Valentin Tertykh

Synthesis and adsorption properties of chitosan-silica nanocomposite prepared by sol-gel method

A hybrid nanocomposite material has been obtained by in situ formation of an inorganic network in the presence of a preformed organic polymer. Chitosan biopolymer and tetraethoxysilane (TEOS), which is the most common silica precursor, were used for the sol-gel reaction. The obtained composite chitosan-silica material has been characterized by physicochemical methods such as differential thermal analyses (DTA); carbon, hydrogen, and nitrogen (CHN) elemental analysis; nitrogen adsorption/desorption isotherms, scanning electron microscopy (SEM); and Fourier transform infrared (FTIR) spectroscopy to determine possible interactions between silica and chitosan macromolecules. Adsorption of microquantities of V(V), Mo(VI), and Cr(VI) oxoanions from the aqueous solutions by the obtained composite has been studied in comparison with the chitosan beads, previously crosslinked with glutaraldehyde. The adsorption capacity and kinetic sorption characteristics of the composite material were estimated.

Behaviour of pure water and water mixture with benzene or chloroform adsorbed onto ordered mesoporous silicas

Structural characteristics of synthesized ordered mesoporous silicas MCM-41, MCM-48 and SBA-15 were studied using XRD, nitrogen adsorption and FTIR methods. Pure water and mixtures with water/benzene and water/chloroform-d adsorbed onto silicas were studied by 1H NMR spectroscopy with layer-by-layer freezing-out of bulk and interfacial liquids. Concentrated aqueous suspensions of MCM-48 and SBA-15 were studied by thermally stimulated depolarization current (TSDC) method. Benzene and chloroform-d can displace a portion of water to broad pores from the pore walls and from narrower pores, especially in the case of a large excess of an organic solvent. This process is accompanied by diminution of both interaction energy of water with an adsorbent surface and freezing temperature depression of adsorbed water. The effect of nonpolar benzene on pore water is much stronger than that of weakly polar chloroform-d. Modifications of the Gibbs-Thomson relation to describe the freezing point depression of mixtures of immiscible liquids confined in pores allow us to determine distribution functions of sizes of structures with unfrozen pore water and benzene.

Chitosan–Silica Hybrid Composites for Removal of Sulfonated Azo Dyes from Aqueous Solutions

In this study, the influence of the chitosan immobilization method on the properties of final hybrid materials was performed. Chitosan was immobilized on the surface of mesoporous (ChS2) and fumed silica (ChS3) by physical adsorption and the sol-gel method (ChS1). It was found that physical immobilization of chitosan allows to obtain hybrid composites (ChS) with a homogeneous distribution of polymer on the surface, relatively wide pores, and specific surface area of about 170 m2/g, pHPZC = 5.7 for ChS3 and 356 m2/g and pHPZC = 6.0 for ChS2. The microporous chitosan-silica material with a specific surface area of 600 m2/g and a more negatively charged surface (pHPZC = 4.2) was obtained by the sol-gel reaction. The mechanisms of azo dye adsorption were studied, and the correlation with the composite structure was distinguished. The generalized Langmuir equation and its special cases, that is, Langmuir-Freundlich and Langmuir equations, were applied for the analysis of adsorption isotherm data. The adsorption study showed that physically adsorbed chitosan (ChS1 and ChS2) on a silica surface has a higher sorption capacity, for example, 0.48 mmol/g for the acid red 88 (AR88) dye (ChS2) and 0.23 mmol/g for the acid orange 8 (AO8) dye (ChS1), compared to the composite obtained by the sol-gel method [ChS1, 0.05 mmol/g for the AO8 dye]. For a deeper understanding of the behavior of immobilized chitosan in the adsorption processes, various kinetic equations were applied: first-order, second-order, mixed 1,2-order (MOE), multiexponential, and fractal-like MOE as well as intraparticle and pore diffusion model equations. In the case of AO8 dye, the adsorption rates were differentiated for three composites: for ChS3, 50% of the dye was removed from the solution after merely 5 min and almost 90% after 80 min. The slowest adsorption process controlled by the diffusion rate of dye molecules into the internal space of the pore structure was found for ChS1 (225 min halftime). In the case of ChS2, the rates for various dyes change in the following order: acid orange (AO7) > orange G (OG) > acid red 1 (AR1) > AR88 > AO8 (halftimes: 10.5 < 15.7 < 23.7 < 34.9 < 42.9 min).

