Chemistry of the surface and structural and adsorption properties of fluorinated carbon fiber and an adsorbent based on it

The chemistry of the surface and structural and adsorption properties of fluorinated carbon fiber were studied by IR spectroscopy, gas chromatography, and static adsorption of vapors and dyes from aqueous solutions. Also, the quantitative characteristics of the influence of a binder (polytetrafluoroethylene) used to prepare a granulated adsorbent on the basis of the fiber were determined. The functional properties of the adsorbent were found to be largely determined by the properties of the initial fluorocarbon fiber. Fluorocarbons were shown to possess a developed porous structure and highly hydrophobic chemically homogeneous nonpolar surface for the adsorption of most of the organic compounds studied.     

Adsorption and structural characteristics of the surface of modified nanodiamond powders

The adsorption of benzene and water vapors on the surface of detonation nanodiamond powders that differed in particle size, degree of their strong aggregation, and chemical state of their surface was studied. Specific features of the processes of adsorption of polar and nonpolar molecules on chemically modified surfaces of nanodiamonds are analyzed.     

Characterization of sorption mechanisms of solid-phase microextraction with volatile organic compounds in air samples using a linear solvation energy relationship approach

The linear solvation energy relationship (LSER) model was used to characterize interactions responsible for sorption of volatile organic compounds (VOCs) in air samples on six different solid-phase microextraction (SPME) fibers at 296K and zero relative humidity. The polydimethylsiloxane and polyacrylate fibers sorption data were also modeled at different relative humidities in the range of 10-90% and influence of water vapors on the extraction process is discussed. The LSER equations were obtained by a multiple regression of the distribution coefficients of 14 probe solutes on an appropriate SPME fiber against the solvation parameters of the solutes. The derived LSER equations successfully predicted the VOC distribution coefficients and the selectivity of individual SPME fibers for the various volatile solutes. The LSER approach coupled with SPME is a relatively simple and reliable tool to rapidly characterize the sorption mechanism of VOCs with various stationary phases and may potentially be applied to design and test new chromatographic materials for sampling or separation of VOCs.     

Sorption interactions of volatile organic compounds with organoclays under different humidities by using linear solvation energy relationships

Organoclays are usually used as sorbents to reduce the spread of organic compounds and to remove them at contaminated sites. The sorption equilibrium and the mechanisms of volatile organic compounds (VOCs) on organoclays under different humidities are helpful for developing efficient organoclays and for predicting the fate of VOCs in the environment. In this study, the organoclay was synthesized through exchanging inorganic cations by hexadecyltrimethyl ammonium (HDTMA) into montmorillonite, resulting in 12?% of organic content. The surface area of organoclay was smaller than the unmodified clay due to the incorporation of organic cations into the interlayer. Both adsorption on organoclay surface and partition into the incorporated HDTMA in organoclay played roles on the sorption process. Compared the sorption coefficients in montmorillonite and different modified clays, the incorporated organic cations overcame the inhibition effect of hydrophilic surface of clay on the sorption process of hydrophobic organic compounds from water. The sorption coefficients of VOC vapors on organoclay were further characterized using a linear solvation energy relationship (LSER). The fitted LSER equations were obtained by a multiple regression of the sorption coefficients of 22 probe chemicals against their solvation parameters. The coefficients of the five-parameter LSER equations showed that high HDTMA-content montmorillonite interacts with VOC molecules mainly through dispersion, partly through dipolarity/polarizability and hydrogen-bonds as well as with negative π-/n-electron pair interaction. The interaction analysis by LSERs suggests that the potential predominant factors governing the sorption of VOCs are dispersion interactions under all tested humidity conditions, similar with the lower level modified clay. The derived LSER equations successfully fit the sorption coefficients of VOCs on organoclay under different humidity conditions. It is helpful to design better toxic vapor removal strategy and evaluate the fate of organic contaminants in the environment.     

