Low-temperature Nitrogen Adsorption-desorption Research Articles

Sphere-shaped ZnO photocatalyst synthesis for enhanced degradation of the Quinolone antibiotic, Ofloxacin, under UV irradiation.

The sphere-shaped zinc oxide (ZnO) photocatalyst was synthesized by the homogeneous precipitation method, using Zn(CH3COO)2·2H2O as a zinc precursor and NH4OH as a precipitating agent. The morphology and crystal structure of the prepared ZnO sample were studied by XRD, SEM, FT-IR, XPS, zetapotential measurements, and a low-temperature nitrogen adsorption-desorption technique. The optical characteristics of ZnO were determined by UV - Vis diffuse reflectance spectroscopy. ZnO photocatalyst performance of up to 100% within 210min was observed in the photodegradation of the ofloxacin antibiotic under ultraviolet (UV) irradiation. The effect of antibiotic concentration, heavy metal ions, and water sources on the photocatalytic activity of ZnO demonstrated both the potential of its application under different conditions, and a good adaptability of this photocatalyst. The photodegradation reaction correlated well with the first-order kinetics model, with a rate constant of 0.0173min-1. The reusability of the photocatalyst was verified after three cycles of use. Admittedly, photogenerated electrons and holes played a key role in removal of the antibiotic. This work showed the suitability of prepared ZnO for antibiotic removal, and its potential use for environmental protection.

Engineering a staggered type-II Bi2WO6/WO3 heterojunction with improved photocatalytic activity in wastewater treatment

In recent years, the removal organic pollutants from wastewater by advanced oxidation processes, especially photocatalysis, has become a meaningful approach due to its eco-friendliness and low cost. Herein, staggered type-II Bi2WO6/WO3 heterojunction photocatalysts were prepared by a facile hydrothermal route and investigated by modern physicochemical methods (X-ray diffraction, scanning electron microscopy, low-temperature nitrogen adsorption-desorption, and diffuse reflectance spectroscopy). The optimized BWOW-5 photocatalyst exhibited a H2O2-assisted photocatalytic methylene blue removal efficiency of 94.1% (k = 0.01414 min−1) within 180 min under optimal reaction conditions, which is much higher than that of unmodified Bi2WO6 and WO3 due to efficient separation of the photogenerated charge carriers. The trapping experiments demonstrated that photogenerated hydroxyl radicals and holes play a key role in the photodegradation reaction. Moreover, the optimized BWOW-5 heterojunction photocatalyst exhibited excellent activity in the H2O2-assisted degradation of other pollutants, namely phenol, isoniazid, levofloxacin, and dibenzothiophene with the removal rate of 63.1, 73.6, 95.0, and 72.4%, respectively. This investigation offers a design strategy for Bi2WO6-based multifunctional photocatalytic composites with improved activity for organic pollutant degradation.

Synthesis, properties and applications of new hybrid material based on native/magnetically modified sepiolite and chitosans

The study introduces novel hybrid materials containing native and magnetite-containing sepiolite (Sep, SepM respectively) and chitosans (Ch) of different molecular weights. The main objective of this work was to determine the properties of these materials, including the different types of stability (colloidal, gravitational and thermal) in systems containing sepiolite, in order to obtain effective, stable and easily producible hybrid materials with great potential for water and wastewater treatment. The following measurements and methods were performed to characterize the investigated system: low-temperature nitrogen adsorption–desorption, zeta potential analysis, UV–Vis, FT-IR, XRD, XRF, SEM-EDS, TGA, DSC and DTG. It was found that the complexes with high molecular weight chitosan exhibited the best stability of the systems. The same tendency was observed for the concentration dependence: the higher the chitosan concentration, the better the stabilization of the composites. Overall, this study shows that chitosan effectively improves the colloidal and gravitational stability of the composites. Due to its unique structure, the synthesized magnetic hybrid material has shown great advantages in the adsorptive removal of textile dyes such as anionic acid red 88 (AR88) and cationic methylene blue (MB) which can be easily removed from the dye solutions after its use using an external magnetic field.

