Heat of Adsorption of Pure Sulfur Hexafluoride on Micro-Mesoporous Adsorbents

The isotherms and the isosteric heats of adsorption of pure SF₆ were measured on two microporous zeolites (NaX and Silicalite), one mesoporous alumina, and two activated carbons (BPL and PCB) at 305 K. The adsorption isotherms were Type I by Brunauer classification. The PCB carbon adsorbed SF₆ most strongly and the alumina adsorbed SF₆ most weakly. The adsorption of SF₆ on the other three materials were comparable in the low pressure region despite their drastic differences in the physicochemical properties. The heat of adsorption of SF₆ on the silicalite and the alumina remained practically constant over a large range of coverage. The heat of adsorption of SF₆ increased with increasing adsorbate loading on the NaX zeolite in the high coverage region. The heat of adsorption of SF₆ on the activated carbons decreased with increasing adsorbate loading before leveling off in the high coverage region.     

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.     

Cluster-Mediated Water Adsorption on Carbon Nanopores

The adsorption isotherms of water at 303 K and N2 at 77 K on various kinds of porous carbons were compared with each other. The saturated amounts of water adsorbed on carbons almost coincided with amounts of N2 adsorption in micropores. Although carbon aerogel samples have mesopores of the great pore volume, the saturated amount of adsorbed water was close to the micropore volume which is much small than the mesopore volume. These adsorption data on carbon aerogels indicated that the water molecules are not adsorbed in mesopores, but in micropores only. The adsorption isotherms of water on activated carbon having micropores of smaller than 0.7 nm in width had no clear adsorption hysteresis, while the water adsorption isotherms on micropores of greater than 0.7 nm had a remarkable adsorption hysteresis above P/P0 = 0.5. The disappearance of the clear hysteresis for smaller micropores suggested that the cluster of water molecules of about 0.7 nm in size gives rise to the water adsorption on the hydrophobic micropores; the formation and the structure of clusters of water molecules were associated with the adsorption mechanism. The cluster-mediated pore filling mechanism was proposed with a special relevance to the evidence on the formation of the ordered water molecular assembly in the carbon micropores by in situ X-ray diffraction.     

Adsorption of aqueous metal ions on oxygen and nitrogen functionalized nanoporous activated carbons

In this study, the adsorption characteristics of two series of oxygen and nitrogen functionalized activated carbons were investigated. These series were a low nitrogen content (approximately 1 wt % daf) carbon series derived from coconut shell and a high nitrogen content (approximately 8 wt % daf) carbon series derived from polyacrylonitrile. In both series, the oxygen contents were varied over the range approximately 2-22 wt % daf. The porous structures of the functionalized activated carbons were characterized using N(2) (77 K) and CO(2) (273 K) adsorption. Only minor changes in the porous structure were observed in both series. This allowed the effect of changes in functional group concentrations on metal ion adsorption to be studied without major influences due to differences in porous structure characteristics. The surface group characteristics were examined by Fourier transform infrared (FTIR) spectroscopy, acid/base titrations, and measurement of the point of zero charge (pH(PZC)). The adsorption of aqueous metal ion species, M(2+)(aq), on acidic oxygen functional group sites mainly involves an ion exchange mechanism. The ratios of protons displaced to the amount of M(2+)(aq) metal species adsorbed have a linear relationship for the carbons with pH(PZC) < or = 4.15. Hydrolysis of metal species in solution may affect the adsorption of metal ion species and displacement of protons. In the case of basic carbons, both protons and metal ions are adsorbed on the carbons. The complex nature of competitive adsorption between the proton and metal ion species and the amphoteric character of carbon surfaces are discussed in relation to the mechanism of adsorption.     

Potassium bromate modification of the granular activated carbon and its effect on nickel adsorption

Granular Activated Carbon (GAC), a commercial adsorbent for the removal of heavy metals was treated chemically with potassium bromate for it’s surface modification and it’s adsorption capacity was investigated with nickel ions. There was an increase in the adsorption capacity of the modified carbon by 90–95% in comparison to the raw granular activated carbon towards nickel ion adsorption. Potassium Bromate oxidation treatment was employed for a period of about 30 mins initially followed by 60 mins and the oxidized carbons were adsorbed with nickel ions. Metal sorption characteristics of as received and modified activated carbons were measured in batch experiments. Batch adsorption was successfully modeled by Langmuir Isotherm Model which indicates monolayer adsorption. The adsorption isotherms also fit well to the Freundlich Model. Effects of pH of initial solution, time of oxidation and mode of treatment on the adsorption process were studied. Experimental results showed that metal uptake increased with an increase in pH and oxidation time. The samples were characterized by Scanning Electron Microscope (SEM) studies and surface area analyzer.     