Effects of pore structure and surface chemical characteristics on the adsorption of organic vapors on titanate nanotubes

Effects of pore structure and surface chemical characteristics of titanate nanotubes (TNTs) on their adsorptive removal of organic vapors were investigated. TNTs were prepared via a hydrothermal treatment of TiO₂ powders in a 10 M NaOH solution at 150?°C for 24?h, and subsequently washed with HCl aqueous solution of different concentrations. Effects of acid washing process (or the sodium content) on the microstructures and surface chemical characteristics of TNTs were characterized with nitrogen adsorption-desorption isotherms, FTIR, and water vapor adsorption isotherms. For the adsorption experiments, gravimetric techniques were employed to determine the adsorption capacities of TNTs for four organic vapors with similar heats of vaporization (i.e., comparable heats of adsorption) but varying dipole moments and structures, including n-hexane, cyclohexane, toluene, and methyl ethyl ketone (MEK), at isothermal conditions of 20 and 25?°C. The experimental data were correlated by well-known vapor phase models including BET and GAB models. Isosteric heats of adsorption were calculated and heat curves were established. Equilibrium isotherms of organic vapors on TNTs were type II, characterizing vapor condensation to form multilayers. The specific surface area (and pore volume) and hydrophilicity of TNTs were the dominating factors for the determination of their organic vapors adsorption capacity. The GAB isotherm equation fitted the experimental data more closely than the BET equation. The heats of adsorption showed that the adsorption of organic vapors on TNTs was primarily due to physical forces and adsorbates with larger polarity might induce a stronger interaction with TNTs.     

Contact angles of aluminosilicate clays as affected by relative humidity and exchangeable cations

Contact angles of aluminosilicate clays are difficult to determine. Not only does their small particle size present measurement difficulties, but contact angles may vary with relative humidity and cation composition. In this paper, we determined the effects of relative humidity and exchangeable cations on contact angles of three aluminosilicate clays (smectite, kaolinite, illite). Contact angles were measured on clay films with the sessile drop method under different relative humidity (19, 33, 75, 100%), and with clays saturated either with Na, K, Mg, or Ca. The results showed that the water contact angles on smectite increased with relative humidity between 19 and 75%, but for kaolinite and illite, little differences in water contact angles between 19 and 75% relative humidity were observed. For all three clays, however, the water contact angles decreased at 100% relative humidity as compared to the lower relative humidities. Cations affected not only the adsorption of water but also the surface charge, and both factors influenced the contact angles of the clays. Negligible effect of the different cations Na⁺, K⁺, Mg²⁺, or Ca²⁺ on contact angles was observed.     

A gas-chromatographic study of the adsorption of vapors of oxygen-containing compounds on fluorinated carbon

The adsorption of the vapors of a number of oxygen-containing compounds (alcohols, ketones, acids, and other functional derivatives of hydrocarbons) on fluorinated carbon (FC) was studied by the gas chromatography method at low surface coverages. The Henry law constants, heats of adsorption, standard entropies of adsorption, and retention indices were determined. An analysis of adsorption and IR-spectroscopy measurements suggests that FC contains no surface active sites capable of forming hydrogen bonds. It was established that the adsorption of oxygen-containing compounds on a FC surface is primarily governed by dispersion interactions. The adsorbent under study was found to exhibit a high selectivity in separation of isomeric alcohols.     

Gaseous adsorption properties of a silica-pillared layered manganese oxide

Adsorptions of N(2), H(2)O, and organic vapors including CH(2)Cl(2), CCl(4), c-C(6)H(12), C(6)H(6), n-C(6)H(14), and n-C(9)H(20) on a silica-pillared layered manganese oxide (SiHMnO) and nonane-preadsorbed SiHMnO were examined. It is found that SiHMnO has a microporosity with a wide pore width distribution showing different pore wall affinities. Micropores with smaller width preferentially accommodate the nonane preadsorbate while the surface hydrophilicity of pore wall leads to an easier detachment of the adsorbed nonane molecules. H(2)O adsorption influences both the porosity and the surface properties by accelerating a sufficient hydrolysis of the remained TEOS molecules in SiHMnO. Examinations using Dubinin-Radeshkevich (DR) equation and isosteric heat of adsorption of organic molecules provide evidences that the wall surface of micropores with smaller and larger width have less affinity toward nonpolar and polar organic vapors, respectively.     

Use of inverse gas chromatography to characterize cotton fabrics and their interactions with fragrance molecules at controlled relative humidity

