Surface-layer composite sorbents for the rapid preconcentration of volatile organic substances from aqueous solutions and gas atmospheres

The regularities of the dynamic sorption of volatile organic substances from aqueous solutions and atmospheric air on surface-layer composite sorbents, in which a finely dispersed sorption-active material is retained due to adhesion on the surface of a relatively coarsely dispersed macroporous carrier, were determined. The analytical capabilities of such sorbents were studied, and they were found more effective than traditional porous bulk sorbents used for the concentration of volatile organic compounds from aqueous solutions and gas atmospheres.     

Graphitized carbons for solid-phase extraction

The objective of this review is to provide updated information about the most important features of graphitized carbonaceous sorbents used for solid-phase extraction (SPE) of organic compounds from liquid natural matrices or extracts. The surface characteristics of graphitized carbon blacks and porous graphitic carbons are described which are responsible for the various types interactions (hydrophobic, electronic and ion-exchange) with analytes. The method development is given which is based on the prediction from liquid chromatographic retention data obtained using porous graphitic carbon. Emphasis is placed on their capability for trapping very polar and water-soluble analytes from aqueous samples. Comparison is made between carbon-based SPE sorbents and other reversed-phase materials such as octadecyl silicas and highly cross-linked copolymers. Especially, the difficulty encountered for the desorption of some strongly retained analytes is explained by LC data and solutions are given for optimizing the composition and volume of the desorption solution. Many examples illustrate the various common features of graphitized carbons which are the extraction of very polar analytes and multiresidue extractions. Some applications are specific to graphitized carbon black due to the presence of surface functional groups. They include the extraction of anionic compounds such as benzene and naphthalene sulfonates or acidic pesticides. Other applications are specific to porous graphitic carbon due to its flat and homogeneous surface. One example is the trace extraction of coplanar polychlorinated biphenyls (PCBs), dibenzo-p-dioxins and dibenzofurans from other PCB congeners.     

Sorption of cesium on copper hexacyanoferrate/polymer/silica composites in batch and dynamic conditions

The sorption of cesium ions from aqueous solutions on composite sorbents was investigated in static (by the batch method) and dynamic (on column) conditions. The composite sorbents consisted of copper hexacyanoferrate retained by an anion-exchange polymeric layer bound to porous silica beads. The influence of cesium concentration and solution flow rates on cesium sorption were studied. The cesium sorption isotherm obtained is of the Langmuir type. The shape of the breakthrough curves and the sorption capacity for cesium depend on the preparation procedure of the composites.     

Effect of surface area and heteroatom of porous carbon materials on electrochemical capacitance in aqueous and organic electrolytes

A series of porous carbon materials with wide range of specific surface areas and different heteroatom contents had been prepared using polyaniline as carbon precursor and KOH as an activating agent. Effect of surface area and heteroatom of porous carbon materials on specific capacitance was investigated thoroughly in two typical aqueous KOH and organic 1-butyl-3- methylimidazolium tetrafluoroborate/acetonitirle electrolytes. The different trends of capacitance performance were observed in these two electrolytes. Electrochemical analyses suggested that the presence of faradaic interactions on heteroatom-enriched carbon materials in organic environment is less significant than that observed in aqueous electrolytes. Thus, in aqueous electrolyte, a balance between surface area and heteroatom content of activated porous carbon would be found to develop a supercapacitor with high energy density. In organic electrolyte, the capacitance performance of porous carbon is strongly dependent on the surface area. The results may be useful for the design of porous carbon-based supercapacitor with the desired capacitive performance in aqueous and organic electrolytes.     

Palladium(II) recovery in extraction and sorption systems with 5-amino-1,2,4-thiadiazole derivatives

The distribution of palladium(II) between the solutions of hydrochloric and nitric acids and the solutions of 5-amino-1,2,4-thiadiazole derivatives in 1,2-dichloroethane depending on acid and extractant concentrations in the aqueous and organic phases, respectively, was studied. The stoichiometry of the extracted complexes was determined, and the concentration constants of extraction were calculated. The applicability of macroporous polymer sorbents noncovalently modified with the test reagents to the sorption recovery of palladium(II) from nitric acid solutions was demonstrated.     