Studies on the Process of Basic Dyes Adsorption on Uniform Spherical Carbons.

The influence of carbon pore structure on the sorption process of selected cationic dyes has been investigated. The structure and surface of carbonaceous materials have been characterized basing on various techniques: scanning electron microscopy, low temperature nitrogen adsorption-desorption measurements, X-ray photoelectron spectroscopy and thermal analysis combined with identification of gaseous products. The kinetic and equilibrium adsorption measurements of Basic Violet 3, Basic Red 1 and Basic Blue 9 from aqueous media were performed. The studied carbons seem to be promising adsorbents towards dyes, taking into account the easy-to-use uniform spherical form of the granules and a complex type of porosity with micro-, meso- and macropores appropriate for large molecule adsorption.

Feroxyhyte - from synthesis and characterization to application.

Feroxyhyte (δ-FeOOH) was synthesized and characterized using X-ray diffractometry (XRD), simultaneous thermal analysis (STA), scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDS), and low-temperature nitrogen adsorption-desorption measurements. Its potential application as adsorbent of an anionic and cationic dyes such as C.I. Acid Violet 1 (AV1) and C.I. Basic Blue 3 (BB3) was investigated by determining the adsorption capacities based on the Langmuir (36.6 mg/g for AV1 and 187 mg/g for BB3), Freundlich and Dubinin-Radushkevich isotherm models. Adsorption of AV1 and BB3 by δ-FeOOH drops with the presence of additives such as cationic and anionic surfactants (CTAB, SDS) and ionic polymers (PAA, PEI). The surface and electrokinetic properties of examined suspensions were also described. They include determination of the solid surface charge density and the zeta potential, as well as values of point of zero charge and isoelectric point of feroxyhyte particles without and with adsorbed layers of organic substances. Their analysis made possible to propose the most probable structure of electrical double layer formed at the iron mineral/aqueous solution interface.

SOFT MECHANOCHEMICAL SYNTHESIS OF CuO/ZnO/AL2O3 CATALYST FOR METHANOL PRODUCTION

In the work, using a set of methods for physicochemical studies, such as X-ray phase, X-ray diffraction, synchronous thermal and energy-dispersion analysis, scanning electron microscopy, low-temperature adsorption-desorption of nitrogen, IR-Fourier spectroscopy, the processes occurring at the stage of mechanochemical activation and further heat treatment of the Cu(NO3)3·3H2O/Zn(NO3)3·2H2O/Al(NO3)3·9H2O/H2C2O4·2H2O were studied. It has been established that at the stage of mechanochemical activation, intensive interaction of copper and zinc nitrates with oxalic acid occurs with the formation of one-water copper oxalate (CuC2O4∙Н2О) and two-water zinc oxalate (ZnC2O4∙2Н2О). The formation of oxalates occurs at the initial moment of activation 0-15 min, which is confirmed by the data of IR spectroscopy, X-ray phase and thermal analysis. The calcination of the samples leads to the formation of the ternary oxide system CuO/ZnO/Al2O3 and the interaction of copper and zinc oxides with the formation of a solid solution. It is shown that with an increase in the MCA time, the size of the coherent scattering regions decreases from 152 Å for the initial sample to 115 Å after 60 min of treatment. In this case, the accumulation of defects in the crystal structure occurs from 0.24 to 0.72%, respectively. The value of the specific surface passes through a maximum and at 30 min of treatment is 67.1 ± 0.3 m2/g. During processing, a mesoporous structure of the catalyst is formed with a total pore volume of 0.132 cm3/g. For the scaling process or the selection of other types of mills, the values of the supplied energy were calculated. It has been established that in order to obtain a catalyst with properties close to industrial analogs of leading foreign manufacturers, it is necessary to carry out treatment with an input energy of 79 kJ/g, and the calcination process should be carried out at a temperature of 350 °C and a duration of 360 min.