The present work focused on the surface characterization and fragrance interactions of a common cotton towel at different relative humidities (RHs) using inverse gas chromatography (IGC) and dynamic vapour sorption. The sigmoidal water sorption isotherms showed a maximum of 16% (w/w) water uptake with limited swelling at 100% RH. This means that water interacts strongly with cotton and might change its initial physico-chemical properties. The same cotton towel was then packed in a glass column and characterized by IGC at different relative humidities, calculating the dispersive and specific surface energy components. The dispersive component of the surface energy decreases slightly as a function of relative humidity (42 mJ/m2 at 0% RH to 36 mJ/m2 at 80% RH) which would be expected from swelling of the humidified cotton. The Gutmann's donor constant Kd increased from 0.28 kJ/mol at 0% RH to 0.42 kJ/mol at 80% RH, indicating that a greater hydrophilic surface exists at 80% RH, which is also as expected. Water, undecane and four fragrance molecules (dimetol, benzyl acetate, decanal and phenylethanol) were used to investigate cotton-fragrance interactions between 0 and 80% RH. The adsorption enthalpies and the Henry's constants were calculated and are discussed. The higher values for the adsorption enthalpies of polar molecules such as dimetol and phenylethanol suggest the presence of hydrogen bonds as the main adsorption mechanism. The Henry's constant of dimetol was also determined by headspace gas chromatography measurements at 20% RH, giving a similar value (230 nmol/Pa g by IGC and 130 nmol/Pa g by headspace GC), supporting the usefulness of IGC for such determinations. This work confirms the usefulness of chromatographic methods to investigate biopolymers such as textiles, starches and hairs.     

Adsorption of water vapour from humid air by selected carbon adsorbents

The water uptake by carbon molecular sieves (CMS) and graphitized carbons, all of which are used to determine volatile organic compounds in air, was investigated using a direct experimental approach. CMS, e.g. Carboxen 1002, Carboxen 1003 and Anasorb CMS adsorb substantial amounts of water, in the range 400 to 450 mg per gram of adsorbent. Graphitized carbons, e.g. Carbrogaph 5TD and Carbopack X show low water trapping, less than 30 mg g(-1) and Carbopack Y as little as 5 mg g(-1) or less. The water sorption capacity for graphitized carbons is strongly dependent on the relative humidity (RH). The change of RH from 95 to 90% decreases the amount of adsorbed water by more than a factor of 2. Two different water adsorption mechanisms are operative: adsorption on polar centers and micropore volume filling. For graphitized carbons and CMS at low RH, adsorption on polar centers is involved. For CMS, once the threshold value of relative humidity (RHth) is surpassed, micropore volume filling becomes predominant. RHth is 44 +/- 3 and 42 +/- 3% for Carboxen 1002 and 1003, respectively, and 32 +/- 3% for Anasorb CMS. The CMS mass in the trap was found not to affect the mass of retained water under condition of incomplete saturation of adsorbent bed with water. Thus, the restrictions commonly imposed on the CMS mass are not necessary. The dry purging technique is suggested to remove adsorbed water. Carbograph 5TD and Carbopack X require only a few hundred ml of dry air to remove adsorbed water entirely. Water can also be purged out from CMS; however, much larger volumes of dry air are needed.     

Determination of standard isotherms of the sorption of some vapors with cellulose

Standard isotherms of the sorption of water, methanol, and benzene vapors on cellulose using a cellulose standard are determined. The standard, namely, mesoporous cellulose with specific surface of up to 350 m2/g, is obtained by the method of exchanging water in swollen cellulose with organic solvents. A comparison of the experimental sorption isotherm with the standard isotherm makes it possible to determine the specific surface of celluloses accessible a the given sorbate and, in combination with the Brunauer-Emmett-Teller adsorption equation, to characterize their surface properties. The identity of the sorption properties of the initial and dewatered (porous) celluloses relative to active vapors is shown, which evidences the assumed mechanism of swelling as the sorbent's division into morphological structures with the formation of new surface. A comparative analysis of the sorption properties of cellulose and silica, whose nature of active sorption centers is similar (weak acid hydroxyl groups), has been made. The affinity of the standard isotherms and close values of the cross-sectional area of different sorbates on both sorbents testify the similarity in their sorption behavior. Thus, the processes of sorption with rigid and swelling sorbents can be regarded in a unified context. Therefore, the adsorption models developed for rigid sorbents can be applied to cellulose sorbents to analyze their sorption properties.     

Organic vapour sensing using localized surface plasmon resonance spectrum of metallic nanoparticles self assemble monolayer

The response of localized surface plasmon resonance (LSPR) spectra of gold and silver nanoparticles, and gold nanoshells to organic vapors was investigated. The surface area of nanomaterials was sufficiently high for quantitative adsorption of volatile organic compounds (VOCs). Surface adsorption and condensation of VOCs caused the environmental refractive index to increase from n = 1.00 in pure air to as high as n = 1.29 in near saturated toluene vapor. The extinction and wavelength shift of the LSPR spectra were very sensitive to changes in the surface refractive index of the nanoparticles. Responses of the LSPR band were measured with a real-time UV-vis spectrometer equipped with a CCD array detector. The response of silver nanoparticles to organic vapors was most sensitive in changes in extinction, while gold nanoshells exhibited red-shifts in wavelength (∼250 nm/RIU) when exposed to organic vapors. The LSPR spectral shifts primarily were determined by the volatility and refractive indices of the organic species. The T₉₀ response time of the VOC-LSPR spectrum was less than 3 s and the response was completely reversible and reproducible.     