Analytical potential of fullerene as adsorbent for organic and organometallic compounds from aqueous solutions

In this work, the analytical potential of C60 fullerene as a sorbent for organic and organometallic compounds from aqueous solutions was studied for the first time. Fullerene adsorbs many types of organic substances (e.g., N-methylcarbamates, phenols, polycyclic aromatic hydrocarbons, amines) with efficiencies that depend on the nature of the compound concerned and never exceed 60%. Conventional sorbents such as XAD-2 or polyurethane foam are more efficient than C60 for this purpose. Organometallic compounds (viz. metalocenes and organoleads) are quantitatively adsorbed on C60 via the formation of neutral complexes or chelates; the adsorption constant is dramatically increased by the use of classical reagents such as pyrrolidinedithiocarbamate or diethyldithiocarbamate. A complementary comparative study on the adsorption of organometallic complexes on RP-C18 and silica gel 100, among others, showed C60 to be superior as sorbent. All experiments in this work were carried out by using continuous flow configurations and gas chromatography-atomic absorption spectrometry techniques.     

A porous carbon material prepared by template synthesis using Aerosil

Synthesis of a porous carbon material using Aerosil as template is suggested. The material obtained has high specific surface area (2800 m² g^?1) and high limiting sorption volume (6.2 cm³ g^?1). The porous carbon material prepared by this procedure can be used in solid-phase extraction of organic toxicants from aqueous solutions.     

Flexibility in metal-organic framework materials: Impact on sorption properties

Recent years have seen the development of a new class of porous coordination polymers known collectively as metal organic framework materials (MOFs). This review outlines recent progress in understanding how adsorption characteristics of these systems differ from rigid classical sorbents such as activated carbon and zeolites. Gas/vapor adsorption studies for characterization of the porous structures of MOF materials are reviewed and differences in adsorption characteristics based on detailed measurement of equilibrium and dynamical sorption behavior, compared with previous generations of sorbents, are highlighted. The role of framework flexibility and specific structural features, such as windows and pore cavities, within the MOF porous structures are discussed in relation to adsorption mechanisms.     

Advantages and disadvantages of various kinds of adsorbents used in industrial extraction of [Au(CN)<Subscript>2</Subscript>]<Superscript>–</Superscript> anions from cyanide solutions and pulps

Comparative study of an industrially used activated carbon of WSC-207C-GR brand, strongly basic anion exchanger MINIX, and weakly basic anion exchanger Purogold S992 in recovery of [Au(CN)₂]^– ions from cyanide aqueous solutions and slurries was carried out. It was found that the strongly basic anion exchanger MINIX has the highest adsorption rate of the cyanide complex of gold(I), whereas the activated carbon and the weakly basic ion exchanger possess a substantially higher selectivity toward the complex of gold(I). Use of each of the three sorbents makes it possible to solve the problem of the cyanide leaching of gold from ores containing natural substances that exhibit adsorbent properties with respect to the dicyanoaurate(I) ion. The influence exerted by the amount of kerosene additive and volume fraction of a sorbent on the efficiency of gold recovery by the sorbent in cyanidation of ores in the “carbon-in-pulp” and “resin-in-pulp” modes.     

Establishing the feasibility of coupled solid-phase extraction-solid-phase derivatization for acidic herbicides

The significance of this research is that it improves analytical methodology used for organic chemicals in aqueous solutions by establishing the feasibility of heterogeneous chemical derivatization at the liquid-solid interface (i.e., solid-phase reaction or solid-phase derivatization). A solid-phase derivatization method for determining chlorinated herbicide acids was developed. Solid-phase extraction was used to concentrate and retain analytes on sorbents for subsequent solid-phase derivatization. Background interferences were removed from the chromatograms by electronically subtracting the responses of blank, nonfortified analyses from spiked samples. Two extraction sorbents (octadecyl bonded silica and polystyrene-divinylbenzene) and two derivatizing reagents (BF3-MeOH and trimethylsilyldiazomethane) were investigated. Recovery of 13 chlorinated herbicide acids--including pentachlorophenol, dinoseb, and bentazon (having a derivatizable functional group, -OH or -NH, bonded directly to a phenyl group); dicamba, picloram, acifluorfen, 3,5-dichlorobenzoic acid, and dacthal (having a derivatizable functional group, -COOH, bonded directly to a phenyl group); and 2,4-D, 2,4,5-T, dichlorprop, 2,4,5-TP, and 2,4-DB (having a derivatizable functional group, -COOH, bonded directly to a sp3 carbon atom)--was tested. The analytical method developed was proven successful for determining acidic herbicides, except for the dacthal diacid metabolite, in aqueous samples.     