A study of the static and dynamic adsorption of Zn(II) ions on carbon materials from aqueous solutions

The effect of surface oxidation, solution pH, and ionic strength on the adsorption of Zn(II) ions from aqueous solution under static conditions was studied using commercial activated carbons in the form of grains and cloth. In addition, the effects of surface oxidation and the presence of dissolved natural organic matter (tannic acid) were studied under dynamic conditions using activated carbon cloth column beds. Under static conditions, surface oxidation largely increased Zn2+ uptake and two H+ ions were displaced from the oxidized carbon surface per Zn(II) ion adsorbed. It is proposed that adsorption of Zn(II) on the as-received basic carbons was due to C(pi)-cation interactions. An increase in solution pH in the range 3-6 increased Zn(II) uptake, whereas an increase in ionic strength decreased Zn(II) uptake because of the screening effect of the added salt. In the experiments carried out with carbon column beds, the oxidized activated carbon cloth was also more effective than the as-received carbon to remove Zn(II) ions. In this case, the presence of tannic acid decreased the efficiency of the oxidized activated carbon cloth bed to remove Zn(II) ions. An increase in the tannic acid initial concentration had a greater effect on the removal of tannic acid than on the removal of Zn(II) by the column bed. This may be a consequence of the greater size of tannic acid molecules and their low affinity for oxidized carbon surfaces.     

Characteristics of Nonafluorobutyl Methyl Ether (NFE) Adsorption onto Activated Carbon Fibers and Different-Size-Activated Carbon Particles

The characteristics of adsorption of 1,1,1,2,2,3,3,4,4-nonafluorobutyl methyl ether (NFE), a chlorofluorocarbon (CFC) replacement, onto six different activated carbon; preparations (three activated carbon fibers and three different-sized activated carbon particles) were investigated to evaluate the interaction between activated carbon surfaces and NFE. The amount of NFE adsorbed onto the three activated carbon fibers increased with increasing specific surface area and pore volume. The amount of NFE adsorbed onto the three different-sized-activated carbon particles increased with an increase in the particle diameter of the granular activated carbon. The differential heat of the NFE adsorption onto three activated carbon fibers depended on the porosity structure of the activated carbon fibers. The adsorption rate of NFE was also investigated in order to evaluate the efficiency of NFE recovery by the activated carbon surface. The Sameshima equation was used to obtain the isotherms of NFE adsorption onto the activated carbon fibers and different-sized-activated carbon particles. The rate constant k for NFE adsorption onto activated carbon fibers was larger for increased specific surface area and pore volume. The rate of NFE adsorption on activated carbons of three different particle sizes decreased with increasing particle diameter at a low initial pressure. The adsorption isotherms of NFE for the six activated carbons conformed to the Dubinin-Radushkevich equation; the constants BE(0) (the affinity between adsorbate and adsorbent) and W(0) (the adsorption capacity) were calculated. These results indicated that the interaction between the activated carbon and NFE was larger with the smaller specific surface area of the activated carbon fibers and with the smaller particle diameter of the different-sized-activated carbon particles. The degree of packing of NFE in the pores of the activated carbon fibers was greater than that in the pores of the granular activated carbons. Copyright 2000 Academic Press.     

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.     

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.     

Adsorption of lignite-derived humic acids on coal-based mesoporous activated carbons

The adsorption by a coal-based mesoporous activated carbon of humic acids (HAs) isolated from two Polish lignites was studied. For comparison, a commercial Aldrich humic acid was also included into this study. The differences in chemical structure and functional groups of HAs were determined by elemental analysis and infrared spectroscopy DRIFT. Two activated carbons used differed in terms of mesopore volume, mesopore size distribution, and chemical properties of the surface. The kinetics of adsorption of HAs have been discussed using three kinetic models, i.e., the first-order Lagergren model, the pseudo-second-order model, and the intraparticle diffusion model. It was found that the adsorption of HAs from alkaline solution on mesoporous activated carbon proceeds according to the pseudo-second-order model. The correlation coefficients were close to 1. The intraparticle diffusion of HA molecules within the carbon particle was identified to be the rate-limiting step. Comparing the two activated carbons, the carbon with a higher volume of pores with widths of 10-50 nm showed a greater removal efficiency of HA. An increase in the Freundlich adsorption capacity with decreasing carbon content of HA was observed. Among the HAs studied, S-HA shows characteristics indicating the highest contribution of small-size fraction. The S-HA was removed by both activated carbons to the highest extent. The effect of pH solution on the adsorption of HA was examined over the range pH 5.4-12.2. It was found that the extent of adsorption decreased with decreasing pH of the solution.     