Evolution of the adsorbed water layer structure on silicon oxide at room temperature

The molecular configuration of water adsorbed on a hydrophilic silicon oxide surface at room temperature has been determined as a function of relative humidity using attenuated total reflection (ATR)-infrared spectroscopy. A completely hydrogen-bonded icelike network of water grows up to three layers as the relative humidity increases from 0 to 30%. In the relative humidity range of 30-60%, the liquid water structure starts appearing while the icelike structure continues growing to saturation. The total thickness of the adsorbed layer increases only one molecular layer in this humidity range. Above 60% relative humidity, the liquid water configuration grows on top of the icelike layer. This structural evolution indicates that the outermost layer of the adsorbed water molecules undergoes transitions in equilibrium behavior as humidity varies. These transitions determine the shape of the adsorption isotherm curve. The structural transitions of the outermost adsorbed layer are accompanied by interfacial energy changes and explain many phenomena observed only for water adsorption.     

Kinetics of saturated water vapor sorption on soot particles

In order to study the condensation activity of carbon-containing aerosols, the kinetics of sorption of saturated water vapors was investigated on model soot samples modified by the deposition of organic and inorganic substances corresponding to different classes of compounds contained in solid state products of natural fuel combustion. The values of limiting water sorption were determined and rate constants were calculated. It was established that the limiting sorption on graphitized thermal soot (GTS) modified by acids and salts (e.g., phenol, benzoic, phthalic, trimellitic, and sulfuric acids; sodium benzoate; and ammonium sulfate) per modifier molecule rose by two orders of magnitude, relative to the initial carbon matrix, and ranged from ≈2 to 200 molecules. It was found that hydrophilic centers covalently bound to the surface of furnace black (FB) and its oxidized form are shielded to a considerable degree as a result of modification by hydrophobic substances (hexadecane, octacosane, anthracene, and stearic acid). We conclude that hexadecane modification of GTS containing hydrophilic centers not bound to its surface (sulfuric acid and ammonium sulfate molecules) have no effect on the sorption of saturated water vapors.     

Minimization of water vapor interference in the analysis of non-methane volatile organic compounds by solid adsorbent sampling

Water vapor can be a significant interference in the analysis of air for non-methane volatile organic compounds (NMVOCs) using solid-adsorbent sampling techniques. The adsorbent materials used in sampling cartridges have different hydrophobic characteristics, and it is therefore necessary to characterize solid-adsorbent cartridges over a wide range of humidity. Controlled humidity experiments were performed to assess the extent of water vapor interference when samples are collected onto AirToxics solid-adsorbent cartridges. It was found that elevating the temperature of the cartridge to 10 degrees C above the temperature of the air sample greatly reduced water vapor adsorption and interferences and resulted in > or = 90% recovery of NMVOCs, biogenic VOCs and chlorofluorocarbons. Similar collection efficiencies were obtained at ambient temperature by reducing the relative humidity to > or = 60% in the sample by dilution with dry, scrubbed ambient air. A procedure also was developed and optimized for dry-purging cartridges prior to analysis. However, under optimized conditions, significant losses of C3-C5 compounds still occurred under highly humid conditions. It was determined that these losses were due to reduced retention during sampling rather than loss during the dry purge procedure. The dry purge method was shown to be adequate at high humidities for sampling NMVOCs with retention indices greater than 500.     

Regioselective competitive adsorption of water and organic vapor mixtures on pristine single-walled carbon nanotube bundles

Sequential adsorption of water and organic vapor mixtures onto single-walled carbon nanotube (SWNT) bundles is studied experimentally and by grand canonical Monte Carlo (GCMC) simulation to elucidate the distinct interactions between select adsorbates and the nanoporous structure of SWNTs. Experimental adsorption isotherms on SWNT bundles for hexane, methyl ethyl ketone, cyclohexane, and toluene individually mixed in carrier gases that were nearly saturated with water vapor are compared with the GCMC-simulated isotherms for hexane, as a representative organic, on the external surface of the heterogeneous SWNT bundles. From the nearly perfect overlap between the experimental and simulated isotherms, it is concluded that until near saturation only the internal pore volume of pristine SWNT bundles fills with water. The adsorption of water vapor on the peripheral surface of the bundles remains insignificant, if not negligible, in comparison to the adsorption of water in the internal volume of the bundles. This is in contrast with the adsorption of pure hexane, which exhibits appreciable adsorption both inside the bundles and on their external surface. It is also suggested that during competitive adsorption, water molecules take precedence over small nonpolar and polar organic molecules for adsorption inside SWNTs and leave unoccupied the hydrophobic external surface of the bundles for other more compatible adsorbates.     

