Structural characteristics of activated carbons and ibuprofen adsorption affected by bovine serum albumin

Structural characteristics of a series of MAST carbons were studied using scanning electron microscopy images and the nitrogen adsorption isotherms analyzed with several models of pores and different adsorption equations. A developed model of pores as a mixture of gaps between spherical nanoparticles and slitlike pores was found appropriate for MAST carbons. Adsorption of ibuprofen [2-(4-isobutylphenyl)propionic acid] on activated carbons possessing different pore size distributions in protein-free and bovine serum albumin (BSA)-containing aqueous solutions reveals the importance of the contribution of mesopores to the total porosity of adsorbents. The influence of the mesoporosity increases when considering the removal of the drug from the protein-containing solution. Cellulose-coated microporous carbon Norit RBX adsorbs significantly smaller amounts of ibuprofen than uncoated micro/mesoporous MAST carbons whose adsorption capability increases with increasing mesoporosity and specific surface area, burnoff dependent variable. A similar effect of broad pores is observed on adsorption of fibrinogen on the same carbons. Analysis of the ibuprofen adsorption data using Langmuir and D'Arcy-Watt equations as the kernel of the Fredholm integral equation shows that the nonuniformity of ibuprofen adsorption complexes diminishes with the presence of BSA. This effect may be explained by a partial adsorption of ibuprofen onto protein molecules immobilized on carbon particles and blocking of a portion of narrow pores.     

Adsorption of dyes on carbon xerogels and templated carbons: influence of surface chemistry

The removal of textile dyes by adsorption onto carbon materials with extended mesoporosity is addressed in the present work. Two types of high surface area carbon adsorbents were prepared, namely a carbon xerogel and a templated carbon. Both materials were subsequently subjected to appropriate treatments in order to modify their surface chemistries, while keeping their textural properties relatively unchanged. The carbon adsorbents were extensively characterized by different techniques in order to correlate their adsorption performances with the corresponding surface properties. The behavior of the different materials was evaluated by determining equilibrium adsorption isotherms of two anionic dyes (Reactive Red 241 and Acid Blue 113) at different pH values. The results are compared with data previously obtained with commercial activated carbons subjected to the same treatments, and discussed in terms of the carbon surface chemistry and the interaction between the dye molecules and the adsorbent surface (dispersive and electrostatic interactions).     

Porosity characteristics and pore developments of various particle sizes palm kernel shells activated carbon (PKSAC) and its potential applications

The adsorption behaviour and the micro- and mesopore size distributions of commercial palm kernel shell activated carbons (PKSAC) and other commercial activated carbon are characterized. The results showed that PKSAC are predominantly microporous materials, where micropores account 68–79% of total porosity. On the other hand, commercial activated carbons: Norit SX Plus, Calgon 12×40, and Shirasagi “A” activated carbons contained high mesopore fraction ranging from 33 to 52%. The analysis showed that the degree of mesoporosity of PKSAC is increased steadily with the decrease of particle size. This is due to the presence of channels interconnect the smaller pores in the interior of smaller particle size PKSAC. The smaller size PKSAC particle that is highly mesoporous has preformed better on the adsorption of larger molecules such as methylene blue. On the other hand, bigger size PKSAC particle has better performance on the adsorption of smaller adsorbates such as iodine.     

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.     

Assessing surface chemistry and pore structure of active carbons by a combination of physisorption (H2O, Ar, N2, CO2), XPS and TPD-MS

In order to address open questions concerning the surface chemistry and pore structure characterization of nanoporous carbons, we performed extensive experiments by combining various experimental techniques on a series of commercially available activated carbons which exhibit diverse surface chemistry characteristics. Pore size analysis was performed on Ar (87 K), N₂ (77 K) and CO₂ (273 K) adsorption isotherms using state-of-the art methods based on density functional theory, including the recently developed quenched solid density functional theory (QSDFT). A detailed study of the surface chemistry was obtained by applying temperature programmed desorption coupled with mass spectrometry (TPD-MS) as well as XPS (X-Ray-Photoelectron Scattering). This information together with the pore structure information leads to a reliable interpretation of systematic water adsorption measurements obtained on these materials. Our results clearly suggest that water adsorption is indeed a sensitive tool for detecting differences in surface chemistry between chemically and physically activated active carbon materials with comparable ultramicropore structure. The occurrence of sorption hysteresis associated with the filling of micro- and narrow mesopores (in a range where nitrogen and argon isotherms are reversible) provides additional structural information, complementary to the insights from argon/nitrogen/carbon dioxide adsorption.     