APPLICATION OF ACTIVATING INFLUENCES IN OBTAINING TiO2-PILLARED MONTMORILLONITE WITH IMPROVED PHOTOCATALYTIC PROPERTIES

A new approach to the obtaining of a highly efficient photocatalyst - TiO2-pillared montmorillonite – by hydrothermally activated intercalation of mechanically dispersed bentonite matrix with the polyhydroxocomplexes of titanium is proposed. The material was characterized by the X-ray diffractometry, low-temperature nitrogen adsorption-desorption, scanning electron microscopy, energy dispersive microanalysis, and zeta potential measurement. The use of short-term (up to 3 min) mechanical dispersion in a planetary mill significantly increases the capacity of cation exchange during intercalation, and the photocatalysts obtained after annealing at 500 °C are characterized by significantly higher values of specific surface area and total pore volume compared with mechanically untreated and initial montmorillonite. The average size of TiO2 crystallites is about 10 nm and the content of anatase is over 90%. Mechanical activation leads to a significant change in the ζ-potential of montmorillonite particles from a significantly negative value in the source material to almost zero, which is an additional argument for more efficient intercalation. Hydrothermal treatment leads to the appearance of coral-like formations of titania on the surface of montmorillonite, and after mechanical treatment they significantly increase in size. Adsorption and photocatalytic properties were studied in a quartz reactor using the rhodamine B dye as example. Complete photocatalytic destruction of the dye was achieved within about 100 min (initial concentration of 40 mg/l, amount of photocatalyst 1 g/l, UV lamp power 250 W). Adsorption kinetics is described by pseudo-first and pseudo-second order models. The kinetics of photocatalysis is described by the Langmuir-Hinshelwood model. The high photoactivity is explained both by the improvement of textural properties and the appearance of additional photocatalytic centers due to the defective structure of mechanically activated montmorillonite.

SYNTHESIS, STRUCTURE AND PROPERTIES OF BENTONITE - ACTIVATED CARBON COMPOSITE

The development of adsorption purification technology in industry is divorced from research in the development of new methods for the synthesis and modification of composites, while the efficiency of the adsorbent directly depends on its structural and surface properties. Currently, there is an increasing demand for hydrogel adsorbents used in pharmaceuticals, medicine, and the chemical industry for wastewater treatment. Dash-Salakhlinsky bentonite, a natural clay mineral and activated carbon of the BAU-A brand, was used as an object of study. By intercalation of bentonite with activated carbon, a bentonite-coal composite was obtained. Grinding equipment of medium energy density was used: roller-ring vibrating mill VM-4. Activation time was 15 min. The average particle size of the initial bentonite and bentonite-carbon composite was determined by laser diffraction on a particle size analyzer. During mechanical activation of bentonite, the nature of the distribution of particles indicates the predominant process of aggregation over grinding. The morphology, structure, and textural properties of the composite were studied by the methods of low-temperature nitrogen adsorption-desorption and IR spectroscopy. An increase in the specific surface area and porosity after mechanochemical activation as compared to the calculated values indicates the interaction between the components. IR spectroscopy established the formation of additional functional groups that can act as active centers, which positively affects the adsorption properties. It is shown that the bentonite-charcoal composite has a high sorption activity with respect to the brilliant green dye. The data obtained can be useful in the development of effective sorbents for wastewater treatment from pollution by organic compounds, as well as in medicine and pharmaceuticals.

