ozone on the surface and the generation of highly reactive radicals in the system. (ii) The greater catalytic activity of carbon W-U may also be partly related to its greater surface area and higher volume of mesopores and macropores; these large pores facilitate access of the ozone to the surface active centers of the carbon, increasing its catalytic activity. The presence of the activated carbon samples during NTS ozonation also favored the removal of total organic carbon present in the solution, due to (a) transformation of organic matter into CO2 through the generation of highly reactive species catalyzed by the presence of the activated carbons (catalytic contribution) and (b) adsorption of NTS oxidation byproducts on the activated carbon (adsorptive contribution). The results obtained show that activated carbons treated with nitrogenating agents are very promising catalysts for application in the ozonation of aromatic compounds.     

活性炭液相吸附去除噻吩硫化物的研究

迄今为止，国内外降低汽油硫含量的方法主要有原料加氢脱硫、汽油加氢脱硫、溶剂抽提脱硫、催化裂化脱硫、氧化脱硫、生物脱硫、吸附脱硫及组合技术，同时一些非常规技术如膜过程脱硫、等离子体和光脱硫也在积极探索之中。     

Empirical Relationships Describing Energetics of Adsorption at Low Coverages on Microporous Carbons

The fundamental empirical relationships that correlate the adsorption energy with physicochemical parameters of adsorbates are discussed. Based on the experimental data of the adsorption enthalpy of different organic adsorbates on microporous activated carbons some new correlations between adsorption enthalpy and entropy at zero surface coverage and physicochemical parameters of adsorbed molecules are proposed. It is shown that they can be applied for the calculation of carbon porosity. The influence of carbon surface oxidation on its energetic heterogeneity is also discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Analysis of oxidation behavior under dry air of neat and Ta‐alloyed furan‐resin‐derived carbons heat treated at 3000 °C

Oxidation behavior and structural changes of furan‐resin‐derived carbons heat treated at 3000 °C were investigated at 500 and 700 °C under dry air. Thermogravimetric analysis (TGA), Raman spectroscopy and X‐ray photoelectron spectroscopy (XPS) were employed to detect and understand this behavior and the changes. Effect of tantalum on antioxidation property of Ta‐alloyed carbon was also analyzed. The neat and Ta‐alloyed carbons had insignificant weight losses even after being kept at 500 °C for 12 h, while the Ta‐alloyed carbon had weight loss lower than that of the neat carbon after being kept at 700 °C for 6 h. It has been found by XPS that oxidation involves oxygen in internal area as well as on external surface of the carbons. It was also inferred that the carbon stored with oxygen in deeper internal area was easily oxidized. Ta alloying leads to change of the state of the Fermi energy on the specimens, which may cause the antioxidation property. Copyright © 2005 John Wiley & Sons, Ltd.     

Changes in microporosity and CH4 adsorptivity of preoxidized pitch-based activated carbon fibers by Mg deposition

Magnesium oxide/hydroxide was deposited on pitch-based activated carbon fibers which were previously oxidized in air at different temperatures, and the changes in carbon oxidation activity, microporosity, and CH4 adsorptivity of the parent carbons due to Mg deposition were examined. DTA results, chemical analysis, and DRIFT spectra indicate that Mg species are mainly supported on the -COOH groups of the parent carbons, which serve as the catalysts to improve the oxidation activity of carbon. Mg deposition either increases or decreases the specific surface area, pore volume, and average micropore width of the parent carbon depending on the preoxidation temperatures. Mg deposition does not simply enhance CH4 adsorptivity: the complex changes are due to the differences in the supporting states of Mg species and slight modifications in micropore structure.     

微波辐射法制备活性炭的应用研究进展

对微波辐射技术在活性炭的活化、表面改性及再生过程中的研究进展进行了概述。微波功率是影响活性炭的活化、改性、再生及其吸附性能和产率的主要因素之一。众多实验结果表明微波辐射技术是制备活性炭材料和提高活性炭吸附性能的有效途径。     

改性活性炭对噻吩的吸附性能研究

用过硫酸铵、臭氧对椰壳活性炭和煤基活性炭进行氧化改性,研究了改性活性炭对噻吩的吸附性能,材料结构袁征结果表明,经两种方法氧化处理后,椰壳炭的孔结构基本保持不变,而煤基炭的比表面积和孔容有所增加.Boehm滴定发现氧化后活性炭表面含氧官能团数量增加并由FT-TR图谱得到证实.氧化处理提高了噻吩在活性炭表面的吸附容量与Langmuir和Freundlich两种吸附等温线方程的相关性.采用拟一级、拟二级和粒子内扩散模型速率方程来考察吸附动力学,并计算了这些动力学模型的速率常数,拟二级模型和实验数据之间有较好的相关性.同时对影响吸附性能的因素进行了分析.     