Structural characteristics of modified activated carbons and adsorption of explosives

Several series of activated carbons prepared by catalytic and noncatalytic gasification and subsequent deposition of pyrocarbon by pyrolysis of methylene chloride or n-amyl alcohol were studied by FTIR, chromatography, and adsorption methods using nitrogen and probe organics (explosives). The relationships between the textural characteristics of carbon samples and the recovery rates (eta) of explosives on solid-phase extraction (SPE) using different solvents for their elution after adsorption were analyzed using experimental and quantum chemical calculation results. The eta values for nitrate esters, cyclic nitroamines, and nitroaromatics only partially correlate with different adsorbent parameters (characterizing microporosity, mesoporosity, pore size distributions, etc.), polarity of eluting solvents, or characteristics of probe molecules, since there are many factors strongly affecting the recovery rates. Some of the synthesized carbons provide higher eta values than those for such commercial adsorbents as Hypercarb and Envicarb.     

Comparative study for the removal of methylene blue via adsorption and photocatalytic degradation

Physically and chemically activated carbons were prepared from date pits and olive stones. Titania and WO(x)-TiO(2)/MCM-41 were prepared as photoactive catalysts. Surface characterizations were investigated from ash content, pH, base neutralization capacities and FT-IR techniques. The textural characteristics, namely specific surface area (S(BET)) and pore texture, were determined from low temperature adsorption of N(2) at 77 K. The decolorization of aqueous solution of methylene blue was performed by means of two alternative methods. Steam-activated carbons own higher surface area compared with ZnCl(2)-activated carbons, and the micropore surface area represents the major contribution of the total area. Steam-activated carbons were the most efficient decolorizing adsorbents owing to its higher surface area, total pore volume and the basic nature of the surface. The calculated values of DeltaG(0), DeltaH(0) and DeltaS(0) indicate the spontaneous behavior of adsorption. The photocatalytic degradation is more convenient method in decolorizing of methylene blue compared with the adsorption process onto activated carbons.     

A TPD-MS study of the adsorption of ethanol/cyclohexane mixture on activated carbons

The adsorption of ethanol/cyclohexane binary mixtures on different types of activated carbons was studied in this work by temperature programmed desorption coupled with mass spectroscopy (TPD-MS). The texture, morphology and surface chemistry of the carbons were evaluated by N₂ adsorption, scanning electron microscopy (SEM) and TPD-MS techniques. The ethanol and cyclohexane TPD-MS desorption profiles showed that specific interactions between the carbon material and the adsorbate are involved during the adsorption. Most of the activated carbons adsorb strongly ethanol on the surface, leading to desorption temperatures above 100 °C. Only one carbon exhibits an affinity for cyclohexane. These observations were correlated to the different surface chemistry of the materials.     

Adsorption characteristics of activated carbons obtained from corncobs

Dried, crushed, corncobs were carbonized at 500°C and steam activated (in one- or two-step schemes), or activated with H₃PO₄. The products were characterized by N₂ adsorption at 77 K, using the BET, _s and DR methods. Adsorption capacity was demonstrated by the iodine and phenol numbers, and the isotherms of methylene blue and Pb²⁺ ions, from aqueous solutions. A distribution of porosity in the carbons was estimated within the various ranges (ultra-, super-, meso- and macropores). Simple carbonization yields a poor adsorbing carbon; only its uptake for iodine was high and proposed to be due to an addition reaction on residual unsaturation of the parent lignocellulosic structures. Enhanced porosity was best associated with chemical activation and/or steam pyrolysis at 700°C. These activated carbons proved highly porous and rich in mesopores, and showed high adsorption capacity for methylene blue and Pb²⁺ ions. Phenol uptake was found to depend on surface chemical nature of the carbon rather than its porous properties. Corncobs were postulated to be feasible as feedstock to produce good adsorbing carbons, under the one-step activation schemes outlined here.     