In English

Silicas of MCM-41‑type with reactive functional groups are widely used as starting substrates in large variety of post‑synthetic chemical modification pathways. Therefore, variation of their structural characteristics in the process of templated sol‑gel synthesis or post-synthetic treatment is of great importance. The aim of this work was to elucidate the influence of template agent selection on structural features of MCM-41‑type materials with surface silanol and 3‑chloropropyl groups. For this purpose, template-assisted sol-gel condensation of structure forming silanes (tetraethyl orthosilicate and 3‑chloropropyltriethoxysilane) was carried out in the presence of decyltrimethylammonium bromide as structure-directing agent. The capability of cyclic oligosaccharide (β-cyclodextrin) to interact with surfactant micelles in the process of hydrothermal sol-gel synthesis and to influence the formation of mesoporous structure of silica materials was studied. The IR spectroscopy was applied to carry out control under the complete removal of template moieties from pores by extraction procedure and to confirm introduction of 3‑chloropropyl groups into the surface layer of synthesized silicas. Arrangement of mesoscale pores and structural parameters were estimated from the results of X‑ray diffraction and low-temperature adsorption-desorption of nitrogen. It has been found that β‑cyclodextrin as component of hybrid template has positive effect on porous structure of 3-chloropropyl-functionalized MCM-41-type silica causing increase of surface area accompanied with preservation of pore ordering. Moreover, both ionic surfactant and oligosaccharide components of hybrid template act as porogens during sol-gel condensation of structure forming silanes enable to prepare silica materials with micro-mesoporosity. Proposed approach can be useful in synthesis of MCM‑41‑type silicas with surface linker groups and controlled structural characteristics (pore size, geometry and ordering), which have great potential as substrates in design of sophisticated materials.

Effect of Ti-containing precursors on structure and adsorption performance of Li4Ti5O12 and Li2TiO3 oxides to Li+ ions

Using solid-phase synthesis method, Li4Ti5O12 and Li2TiO3 oxides were synthesized and used as adsorbents for Li+ ions. The physical–chemical properties were studied, using X-ray diffraction analysis, IR-spectroscopy, low-temperature adsorption–desorption of nitrogen, and scanning electron microscopy. It was shown that, using anatase as a Ti-containing precursor, single-phase oxides Li4Ti5O12 (d 26.5 nm, a 8.401 Å, V 569.5 Å3) and Li2TiO3 (d 26.5 nm, a 7.731 Å, V 462.1 Å3) with macro-mesoporous structure (ABET 11 and 16 m2/g, VBJH des 0.03 and 0.03 cm3/g, DBJH des 6 and 6 nm, respectively) and spherical-like morphology were obtained. For the samples obtained from rutile, an impurity of unreacted Ti-containing precursor was detected. The effect of the nature of Ti-containing precursors, concentration and temperature of HCl regeneration solution, and contact time on the degree of conversion to H-form and adsorption capacity of the obtained adsorbents was studied. The highest efficiency of ion exchange of Li+ ions with H+ (γH+ 96.7–100 %) was reached in conversion of adsorbents to H-form, during treatment with 0.1 M HCl at temperature of 70 °C for 48 h. Adsorbents H4Ti5O12 and H2TiO3 prepared from anatase showed higher adsorption efficiency of Li+ ions (qe 95.1 and 84.0 mg/g, α 34.7 and 32.9 %, respectively) compared to samples obtained from rutile (qe 75.7 and 81.2 mg/g, α 23.8 and 29.9 %, respectively). After three cycles of acid regeneration, the adsorption capacity was maintained at 40.6–47.0 mg/g for Li4Ti5O12, and at 34.8–38.4 mg/g for Li2TiO3, respectively. The hydrogen demonstration during adsorption–desorption cycles increased from 8.4 to 10.8 for Li4Ti5O12, and from 8.0 to 11.2 for Li2TiO3. Anatase Ti-containing precursor recrystallization into rutile modification and further amorphization was determined. The presented results are interesting for developing highly efficient adsorbents for Li+ ions recovery from aqueous solutions.