Cadmium ion adsorption on different carbon adsorbents from aqueous solutions. Effect of surface chemistry, pore texture, ionic strength, and dissolved natural organic matter

Adsorption of Cd(II) species at pH = 5 was studied on three carbon adsorbents: granular activated carbon, activated carbon fiber, and activated carbon cloth. As-received and oxidized adsorbents were used. Cd(II) adsorption greatly increased after oxidation due to the introduction of carboxyl groups. The use of a buffer solution to control the pH introduced some changes in the surface chemistry of carbons through the adsorption of one of the compounds used, biphthalate anions. The increase in ionic strength reduced Cd(II) uptake on both as-received and oxidized carbons due to a screening of the electrostatic attractions between the Cd(II) positive species and the negative surface charge, which in the case of as-received carbons derived from the biphthalate anions adsorbed and in the oxidized ones from the carboxyl groups. Tannic acid was used as a model compound for natural organic matter. Its adsorption was greatly reduced after oxidation, and most of the carbon adsorbents preadsorbed with tannic acid showed an increase in Cd(II) uptake. In the case of competitive adsorption between Cd(II) species and tannic acid molecules, there was a decrease in Cd(II) uptake on the as-received carbon whereas the contrary occurred with the oxidized carbons. These results illustrate the great importance of carbon surface chemistry in this competitive adsorption process. Finally, under all experimental conditions used, when the adsorption capacity of carbons was compared under the same conditions it increased in the following order: granular activated carbon < activated carbon fiber < activated carbon cloth.     

Optimum conditions for adsorptive storage

The storage of gases in porous adsorbents, such as activated carbon and carbon nanotubes, is examined here thermodynamically from a systems viewpoint, considering the entire adsorption-desorption cycle. The results provide concrete objective criteria to guide the search for the "Holy Grail" adsorbent, for which the adsorptive delivery is maximized. It is shown that, for ambient temperature storage of hydrogen and delivery between 30 and 1.5 bar pressure, for the optimum adsorbent the adsorption enthalpy change is 15.1 kJ/mol. For carbons, for which the average enthalpy change is typically 5.8 kJ/mol, an optimum operating temperature of about 115 K is predicted. For methane, an optimum enthalpy change of 18.8 kJ/mol is found, with the optimum temperature for carbons being 254 K. It is also demonstrated that for maximum delivery of the gas the optimum adsorbent must be homogeneous, and that introduction of heterogeneity, such as by ball milling, irradiation, and other means, can only provide small increases in physisorption-related delivery for hydrogen. For methane, heterogeneity is always detrimental, at any value of average adsorption enthalpy change. These results are confirmed with the help of experimental data from the literature, as well as extensive Monte Carlo simulations conducted here using slit pore models of activated carbons as well as atomistic models of carbon nanotubes. The simulations also demonstrate that carbon nanotubes offer little or no advantage over activated carbons in terms of enhanced delivery, when used as storage media for either hydrogen or methane.     

Preparation of activated carbon from date pits: Effect of the activation agent and liquid phase oxidation

Two series of activated carbons have been prepared from date pits; series C, using carbon dioxide as activating agent, and series S, prepared by activation with steam under the same experimental conditions. The obtained samples were oxidized with nitric acid in order to introduce more oxygen surface groups. The surface area and porosity of the parent and oxidized activated carbons were studied by N₂ adsorption at 77 K and CO₂ adsorption at 273 K. The oxygen surface complexes were characterized by temperature-programmed decomposition (TPD). The results show that carbon dioxide and steam activations produce microporous carbons with an increasing amount of CO evolving groups when increasing the burn-off. On the other hand, oxidation with nitric acid increases the amount of CO and CO₂ evolved by the decomposition of surface oxygen groups, this increase being related to the development of porosity in the carbon with the degree of activation and to the activating agent used (CO₂ versus steam).     