Imidazole-2yl-Phosphonic Acid Derivative Grafted onto Mesoporous Silica Surface as a Novel Highly Effective Sorbent for Uranium(VI) Ion Extraction

A new imidazol-2yl-phosphonic acid/mesoporous silica sorbent (ImP(O)(OH)2/SiO2) was developed and applied for uranium(VI) ion removal from aqueous solutions. The synthesized material was characterized by fast kinetics and an extra-high adsorption capacity with respect to uranium. The highest adsorption efficiency of U(VI) ions was obtained for the reaction system at pH 4 and exceeded 618 mg/g. The uranium(VI) sorption proceeds quickly in the first step within 60 min of the adsorbent sites and ion interactions. Moreover, the equilibrium time was determined to be 120 min. The equilibrium and kinetic characteristics of the uranium(VI) ions uptake by synthesized sorbent was found to follow the Langmuir-Freundlich isotherm model and pseudo-second-order kinetics rather than the Langmuir, Dubinin-Radushkevich, and Temkin models and pseudo-first-order or intraparticle diffusion sorption kinetics. The adsorption mechanism for uranium on the sorbent was clarified basing on the X-ray photoelectron spectroscopy (XPS) analysis. The model of UO22+ binding to surface of the sorbent was proposed according to the results of XPS, i.e., a 1:1 U-to-P ratio in the sorbed complex was established. The regeneration study confirms the ImP(O)(OH)2/SiO2 sorbent can be reused. A total of 45% of uranium ions was determined as originating from the sorbent leaching in the acidic solutions, whereas when the basic solutions were used, the removal efficiency was 12%.

Modified silicas with different structure of grafted methylphenylsiloxane layer

The method of a chemical assembly of the surface polymeric layer with high contents of the modifying agent was developed. Powders of nanodispersed silica with chemisorbed polymethylphenylsiloxane (PMPS) were synthesized by solvent-free chemical assembly technique with a dimethyl carbonate (DMC) as scission agent. Samples were characterized using FTIR spectroscopy, transmission electron microscopy (TEM), atomic force microscopy (AFM), and elemental analysis (CHN analysis). Coating microstructure, morphology, and hydrophilic-hydrophobic properties of nanoparticles were estimated. The results indicate a significant effect of the PMPS/DMC ratio at each modification stage on hydrophobic properties of modified silicas. Modification with a similar composition of the PMPS/DMC mixture, even with different polymer amount at each stage, provides the worst hydrophobicity. Results suggest that the highest hydrophobicity (contact angle θ = 135°–140°) is achieved in the case when silica modified with the PMPS/DMC mixture using multistage approach that providing a formation of the monomolecular layer of polysiloxane at the first modification step. The characteristics of surface structure were interpreted in terms of density of polymer-silica bonds at the interfaces that, usually, are reduced for modified surfaces, in a coupling with conformation model that accented the shape of chains (arch- and console-like) adsorbed on solid surfaces.

ADSORPTION PROPERTIES OF FUNCTIONAL SILICAS TOWARDS SOME TOXIC METAL IONS IN WATER SOLUTIONS

bound complexing phenolic-type analytical reagents 8-hydroxyquinoline, 1-(2-pyridylazo)-2-naphthol, 4-(2-pyridylazo)resorcinol have been studied. Structures of the surface complexes of toxic metals with grafted analytical reagents were determined using IR, ESR and electronic diffuse reflectance spectroscopies. Possibility of simultaneous determination of micro amounts of heavy metals was demonstrated using the x-ray fluorescence analysis of modified adsorbents after absorption of metal ions from their multicomponent mixtures in natural and artificial water solutions. Silica gel with adsorbed polyionene (1,4-MePh) was shown to have high adsorption properties towards some metal-containing anions, in particular MoO4, WO4 and Cr2O7 in water solutions. Adsorption isotherms of these metal-containing anions on initial silica gel and silica-supported polyionene were investigated.