Removal of Methyl Red from Aqueous Solution Using Biochar Derived from Fennel Seeds

In this study, fennel (Foeniculum vulgare) seeds were used as a precursor to obtain carbon adsorbents through physical activation with carbon dioxide and chemical activation by impregnating the precursor with sodium carbonate. The physical activation involved the carbonization of the precursor at a temperature of 600 °C for 60 min and activation at a temperature of 800 °C for 30 min with carbon dioxide. Chemical activation included impregnation of the precursor with sodium carbonate at a mass ratio of a precursor to activator of 1:2. The mixture was activated in a nitrogen atmosphere with a flow rate at a temperature of 700 °C for 45 min. The resulting biochar samples were washed with 5% hydrochloric acid and subsequently rinsed with boiling distilled water. The biochar adsorbents were characterized using low-temperature nitrogen adsorption–desorption isotherms, Boehm titration, and pH measurements of their aqueous extracts. The specific surface area of the obtained adsorbents ranged from 89 to 345 m2/g. Biochar adsorbents exhibit a predominance of acidic groups over basic groups on their surfaces. The sorption capacities of the obtained samples towards an aqueous solution of methyl red range from 26 to 135 mg/g. Based on adsorption studies, it was found that the adsorption of the dye on the obtained biochar materials follows a pseudo-second-order model. The Freundlich isotherm best describes the studied process, indicating the formation of a multilayer of adsorbate on the adsorbent surface. The efficacy of adsorption in aqueous solutions of methyl red was found to increase with the elevation of the process temperature. Moreover, thermodynamic studies have shown that the adsorption process is spontaneous and endothermic. Consequently, this work provides a description of the physicochemical parameters of two biochars obtained by physical and chemical activation of a little-studied precursor—fennel seeds—and studies on their potential use as adsorbents for contaminants from the aqueous phase.

Low cross-linked terpenes-based porous polymers with reduced content of divinylbenzene: synthesis, physicochemical properties and sorption abilities

The low cross-linked porous polymers were prepared using terpene compounds (citral, limonene and pinene) and divinylbenzene with a suspension method. The prepared materials were characterized by: ATR-FTIR, low temperature nitrogen adsorption–desorption, TGA, swelling ratio and solid phase extraction (SPE) experiments. ATR-FTIR verified the chemical structures of the polymers. All the materials had developed internal structure with SBET in the range of 45–190 m2/g and high thermal stability. Sorption properties of the terpene-based polymers were tested for phenolic compounds (phenol, 2-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol) and popular non-steroidal anti-inflammatory drugs (aspirin, paracetamol and ibuprofen) and an antibiotic (ampicillin) with a dynamic solid phase extraction (SPE) method. The recoveries of 2,4-dichlorophenol and 2,4,6-trichlorophenol remained at a level 80–100% for all new materials even for 10–13 concentration cycles. Very high recoveries (70–100%) were also obtained for ibuprofen and aspirin from the citral- and limonene-based polymers using one-component solutions. However, when using ternary component solutions, the maximum recoveries of ibuprofen reached 70%. Paracetamol recoveries did not exceed 20%, while these for ampicillin ranged from 40 to 80%. The performed studies have proven that the process is affected by both chemical nature of adsorbents and adsorbates. Especially in the case of multicomponent solutions, the acid—base balance of solutes in the solution and on the polymer—solution interface should be taken into account as an important factor determining obtained recoveries.

Pore Structure Characterizations of Shale Oil Reservoirs with Heat Treatment: A Case Study from Dongying Sag, Bohai Bay Basin, China.