Supplementary research of clinoptilolite-rich tuff composites after adsorption trials using the XPS technique

The paper deals with fabrication of carbonized and hydrophobized clinoptilolite-rich tuff using organic carbon rich substances, here particularly starch and waste vegetable residues, which were pyrolytically combusted and covered the external zeolite surface. Hydrophobization of the zeolite external surface was accomplished by octadecylammonium surfactant. Both surface modified clinoptilolite-rich tuffs were tested and compared with each other with regard to removal of organic (phenol) and inorganic (chromate, arsenate) pollutants from aqueous solutions. These elaborated composites with surface adsorbed pollutant species were analysed by X-ray photoelectron spectroscopy (XPS).     

Simulation of adsorption-coagulation purification of liquid radioactive waste to remove surfactants

Sorption purification of liquid radioactive waste from special laundries of nuclear power plants to remove surfactants was simulated. The adsorption of an anionic surfactant, sodium dodecyl sulfate, on various carbon sorbents from complex-composition aqueous solutions containing mineral salts and complexing additives was studied.     

A Stable Metal–Organic Framework Featuring a Local Buffer Environment for Carbon Dioxide Fixation

A majority of metal–organic frameworks (MOFs) fail to preserve their physical and chemical properties after exposure to acidic, neutral, or alkaline aqueous solutions, therefore limiting their practical applications in many areas. The strategy demonstrated herein is the design and synthesis of an organic ligand that behaves as a buffer to drastically boost the aqueous stability of a porous MOF (JUC‐1000), which maintains its structural integrity at low and high pH values. The local buffer environment resulting from the weak acid–base pairs of the custom‐designed organic ligand also greatly facilitates the performance of JUC‐1000 in the chemical fixation of carbon dioxide under ambient conditions, outperforming a series of benchmark catalysts.     

Extraction of rare-earth,yttrium, and scandium perchlorates by podands bearing diphenylphosphorylacetamide terminal groups

Partition of trace amounts of metal (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, and Sc) perchlorates was studied between aqueous HClO₄ solutions and dichloroethane solutions of phosphorus podands bearing two Ph₂P(O)CH₂C(O)NH-terminal groups linked via di-and triethylene glycol spacers. The stoichiometry of extracted complexes was determined. The efficiency of metal ion recovery to the organic phase was studied as a function of aqueous HClO₄ concentration and nature of the organic solvent. The compounds synthesized have higher metal extraction capacities in HClO₄ solutions than (dibutylcarbamoyl)diphenylphoshine oxide. The utility of macroporous polymer sorbents impregnated by these podands for extracting and concentrating rare earth(III) and scandium(III) ions from aqueous perchlorate solutions was demonstrated.     

Assessment of the possibility of the performance of a chromatomembrane mass-exchange process on granular composite carbon–fluoroplastic sorbents for the generation of standard gas mixtures

A principal possibility of the performance of continuous and discrete versions of a chromatomembrane mass-exchange process (CMP) in a liquid–gas system on granular supports and composite carbon–fluoroplastic sorbents is shown. In contrast to the previously used block (monolithic) composite sorbents, for their granular analogues, an increase in the concentration of sorption-active materials up to 40% of the support weight is possible. It is shown that composite sorbents included in the CMP scheme are most effective for the generation of standard gas mixtures of volatile organic substances.     

Mineral-carbon sorbents based on post-decarbonization lime and mixture of hydrocarbons

Summary An attempt was made to obtain mineral-carbon sorbents from waste products of petrochemical industry: lime from the decarbonization of river water to be used in technology and hydrocarbon wastes obtained in the treatment of industrial waste waters. The sorbents were prepared by thermal decomposition of mixtures of the mineral and carbon components. In order to optimize the preparation conditions, physicochemical studies were performed of both the mineral matrix and the mineral-carbon sorbents. Adsorption measurements involving nitrogen, water, and benzene as adsorbates were used for determining the parameters of porous structure of the obtained materials and their hydrophilic-hydrophobic properties. The properties influencing the sorptive properties of the organic compounds present in the petrochemical wastes were pointed out.     

Adsorption and DSC study of mineral–carbon sorbents obtained from coal tar pitch–polymer compositions

The purpose of this study was to determine the possibility of producing hydrophobic mesoporous mineral–carbon sorbents from aluminum hydroxide and compositions of coal tar pitch–polymers on carbonization at 600 °C in a nitrogen atmosphere. Blends of the products of co-precipitation of aluminum hydroxide in the carbonaceous substances medium were subjected to carbonization process. The extent of porous structure development was evaluated using low temperature nitrogen adsorption, adsorption of benzene vapors, and adsorption of iodine from aqueous solution. The highest value of BET surface area of about 370 m²/g was achieved for the carbonization product obtained from co-precipitated raw components with 10 wt% compositions coal tar pitch–polymer. These materials demonstrated high capacity to reduce organic pollutions from sewage. Pitch–polymer composition containing poly(ethylene terephthalate) or phenol–formaldehyde resin was studied by the means of DSC method in order to determine the high-temperature transformations taking place under the conditions of carbonization. DSC method enables to determine i.a. the decomposition temperatures of carbonizates produced from pitch–polymer compositions and the evaluation of their sorption abilities. The additive of poly(ethylene terephthalate) and phenol–formaldehyde resin caused the increase of thermal resistance of the pitch expressed by higher decomposition temperatures.     