Competitive adsorption and desorption of a bi-solute mixture: effect of activated carbon type

This study aims to clarify the effects of carbon activation type and physical form on the extent of adsorption capacity and desorption capacity of a bi-solute mixture of phenol and 2-chlorophenol (2-CP). For this purpose, two different PACs; thermally activated Norit SA4 and chemically activated Norit CA1, and their granular countertypes with similar physical characteristics, thermally activated Norit PKDA and chemically activated Norit CAgran, were used. The thermally activated carbons were better adsorbers for phenol and 2-CP compared with chemically activated carbons, but adsorption was more reversible in the latter case. 2-CP was adsorbed preferentially by each type of activated carbon, but adsorption of phenol was strongly suppressed in the presence of 2-CP. The simplified ideal adsorbed solution (SIAS) model underestimated the 2-CP loadings and overestimated the phenol loadings. However, the improved and modified forms of the SIAS model could better predict the competitive adsorption. The type of carbon activation was decisive in the application of these models. For each activated carbon type, phenol was desorbed more readily in the bi-solute case, but desorption of 2-CP was less compared with single-solute. This was attributed to higher energies of 2-CP adsorption.     

Adsorption of NH3 onto activated carbon prepared from palm shells impregnated with H2SO4

Adsorption of ammonia (NH3) onto activated carbons prepared from palm shells impregnated with sulfuric acid (H2SO4) was investigated. The effects of activation temperature and acid concentration on pore surface area development were studied. The relatively large micropore surface areas of the palm-shell activated carbons prepared by H2SO4 activation suggest their potential applications in gas adsorption. Adsorption experiments at a fixed temperature showed that the amounts of NH3 adsorbed onto the chemically activated carbons, unlike those prepared by CO2 thermal activation, were not solely dependent on the specific pore surface areas of the adsorbents. Further adsorption tests for a wide range of temperatures suggested combined physisorption and chemisorption of NH3. Desorption tests at the same temperature as adsorption and at an elevated temperature were carried out to confirm the occurrence of chemisorption due to the interaction between NH3 and some oxygen functional groups via hydrogen bonding. The surface functional groups on the adsorbent surface were detected by Fourier transform infrared spectroscopy. The amounts of NH3 adsorbed by chemisorption were correlated with the contents of elemental oxygen present in the adsorbents. Mechanisms for chemical activation and adsorption processes are proposed based on the observed phenomena.     

Mesoporous Carbons of Well-Organized Structure in the Removal of Dyes from Aqueous Solutions

Mesoporous carbons with differentiated properties were synthesized by using the method of impregnation of mesoporous well-organized silicas. The obtained carbonaceous materials and microporous activated carbon were investigated by applying different methods in order to determine their structural, surface and adsorption properties towards selected dyes from aqueous solutions. In order to verify applicability of adsorbents for removing dyes the equilibrium and kinetic experimental data were measured and analyzed by applying various equations and models. The structural and acid-base properties of the investigated carbons were evaluated by Small-Angle X-ray Scattering (SAXS) technique, adsorption/desorption of nitrogen, potentiometric titration, and Transmission Electron Microscopy (TEM). The results of these techniques are complementary, indicating the type of porosity and structural ordering, e.g., the pore sizes determined from the SAXS data are in good agreement with those obtained from nitrogen sorption data. The SAXS and TEM data confirm the regularity of mesoporous carbon structure. The adsorption experiment, especially kinetic measurements, reveals the utility of mesoporous carbons in dye removing, taking into account not only the adsorption uptake but also the adsorption rate.     

Comparative Study of the Adsorption from Aqueous Solutions and the Desorption of Phenol and Nonylphenol Substrates on Activated Carbons

Adsorption of phenol and nonylphenol from aqueous solutions on microporous activated carbons has been studied. The phenol isotherm changes from L-shaped for surface oxygen group free carbon (I sample) to a two-stepped isotherm for oxidized carbon (IN sample, HNO(3) treated) Furthermore, the adsorbed amounts diminish in about 25% on IN carbon. It is proposed that a change in the adsorption mechanism take place; i.e., weak interaction forces between the pi electrons in phenol and the pi electron in carbon are present on the original I carbon, while a donor-acceptor complex on the oxidized IN carbon is operating between basic surface oxygen groups and phenol aromatic rings. The shape of nonylphenol isotherms is two-stepped for both carbons. The introduction of acidic oxygen surface groups on the carbon enhances the specific nonylphenol adsorption by about 40%. This may be interpreted as being due to the fact that nonylphenol is hydrogen-bonded to the oxidized carbon surface by means of acidic groups. Thermal desorption experiments indicate that phenol is mainly physisorbed. Thermal desorption further confirms that nonylphenol is possibly bonded to oxygen surface groups by hydrogen bonds. Copyright 2001 Academic Press.     