In situ study of water-induced segregation of bromide in bromide-doped sodium chloride by scanning polarization force microscopy

The adsorption of water on Br-doped NaCl crystals has been studied in situ using scanning polarization force microscopy, a noncontact electrostatic atomic force microscopy operation mode. Both topography and contact potential images were acquired as a function of relative humidity at room temperature, from 0% to more than 55%. It was found that the surface of the freshly cleaved crystal has an inhomogeneous electrical surface potential distribution with the steps more negative than the terraces below 40% relative humidity. This difference disappears when the humidity reaches 40% and higher. Below 40% the step morphology experiences only small changes due to water adsorption; however, above 40% major changes take place due to solvation, segregation, and redistribution of lattice ions. Bromide-rich islands and crystallites segregate to the surface above 40% relative humidity followed by drying. These islands and crystallites have a negative surface potential relative to the rest of the surface. These effects are attributed to the preferential solvation and segregation of Br- ions.     

Humidity effect on the monolayer-protected gold nanoparticles coated chemiresistor sensor for VOCs analysis

Two gold-thiolate monolayer-protected nanoparticles were synthesized and used as interfacial layers on chemiresistor sensors for the analysis of violate organic compounds (VOCs). Toluene, ethanol, acetone and ethyl acetate were chosen as the target vapors. Both the resistance and capacitance were measured as the function of analyte concentrations. The effect of humidity on the sensor sensitivity to VOCs was investigated. The sensitivity decreases with humidity increasing, depending on the hydrophobicity of the target compounds. Less effect was observed on the higher hydrophobic compounds. While the relative humidity (RH) increased from 0 to 60%, the sensitivity to acetone decreased by 39 and 37%, respectively on the Au-octanethiol (C₈Au) and Au-2-phenylethanethiol (BC₂Au) coated sensors, while the sensitivity to toluene decreased by 12 and 14%, respectively. These results show that the sensors coated with hydrophobic compounds protected-metal nanoparticles can be employed in high humidity for hydrophobic compounds analysis. The resistance responses to VOCs are rapid, reversible, and linear, while the capacitance response is not sensitive and consequently not applicable for VOCs analysis. The response mechanism was also discussed based on the sensor response to water vapor. The capacitance response is not sensitive to the film swelling in dry environment.     

Wetting and adsorption: II. Adsorption of Triton X-100 and Triton X-305 onto carbon black from water and cyclohexane solutions

The adsorption isotherms of nonionic surfactants Triton X-100 and Triton X-305 from water and cyclohexane on carbon black have been determined at 15 and 30°C. The Langmuir-type and BET-type isotherms are obtained for adsorption of Triton X-100 and Triton X-305 from water and cyclohexane respectively. Both the contact angles of water for graphite/water/air and graphite/water/cyclohexane decrease monotonously with increasing surfactant concentration. From these results, it is proposed that the adsorption of Triton X-100 and Triton X-305 on carbon black or graphite from water is monolayer. For the adsorption from cyclohexane solutions, the ethyleneoxide group of the surfactant molecules may be adsorbed onto the polar spot at the surface of carbon black, and the hydrophobic group of adsorbed molecules may direct toward the liquid phase or attaches to the nonpolar surface region around the polar spot. As the concentration increases, the ethylene oxide groups of the adsorbed molecules can be aggregated with each other via polar interactions to form hemi-reversed micelle.     

Humidity sensing properties of ZnO-based fibers by electrospinning

Zinc oxide (ZnO) based fibers with a diameter of 80-100 nm were prepared by electrospinning. Polyvinyl alcohol (PVA) and zinc acetate dihydrate were dissolved in water and the polymer/salt solution was electrospun at 2.5 kV cm⁻¹. The resulting electrospun fibers were subjected to calcination at 500 °C for 2 h to obtain ZnO-based fibers. Humidity sensing properties of the fiber mats were investigated by quartz crystal microbalance (QCM) method and electrical measurements. The adsorption kinetics under constant relative humidity (RH) between 10% and 90% were explained using Langmuir adsorption model. Results of the measurements showed that ZnO-based fibers were found to be promising candidate for humidity sensing applications at room temperature.