Preparation and characterization of nanocomposite polyvinyl chloride films with NO-generating activity

The silica and copper oxide nanoparticles were embedded into the polyvinyl chloride film and obtained filled composites were tested as a catalyst in the reaction of the NO release from appropriate biomolecules. Obtained materials were characterized using scanning electron, atomic-force microscopies and thermomechanical analysis. It has been shown that the introduced particles are distributed uniformly in the polymeric matrix of hybrid composite and such film produces a significant amount of NO when reacts with S-nitrosothiols. At the same time, the unfilled polyvinyl chloride film had no statistically significant catalytic activity.

Polymeric Composite Films with Controlled Release of Natural Antioxidant Enoxil

The investigation was devoted to elaboration of effective carriers of biological active substrate based on natural tannins, namely, Enoxil. Several types of carriers based on silica or biocompatible natural polymers were synthesized and tested. Silica-containing composites have been prepared by impregnation of fumed silica with Enoxil and by sol-gel silica formation into the Enoxil solution. Polymeric films were composed by mixing of gelatin (Gel), chitosan (Chit), and 2-hydroxyethylmethacrylate (HEMA) in different proportions and compositions. Obtained materials were characterized using FTIR, ATR, and DSC. All materials were tested in vitro release and antibacterial static activity. The release rate of Enoxil from the carrier based on fumed silica A-300 was much higher compared with the liberation rate from the composites prepared by sol-gel method. The prolonged release of active substrate was obtained by use of the silica gel with phenolic groups as a carrier. Polymeric films based on gelatin/chitosan were found to show the highest swelling degree and reduced release. The composition with HEMA had more rigid structure, but the best carrier in this line samples was Gel/HEMA composite cross-linked with mixture of functional amino- and vinylsilane (Gel/HEMA/VA).

Bifunctional Silicas with Immobilized Lignin

Silica/lignin biocomposites were obtained by impregnation of the modified pyrogenic silicas with water solutions of polymer. Modification of silica surface was carried out using liquid-phase and gas-phase treatment with alkoxyorganosilanes and hexamethyldisilazane, respectively. The silicas with methyl, amine, and silicon hydride groups in a mono- or bifunctional (methyl-hydride, methyl-amino, amino-hydride) surface layers were impregnated with kraft lignin and characterized using differential scanning calorimetry (DSC), attenuated total reflectance (ATR), Fourier transform infrared (FT-IR), and UV spectroscopies. The influence of nature and amount of silica surface functional groups on physicochemical properties of immobilized lignin has been studied. The data on the structure of the polymer layer and the nature of silica/lignin interactions are discussed.

Immobilization of Polymeric Luminophor on Nanoparticles Surface.

Polymeric luminophors with reduced toxicity are of the priorities in the production of lighting devices, sensors, detectors, bioassays or diagnostic systems. The aim of this study was to develop a method of immobilization of the new luminophor on a surface of nanoparticles and investigation of the structure of the grafted layer. Monomer 2,7-(2-hydroxy-3-methacryloyloxypropoxy)naphthalene (2,7-NAF.DM) with luminophoric properties was immobilized on silica and carbon nanotubes in two ways: mechanical mixing with previously obtained polymer and by in situ oligomerization with chemisorption after carrier’s modification with vinyl groups. The attached polymeric (or oligomeric) surface layer was studied using thermal and spectral techniques. Obtained results confirm the chemisorption of luminophor on the nanotubes and silica nanoparticles at the elaborated synthesis techniques. The microstructure of 2,7-NAF.DM molecules after chemisorption was found to be not changed. The elaborated modification approach allows one to obtain nanoparticles uniformly covered with polymeric luminophor.