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.     

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.     

Cyclodextrins adsorbed onto activated carbons: preparation, characterization, and effect on the dispersibility of the particles in water

We have investigated the adsorption equilibrium of selected cyclodextrins onto activated carbons. A number of parameters were examined including the type of carbon material, the size of macrocyclic cavity, and the chemical nature of the oligosaccharide (e.g., neutral, anionic, or cationic cyclodextrin). Adsorption isotherm studies revealed that the maximum amount of cyclodextrin immobilized on the carbon surface is obtained for the native β-CD, while the adsorption capacity of the ionic cyclodextrins derivatives strongly depends on the net surface charge of the activated carbon. The affinity of cyclodextrins for activated carbons was further utilized to prepare modified activated carbons containing controlled amounts of cyclodextrins through an adsorption process. The resulting materials were characterized by N(2) adsorption-desorption volumetric measurements, FTIR and Raman spectroscopy, while the quantitative determination of the oligosaccharide content on activated carbons was performed by gravimetric measurements. On the basis of the Turbiscan results, it was found that the chemical structure of cyclodextrins, which are incorporated in the carbon framework, had significant influence on the dispersibility and stabilization of the solid particles in water. Agglomeration and precipitation of the carbon particles were markedly suppressed with substituted cyclodextrins whose hydroxyl groups were partially substituted by methyl or alkylammonium groups.     

Competitive adsorption of aqueous metal ions on an oxidized nanoporous activated carbon

Competitive adsorption is the usual situation in real applications, and it is of critical importance in determining the overall performance of an adsorbent. In this study, the competitive adsorption characteristics of all the combinations of binary mixtures of aqueous metal ion species Ca2+(aq), Cd2+(aq), Pb2+(aq), and Hg2+(aq) on a functionalized activated carbon were investigated. The porous structure of the functionalized active carbon was characterized using N2 (77 K) and CO2 (273 K) adsorption. The surface group characteristics were examined by temperature-programmed desorption, Fourier transform infrared spectroscopy, Raman spectroscopy, acid/base titrations, and measurement of the point of zero charge (pHpzc). The adsorption of aqueous metal ion species, M2+(aq), on acidic oxygen functional group sites mainly involves an ion exchange mechanism. The ratios of protons displaced to the amount of M2+(aq) metal species adsorbed have a linear relationship for both single-ion and binary mixtures of these species. Hydrolysis of metal species in solution may affect the adsorption, and this is the case for adsorption of Hg2+(aq) and Pb2+(aq). Competitive adsorption decreases the amounts of individual metal ions adsorbed, but the maximum amounts adsorbed still follow the order Hg2+(aq) > Pb2+(aq) > Cd2+(aq) > Ca2+(aq) obtained for single metal ion adsorption. The adsorption isotherms for single metal ion species were used to develop a model for competitive adsorption in binary mixtures, involving exchange of ions in solution with surface proton sites and adsorbed metal ions, with the species having different accessibilities to the porous structure. The model was validated against the experimental data.     

One‐stage Template‐free KOH Activation for Mesopore‐enriched Carbons and Their Application in CO2 Capture

Activated carbons with a high mesoporous structure were prepared by a one‐stage KOH activation process without the assistance of templates and further used as adsorbents for CO₂ capture. The physical and chemical properties as well as the pore structures of the resulting mesoporous carbons were characterized by N₂ adsorption isotherms, scanning electron microscopy (SEM ), X‐ray diffraction (XRD ), Raman spectroscopy, and Fourier transform infrared (FTIR ) spectroscopy. The activated carbon showed greater specific surface area and mesopore volume as the activation temperature was increased up to 600°C, showing a uniform pore structure, great surface area (up to ~815 m²/g), and high mesopore ratio (~55%). The activated sample exhibited competitive CO₂ adsorption capacities at 1 atm pressure, reaching 2.29 and 3.4 mmol/g at 25 and 0°C, respectively. This study highlights the potential of well‐designed mesoporous carbon as an adsorbent for CO₂ removal and widespread gas adsorption applications.     

一种测量超临界条件下苯酚吸附等温线方法

超临界吸附相平衡是超临界吸附／色谱分离过程设计的基础,通常,研究超临界吸附相平衡的实验不仅需要在高压下操作,而且需使用耐高压的检测器,本文提出一种测量超临界条件下吸附相平衡关系的“扩容减压吸收法”方法,它不需要耐高压检测器,以“苯酚－活性炭－超临界二氧化碳流体”为体系,测定了苯酚在活性炭－超临界二氧化碳流体之间的吸附相平衡关系,测定了苯酚在两种活性炭上的超临界吸附等温线,比较了苯酚在超临界条件和常