Importance of structural and chemical heterogeneity of activated carbon surfaces for adsorption of dibenzothiophene

The performance of various activated carbons obtained from different carbon precursors (i.e., plastic waste, coal, and wood) as adsorbents for the desulfurization of liquid hydrocarbon fuels was evaluated. To increase surface heterogeneity, the carbon surface was modified by oxidation with ammonium persulfate. The results showed the importance of activated carbon pore sizes and surface chemistry for the adsorption of dibenzothiophene (DBT) from liquid phase. Adsorption of DBT on activated carbons is governed by two types of contributions: physical and chemical interactions. The former include dispersive interactions in the microporous network of the carbons. While the volume of micropores governs the amount physisorbed, mesopores control the kinetics of the process. On the other hand, introduction of surface functional groups enhances the performance of the activated carbons as a result of specific interactions between the acidic centers of the carbon and the basic structure of DBT molecule as well as sulfur-sulfur interactions.     

Treatment of colored effluent of the textile industry in Bangladesh using zinc chloride treated indigenous activated carbons

The adsorption of colored compounds from the textile dyeing effluents of Bangladesh on granulated activated carbons produced from indigenous vegetable sources by chemical activation with zinc chloride was studied. The most important parameters in chemical activation were found be the chemical ratio of ZnCl₂ to feed (3:1), carbonization temperature (450-465 °C) and activation time (80 min). The adsorbances at 511 nm (red effluent) and 615 nm (blue effluent) were used for color estimation. It is established that at optimum temperature (50 °C), time of contact (30-40 min) and adsorbent loading (2 g l⁻¹), activated carbons developed from Segun saw-dust and water hyacinth showed substantial capability to remove coloring materials from the effluents. It is observed that adsorption of reactive dyes by all sorts of activated carbons is higher than disperse dyes. It is explained that activated carbon, because of its acidic nature, can better adsorb reactive dye particles containing large number of nitrogen sites and -SO₃Na group in their structure. The use of carbons would be economical, as saw-dust and water hyacinth are waste products and abundant in Bangladesh.     

Wetting and non-wetting fluids in surface-functionalised activated carbons

Pore filling by non-polar and polar molecules is investigated by small-angle X-ray scattering in activated carbons that had been surface-functionalised to different degrees by oxidation. A pseudo-binary model for the scattering response is used to trace the filling characteristics of water and n-hexane in the pore structure. While the pores are uniformly filled by n-hexane, pore filling by water is only partial. In the latter case, a significant contribution from liquid–vapour interfaces appears and the system becomes fully ternary. This feature is direct evidence of the development of water droplets, which form even in the most oxidised carbon. The appreciable differences between the carbons illustrate the influence on the small-angle X-ray scattering response of surface chemistry and of the polarity of the adsorbed molecules.     

Calorimetric evaluation of activated carbons modified for phenol and 2,4-dinitrophenol adsorption

Two commercial activated carbons with differences in their superficial chemistry, one granular and the other pelletised, were modified for use in phenol and 2,4-dinitrophenol adsorption. In this paper, changes to the activated carbon surface will be evaluated from their immersion calorimetry in water and benzene, and they will then be compared with Area BET, chemical parameters, micropore size distributions and hydrophobicity factors of the modified activated carbons. The activated carbons were modified using 60 % solutions of phosphoric acid (H₃PO₄), nitric acid (HNO₃), zinc chloride (ZnCl₂) and potassium hydroxide (KOH); the activated carbon/solution ratio was 1:3 and impregnation was conducted 291 K for a period of 72 h before samples were washed until a constant pH was obtained. Water immersion calorimetry showed that the best results were obtained from activated carbons modified with nitric acid, which increased from ?10.6 to ?29.8 J g^?1 for modified granular activated carbon, and ?30.9 to ?129.3 J g^?1 for pelletised activated carbon. Additionally, they showed the best results in phenol and 2.4-dititrophenol adsorption. Those results indicate that impregnation with nitric acid under the employed conditions could generate a greater presence of oxygenated groups on their surface, which favours hydrogen bond formation and the increased adsorption of polar compounds. It should also be noted that immersion enthalpy in benzene for modified activated carbon with nitric acid is the method with the lowest value, which is consistent with the increased presence of polar groups on its surface. Regarding hydrophobicity factors, it was observed that granular carbons modified with nitric acid and potassium hydroxide have the lowest ratios, indicating greater interaction with water.