Heat treatment plays a significant role in determining the petrophysical properties of shale reservoirs; however, the existing studies on the evolution of pore structures are still insufficient. This study conducts a series of tests, including Rock-Eval, low-temperature nitrogen adsorption-desorption, nuclear magnetic resonance (NMR) T2, and T1-T2 tests on samples from Shahejie Formation, Dongying Sag, Bohai Bay Basin. The tests aim to determine the changes in the shale pore structures under increasing heat treatments (ranging from 110 to 500 °C) and identify the factors that control pore structures. The results show that the gradual decomposition of organic matter leads to an eventual decrease in the total organic carbon (TOC) content. The decrease in TOC is more prominent when the temperature exceeds 300 °C. For shales with lower TOC contents (<2%), the Brunauer-Emmett-Teller specific surface area (BET SSA) first decreases, then increases, but eventually decreases again. However, the average pore diameter demonstrates an opposite trend when the temperature increases. In contrast, for organic-rich shales (TOC > 2%), the BET SSA increases at temperatures above 200 °C. The similarity between the D1 values implies that the complexity and heterogeneity of shale pore surface only undergo minor changes during heat treatment. Porosity shows an increasing trend, and the higher the contents of clay minerals and organic matter in shales are, the greater the change in porosity is. The NMR T2 spectra suggest that micropores (<0.1 μm) in shales first decrease and then increase, whereas the contents of meso- (0.1-1 μm) and macropores (>1 μm) increase, corresponding to the increase in free shale oil. Moreover, shale pore structures are primarily controlled by clay minerals and organic matter contents during heat treatments, with higher contents resulting in better pore structures. Overall, this study contributes to detailing the shale pore structure characteristics during the in situ conversion process (ICP).

THE EFFECT OF THE TYPE AND CONTENT OF CARBONATES ON THE CHARACTERISTICS OF POROSITY OF CERAMIC MEMBRANES

The main issue considered in the work is the creation of a matrix for ceramic membranes, which would be distinguished by low cost and high porosity. In order to reduce the cost of ceramic membranes, a widespread approach was chosen, which is powerfully used by many researchers, namely the use of natural minerals - kaolin and saponite - as the main components of the matrix. Carbonates were used as pore generating agents to achieve the required porosity value. Three series of ceramic membranes (CM) differing in chemical composition were synthesized in the work: KP1, KP2, and KP3 series. The main composition of CM includes: kaolin, saponite, sodium silicate and carbonates. The effect of the type and amount of carbonates (CaCO3, NH4HCO3, (NH4)2CO3) as pore generating agents on the formation of the porous structure of the samples was studied. The type and content of carbonates varied in different samples from 8 wt% up to 40 wt%. The dry pressing method using pressure equivalent to 8 tons and 15 tons was used to form ceramic membranes. The main parameters by which the properties of ceramic membranes were evaluated: water absorption, total and open porosity. Standard methods were used to determine these parameters for synthesized samples. The chemical composition of the dry mixture of the ceramic membrane, for which the porosity is the maximum in the series of manufactured samples, was established. It was established that the addition of calcium carbonate components to the dry mixture increases the porosity of ceramic membranes and water absorption. The chemical composition of a ceramic membrane sample with the best indicators of total and open porosity in the KP2 series is given. The chemical and phase composition of samples of the KP2 series, as well as their structural and adsorption characteristics, were investigated by X-ray fluorescence and diffraction methods of analysis and low-temperature nitrogen adsorption-desorption. The effect of the addition of silicon carbide on the characteristics of the porosity of the samples was determined.

Formation of Zn0.5Ni0.5Fe2O4 Nanocrystals in Conditions of Solution Combustion: Effect of the Type of Fuel on the Structure and Morphology

Nickel-zinc ferrites, which have pronounced ferrimagnetic and semiconductor properties, can be used as promising magnetically controlled photocatalysts for the purification of aqueous media from organic pollutants. The value of the specific surface area largely affects the photocatalytic properties of the material; therefore, the possibility of its control and variation at the stage of synthesis is of great scientific and technical interest. In this study, nanocrystalline ferrite of the Zn0.5Ni0.5Fe2O4 composition is obtained under conditions of solution combustion using various types of organic fuel as the main factor affecting the formation of the specific surface area, and subsequent heat treatment in air at a temperature of 500°C for 2 h. The crystal structure, chemical composition, and morphology of Zn0.5Ni0.5Fe2O4 are studied by methods of X‑ray phase analysis, X-ray spectral microanalysis, and scanning electron microscopy. The values of the specific surface area of the synthesized nanopowders are calculated based on the method of liquid-phase adsorption from a Methylene Blue solution and the low-temperature adsorption-desorption of nitrogen. The results of the X‑ray phase analysis show that a single-phase nanocrystalline product with a spinel structure is formed, where the average crystallite size varies within 11–23 nm and is inversely related to the value of the specific surface area, respectively, after the reaction with succinic acid (39.1 m2/g) and with glycine (20.2 m2/g). It is established that the choice of the fuel largely affects the formation of nanocrystals and the specific surface area of the samples, and the approach used makes it possible to control its values.