Role of surface chemistry in adsorption of phenol on activated carbons

Two samples of activated carbon of wood origin were oxidized using ammonium persulfate. The structural properties and surface chemistry of the samples and their oxidized counterparts were characterized using sorption of nitrogen and Boehm titration, respectively. Phenol adsorption from solution (at trace concentrations) was studied at temperatures close to ambient without maintaining a specific pH of the solution. The results showed, as expected, that the phenol uptake is dependent on both the porosity and surface chemistry of the carbons. Furthermore, phenol adsorption showed a strong dependence on the number of carboxylic groups due to two factors: (1) phenol reacts with carboxylic groups on the carbon surface, forming an ester bond, and (2) carboxylic groups on the carbon surface remove the pi-electron from the activated carbon aromatic ring matrix, causing a decrease in the strength of interactions between the benzene ring of phenol and the carbon's basal planes, which decreases the uptake of phenol.     

Microporous activated carbons prepared from palm shell by thermal activation and their application to sulfur dioxide adsorption

Textural characterization of activated carbons prepared from palm shell by thermal activation with carbon dioxide (CO(2)) gas is reported in this paper. Palm shell (endocarp) is an abundant agricultural solid waste from palm-oil processing mills in many tropical countries such as Malaysia, Indonesia, and Thailand. The effects of activation temperature on the textural properties of the palm-shell activated carbons, namely specific surface area (BET method), porosity, and microporosity, were investigated. The activated carbons prepared from palm shell possessed well-developed porosity, predominantly microporosity, leading to potential applications in gas-phase adsorption for air pollution control. Static and dynamic adsorption tests for sulfur dioxide (SO(2)), a common gaseous pollutant, were carried out in a thermogravimetric analyzer and a packed column configuration respectively. The effects of adsorption temperature, adsorbate inlet concentration, and adsorbate superficial velocity on the adsorptive performance of the prepared activated carbons were studied. The palm-shell activated carbon was found to have substantial capability for the adsorption of SO(2), comparable to those of some commercial products and an adsorbent derived from another biomass.     

Optimization of the Conditions for the Cr (III) Adsorption on Activated Carbon

In order to understand the patterns of the adsorption equilibrium of Cr (III) on activated carbon, the adsorption process was studied by two different ways: classical batch experiments on commercial Norit and Merck activated carbons and their oxidized forms in a wide range of pHs; and extended time-based tests at the same pH values on the same adsorbents. This approach allowed us to understand the role of texture, chemical carbon surface functionality and experimental conditions (initial pH of the solution, contact time and adsorbate/adsorbent ratio) on the effectiveness of Cr (III) removal. The adsorption process of Cr (III) at (24 ± 1^∘C) on Merck and Norit activated carbons and their oxidized forms were studied at pH values between 1.5 and 5 (either adjusted or buffered). Chromium concentration was fixed at 200 ppm. The carbon loading ranged from 1.2 to 20 g/l. The carbon/Cr (III) solution contact time was varied from 0.5–1 month to 5 months, to ensure that the saturation of the carbon level was reached. According to the data obtained, the presence of carboxylic groups on carbon surface seems to enhance Cr (III) uptake at initial pH of the solution in the range between 2 and 4. Depending on the nature of the adsorbent surface chemistry, the contact time to reach equilibrium may range from 3 to 5 months. There is an optimum carbon loading which limits the Cr (III) uptake/removal at given pH value. In order to understand the adsorption process, an ion exchange, surface complex and surface precipitation were considered. This paper was presented in the 5th Brazilian Meeting on Adsorption, held at Natal, Brazil, 18-21 July, 2004.     

