Structural features of polymer adsorbent LiChrolut EN and interfacial behavior of water and water/organic mixtures.

The structural and adsorption characteristics of polymer adsorbent LiChrolut EN and the behavior of adsorbed water and water/organic mixtures were studied using adsorption, microcalorimetry, transmission and scanning electron microscopy, mass spectrometry, infrared spectroscopy, 1H NMR spectroscopy with layer-by-layer freezing-out of liquids (190-273 K), and thermally stimulated depolarization current method (90-265 K). This adsorbent is characterized by large specific surface area (approximately 1500 m2/g) and pore volume (0.83 cm3/g) with a major contribution of narrow pores (R<10 nm) of a complicated shape (long hysteresis loop is in nitrogen adsorption-desorption isotherm). The adsorbent includes aromatic and aliphatic structures and oxygen-containing functionalities and can effectively adsorb organics and water/organic mixtures. On co-adsorption of water and organics (dimethyl sulfoxide, chloroform, methane), there is a weak influence of one on another adsorbate due to their poor mixing in pores. Weakly polar chloroform displaces a fraction of water from narrow pores. These effects can explain high efficiency of the adsorbent in solid-phase extraction of organics from aqueous solutions. The influence of structural features of several carbon and polymer adsorbents on adsorbed nitrogen, water and water/organics is compared on the basis of the adsorption and 1H NMR data.

Morphology and surface properties of fumed silicas.

Several series of fumed silicas and mixed fumed oxides produced and treated under different conditions were studied in gaseous and liquid media using nitrogen and water adsorption-desorption, mass spectrometry, FTIR, NMR, thermally stimulated depolarization current (TSDC), photon correlation spectroscopy (PCS), zeta potential, potentiometric titration, and Auger electron spectroscopy methods. Aggregation of primary particles and adsorption capacity (Vp) decrease and hysteresis loops of nitrogen adsorption-desorption isotherms becomes shorter with decreasing specific surface area (S(BET)). However, the shape of nitrogen adsorption-desorption isotherms can be assigned to the same type independent of S(BET) value. The main maximum of pore size distribution (gaps between primary nonporous particles in aggregates and agglomerates) shifts toward larger pore size and its intensity decreases with decreasing S(BET) value. The water adsorption increases with increasing S(BET) value; however, the opposite effect is observed for the content of surface hydroxyls (in mmol/m2). Associative desorption of water (2(SiOH)-->SiOSi+H2O) depends on both the morphology and synthesis conditions of fumed silica. The silica dissolution rate increases with increasing S(BET) and pH values. However, surface charge density and the modulus of zeta-potential increase with decreasing S(BET) value. The PCS, 1H NMR, and TSDC spectra demonstrate rearrangement of the fumed silica dispersion depending on the S(BET) value and the silica concentration (C(SiO2)) in the aqueous suspensions. A specific state of the dispersion is observed at the C(SiO2) values corresponding to the bulk density of the initial silica powder.

Spectroscopic study of biogenic amine complexes formed at fumed silica surface.

The structure and stability of biogenic amine complexes formed at the fumed silica surface were studied by UV-, IR-spectroscopy and TPD MS techniques. It was found that surface complexes are formed due to electrostatic interactions between amine cations and ionized silanol groups. The mechanism of thermal transformations of surface complexes is proposed. Kinetic parameters of thermal reactions at the fumed silica surface have been calculated.

Interactions between bioactive ferulic acid and fumed silica by UV-vis spectroscopy, FT-IR, TPD MS investigation and quantum chemical methods.

The interactions of bioactive ferulic acid with fumed silica were studied by UV/vis spectroscopy, FT-IR, TPD MS techniques and quantum chemical methods. It was found that surface complexes may form through phenol or carboxyl group of ferulic acid depending on its coverage value. The structure of surface complexes and mechanisms of the ferulic acid chemosorption on the silica surface are discussed. The kinetic parameters of the chemical reactions on silica surface are calculated. The mechanisms of thermal transformations of the ferulic chemosorbed surface complexes are proposed.

Structural and adsorption characteristics and catalytic activity of titania and titania-containing nanomaterials.

Morphological, structural, adsorption, and catalytic properties of highly disperse titania prepared using sulfate and pyrogenic methods, and fumed titania-containing mixed oxides, were studied using XRD, TG/DTA, nitrogen adsorption, (1)H NMR, FTIR, microcalorimetry on immersion of oxides in water and decane, thermally stimulated depolarization current (TSDC) and catalytic photodecomposition of methylene blue (MB). Phase composition and aggregation characteristics of nanoparticles (pore size distribution) of sulfate and pyrogenically prepared titania are very different; temperature dependent structural properties are thus very different. Catalytic activity for the photodecomposition of MB is greatest (per gram of TiO(2) for the pure oxide materials) for non-treated ultrafine titania PC-500, which has the largest S(BET) value and smallest particle size of the materials studied. However, this activity calculated per m(2) is higher for PC-105, possessing a much smaller S(BET) value than PC-500. The activity per unit surface area of titania is greatest for the fumed silica-titania mixed oxide ST20. Calcination of PC-500 at 650 degrees C leads to enhancement of anatase content and catalytic activity, but heating at 800 and 900 degrees C lowers the anatase content (since rutile appears) and diminishes catalytic activity, as well as the specific surface area because of nanoparticle sintering.