State of adsorption layers of fatty acids on the surfaces of iron, manganese, and copper ferrites

States of adsorbed substances in surface layers arising during the adsorption of oleic, linoleic, and linolenic acids from carbon tetrachloride, heptane, and cyclohexane solutions on the surfaces of iron, manganese, and copper ferrites, are investigated. Adsorption isotherms and two-dimensional state diagrams of surface layers of iron, manganese, and copper ferrites are obtained experimentally. It is shown that the adsorption of fatty acids from solutions in organic solvents proceeds via filling the volume of the ferrites?? porous space with adsorption solutions, while the state of ferrite surface layers changes due to the structural rearrangement of adsorption solutions upon an increase in solute concentration.     

Sequestration of naphthenic acids from aqueous solution using β-cyclodextrin-based polyurethanes

The sorption characteristics of naphthenic acids (NAs) in their anion form with β-cyclodextrin (β-CD) based polyurethanes, as sorbents, from aqueous solutions that simulate the conditions of oil sands process water (OSPW) are presented. The copolymer sorbents were synthesized at various β-CD:diisocyanate monomer mole ratios (e.g., 1:1, 1:2, and 1:3) with diisocyanates of variable molecular size and degree of unsaturation. The equilibrium sorption properties of the copolymer sorbents were characterized using sorption isotherms in aqueous solution at pH 9.00 with electrospray ionization mass spectrometry to monitor the equilibrium unbound fraction of anionic NAs in the aqueous phase. The copolymer sorbents were characterized in the solid state using (13)C CP-MAS NMR spectroscopy, IR spectroscopy and elemental analysis. The sorption results of the copolymer sorbents with anion forms of NAs in solution were compared with a commercially available carbonaceous standard: granular activated carbon (GAC). The monolayer sorption capacities of the sorbents (Q(m)) were obtained from either the Langmuir or the Sips isotherm model used to characterize the sorption characteristics of each copolymer sorbent. The estimated sorption capacity for GAC was 142 mg NAs per g sorbent whereas the polymeric materials ranged from 0-75 mg NAs per g sorbent over the experimental conditions investigated. In general, significant differences in the sorption capacities between GAC and the copolymer sorbents were related to the differences in the accessible surface areas and pore structure characteristics of the sorbents. The Sips parameter (K(eq)) for GAC and the copolymer materials reveal differences in the relative binding affinity of NAs to the sorbent framework in accordance with the synthetic ratios and the value of Q(m). The diisocyanate linker plays a secondary role in the sorption mechanism, whereas the β-CD macrocycle in the copolymer framework is the main sorption site for NAs because of the formation of inclusion complexes with β-CD.     

Hydrophilic nature and sorption-diffusion properties of nanocomposite hybrid polysulfone films

Hybrid nanocomposite films containing silica (??11.4 wt.%) or titania (??18.8 wt.%) in the polymer matrix were prepared by the sol-gel method using the hydrolytic polycondensation of tetraethoxysilane and tetrabutoxysilane in a THF solution of aromatic polymer, polysulfone (PSF). The influence of the oxide nature and the film composition on the structure, the interaction of the polymer with oxides, hydrophilicity, and sorption-diffusion properties of the hybrid films were studied by FTIR spectroscopy, atomic force microscopy, dynamic light scattering, and a complex of other physicochemical methods. The absence of chemical or intermolecular hydrogen bonds between the polymer and oxide particles in the PSF films was shown. The average size of the oxides (SiO₂, ??20 nm; TiO₂, ??90 nm) in the films and roughness of their surface (??0.2?C0.8 nm) were determined. The introduction of oxides into the polymer matrix increases the hydrophilic properties and the ability of the PSF films to swell in water; the diffusion coefficients of water and permeability of water vapor in the PSF films also increase. Titania also induces a more considerable change in the structure of the polymer matrix and more strongly affects the sorption-diffusion properties of the hybrid films in aqueous solutions of THF. All prepared nanocomposite films PSF/SiO₂ and PSF/TiO₂ are capable of extracting an organic component from aqueous solutions and can be used as sorbents and membrane films for the removal of organic substances from the aqueous medium.