Synthesis of ferrierite-type zeolite by microwave method using ethylenediamine as an organic structure-directing agent

A new method for the synthesis of ferrierite-type zeolite has been developed using microwave irradiation in the presence of structure-directing agents (templates). The physicochemical characteristics of the synthesized zeolites were investigated by X-ray diffraction analysis, low-temperature nitrogen adsorption–desorption and SEM-EDX. When comparing the synthesis products, it was found that microwave irradiation significantly reduces the crystallization time of the synthesized zeolites compared to traditional hydrothermal treatment

Obtaining and study of physical-chemical properties of porous materials based on kaolin

The object of research is kaolin from the Hlukhovetsky deposit (Ukraine). On its basis, granulated sorbent materials were obtained with the addition of various amounts of cellulose as a pore former. After forming the samples, they were dried and fired at a temperature of 800 °C. The obtained granules with a size of 8–9 mm were modified with zero-valent iron. The physicochemical, including sorption properties of granular composites were studied. Using scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), the morphology of the obtained samples was investigated and the presence of zero-valent iron particles on the surface and in the pores of the sorbents was confirmed. Based on desorption experiments, it was determined by chemical analysis that the Fe0 content in modified samples with increased pore former content increases from 0.01 g/g of granules for a sample containing 1% cellulose to 0.016 g/g for a carrier with 3 % pore former. The specific surface area and pore volume of the samples were determined by the method of low-temperature adsorption-desorption of nitrogen. Thus, with an increase in the content of the pore former in the ceramic mass, the specific surface of both unmodified and modified samples slightly decreases. Thus, with a cellulose content of 1 %, it is 20 m2/g and 17 m2/g, respectively. When the pore former is increased to 3%, these values are 15 m2/g and 12 m2/g. After applying a layer of zero-valent iron on porous granules, the volume of pores decreases, which is due to the formation of agglomerates of iron particles during synthesis. The study of the sorption capacity of the obtained sorbents with respect to Cr(VI) from model solutions containing a mixture of metal cations (copper, cadmium, cobalt, zinc) showed that granular materials exhibit sorption capacity for metal anions, even in the presence of cations. The amount of chromium sorption naturally increases for modified samples with an increase in the cellulose content in them. However, for model solutions that do not additionally contain metal cations, the sorption value is somewhat higher. Thus, for a sample with a 3 % pore former content, the sorption value is 0.7 mg/g and 0.9 mg/g, respectively, at an initial chromium(VI) concentration of 10 mg/g. The obtained experimental data indicate that the obtained porous granular sorbents based on kaolin can be used in the further treatment of wastewater from electroplating enterprises, which contain a mixture of pollutants in both anionic and cationic forms.

Hydroformylation of Alkenes over Phosphorous-Free Rhodium Supported on N-Doped Silica

A new phosphorous-free rhodium supported on a nitrogen-doped silica was successfully used as a catalyst for the hydroformylation of alkenes. The obtained material and the catalyst were characterized by XRD, XPS, FTIR, SEM, TEM, ICP AES, and low-temperature nitrogen adsorption–desorption measurements. The catalytic performance was studied by the example of the hydroformylation of octene-1 at temperatures of 80–140 °C and a pressure of 5.0 MPa. The catalyst provided a 99% conversion of 1-octene with a 98% yield of aldehydes and showed a good conversion of styrene and cyclohexene. The catalyst can be repeatedly used in ten consecutive cycles, with its activity remaining constant.