Surface morphology of nanostructured polymer-based activated carbons

Complementary techniques, including nitrogen adsorption, small-angle X-ray scattering (SAXS), and atomic force microscopy (AFM), have been utilized to characterize the surface features of highly microporous carbon materials prepared from highly aromatic polymers. Nitrogen adsorption measurement interpreted by BET, DR, HK, and NLDFT methods reveals these nanostructured activated carbons exhibit a high surface area of up to 4000 m2/g, a micropore volume up to approximately 1.75 mL/g, and an average pore size of approximately 10-20 angstroms. A modified equation, based on Porod's law, the Debye-Bueche equation, and fractal dimension theories, has been proposed and successfully applied to analyze the SAXS spectra and to extract the porous texture of these unique activated carbons. AFM 3D imaging combined with the Fourier transform technique has been applied to statistically quantify pore sizes on the carbon surface.     

Adsorption Behaviors of CO2 and NH3 on Chemically Surface-Treated Activated Carbons

The adsorption characteristics of activated carbon treated with 30 wt% HCl and 30 wt% NaOH were investigated. The acid and base values were determined by Boehm's method and the surface structures were studied by the BET method with N2 adsorption and iodine adsorption capacity. Also the adsorption properties of the activated carbons treated with acid and base chemical solutions were investigated with CO2 and NH3 adsorptions. Different adsorption behaviors of CO2 and NH3 on the modified activated carbons were observed, even though the physical surfaces of the activated carbons (i.e., specific surface area, pore size, and pore volume) were not significantly changed. Copyright 1999 Academic Press.     

Comparisons of porous and adsorption properties of carbons activated by steam and KOH

In this work, fir woods and pistachio shells were used as source materials to prepare porous carbons, which were activated by physical (steam) and chemical (KOH) methods. Pore properties of these activated carbons including the BET surface area, pore volume, pore size distribution, and pore diameter were first characterized by a t-plot method based on N(2) adsorption isotherms. Highly porous activated carbons with BET surface area up to 1009-1096 m(2)/g were obtained. The steam and KOH activation methods produced carbons with mesopore content in the range 9-15 and 33-49%, respectively. The adsorption equilibria and kinetics of tannic acid, methylene blue, 4-chlorophenol, and phenol from water on such carbons at 30 degrees C were then investigated to check their chemical characteristics. The Freundlich equation gave a better fit to all adsorption isotherms than the Langmuir equation. On the other hand, the intraparticle diffusion model could best follow all adsorption processes. In comparison with KOH-activated carbons, it was shown that the rate of external surface adsorption with steam-activated carbons was significantly higher but the rate of intraparticle diffusion was much lower.     

The physical and surface chemical characteristics of activated carbons and the adsorption of methylene blue from wastewater

Adsorption of a basic dye, methylene blue, from aqueous solutions onto as-received activated carbons and acid-treated carbons was investigated. The physical and surface chemical properties of the activated carbons were characterized using BET-N(2) adsorption, X-ray photoelectron spectroscopy (XPS), and mass titration. It was found that acid treatment had little effect on carbon textural characteristics but significantly changed the surface chemical properties, resulting in an adverse effect on dye adsorption. The physical properties of activated carbon, such as surface area and pore volume, have little effect on dye adsorption, while the pore size distribution and the surface chemical characteristics play important roles in dye adsorption. The pH value of the solution also influences the adsorption capacity significantly. For methylene blue, a higher pH of solution favors the adsorption capacity. The kinetic adsorption of methylene blue on all carbons follows a pseudo-second-order equation.     

Water vapor adsorption and microporous structure of carbon adsorbents. 18. Effect of surface chemistry of activated carbons on water vapor adsorption

This investigation has been devoted to a study of the chemical composition of the surfaces of activated carbons. A study has been made of the way in which changes in the surface chemistry of a series of carbons, as a result of heat treatment, affects the nature of their adsorption of water vapor. A differentiation has been made between oxygen-containing groups found on the surface of activated carbons before and after their heat treatment. It has been established that the original adsorption centers, which play a determining role in water vapor adsorption by activated carbons, comprise functional groups like strongly acidic free hydrogen ions, carboxylic and phenolic groups, situated on on the pore surface of the activated carbons. The number of these functional groups on the pore surface of the activated carbons has been correlated with the parametera ₀ (the number of original adsorption centers) in the isotherm equation for water vapor adsorption. The relative pressure corresponding to the formation of an adsorption layer on the surface of the activated carbons has been shown to depend on the number of original adsorption centers, the acidic functional groups.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 35–40, January, 1991.     

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).