РАЗРАБОТКА И ПОИСК ФУНКЦИОНАЛЬНОСТЕЙ НОВЫХ ОРГАНОКРЕМНЕЗЕМНЫХ ГИБРИДНЫХ НАНОКОМПОЗИТОВ С ВКЛЮЧЕНИЕМ БИОПОЛИМЕРОВ ХИТОЗАНА В СИЛОКСАНОВУЮ ОСНОВУ ПРИ ИХ ПРЕОБРАЗОВАНИИ В МОНОДИСПЕРСНЫЕ ЧАСТИЦЫ МЕЗОПОРИСТОГО КРЕМНЕЗЕМА

A new universal approach to the biomimetic synthesis of hybrid organosilicate nanocomposites with texture and functionality good control has been developed, which consists in the use of biomacromolecules as mesogenic templates. The main strategy is to combine the self-association of polysaccharide nanorods with the flexibility of the sol-gel process in the chemistry of siloxane oligomers formed at various pH values of 3, 5, 8. The measured isotherms of low-temperature nitrogen adsorption-desorption by samples obtained at pH 5 and 8 refer to isotherms of type IV (a) characteristic of mesoporous adsorbents. The isotherms are dominated by the triangular hysteresis H2(a), which is due to network effects in ordered mesoporous materials of the SBA-16 and KIT-5 types. The isotherms of the samples obtained at pH 3 are of the hybrid type (I+IV) with the H4 hysteresis inherent in microporous adsorbents with slit-like mesopores between agglomerates of silica particles. It is shown that the control of the textural properties of hybrid nanocomposites and porous silica is possible by changing the temperature of thermal activation of organosilicate samples and the pH value of the silica gel precipitation medium. The advantage of the developed synthesis is the formation of new functionalities on the surface of silica through its heat treatment while maintaining the polysaccharide template either as its own functional basis or as a carbon resource.

In Ukrainian

Aromatic organic acids are among the common environmental pollutants that enter the water with washouts from agricultural lands, wastewater from chemical and pharmaceutical industries. Taking into account the high toxicity of aromatic substances, the important task of water purification is the removal of their trace amounts. This problem can be solved by using chemically modified inorganic materials, such as silicas, which have high mechanical, chemical, hydrolytic, and radiation stability. Therefore, they do not lose their sorption capacity during long-term use and do not pollute water with sorbent degradation products. The purpose of this work is the synthesis of a sorption-active material for removal of toxic aromatic acids by chemical immobilization of β-cyclodextrin functional groups on an aerosilogel (highly dispersed type of amorphous silica). A β-cyclodextrin-containing aerosilogel was synthesized by two-stage liquid-phase chemical modification of hydroxylated silica surface. Using the methods of IR spectroscopy, spectrophotometry, thermogravimetry, pH metry, low-temperature adsorption-desorption of nitrogen, chemical and elemental analysis of the surface, the surface structure and its quantitative chemical composition, and also parameters of porous structure of initial and chemically modified aerosilogels were determined. Sorption of benzoic, salicylic and β-resorcylic acids on aerosilogels from aqueous buffer solutions with pH=1 was studied. The insignificant contribution of silanol and aminopropyl groups and complete participation of chemically fixed β-cyclodextrin in the sorption of aromatic acids were proved. The results obtained are analyzed using kinetic models for pseudo-first and pseudo-second order processes, as well as Langmuir and Freundlich models for equilibrium adsorption on homogeneous and heterogeneous surfaces. It has been found that the sorption kinetic processes are well described by a pseudo-first order equation (in the presence of one type of functional groups on the surface) and a pseudo-second order equation for bi- and trifunctional aerosilogels. Experimental results on the equilibrium sorption of aromatic acids on β-cyclodextrin-containing aerosilogel are in good agreement with the Langmuir adsorption equation. This is evidence of decisive contribution of grafted oligosaccharide groups to the sorption of organic acids. The proposed chemical approach to increasing the sorption activity of aerosilogel can be used to obtain specific chromatographic carriers, as well as inorganic sorbents for the effective removal of small amounts of highly toxic organic substances from water and aqueous solutions.