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2022 год

1.

Recent Advances in the Preparation of Barium Sulfate Nanoparticles: A Mini-Review

ChemEngineering (2022), 6(2), 30.

doi.org/10.3390/chemengineering6020030

The potential for barium sulphate nanoparticles to be used in a variety of important fields has sparked a lot of attention. Methods for obtaining this material by milling (top-down approach) are not very popular due to the difficulty of controlling the size and shape of particles, as well as changes in their physicochemical properties during milling. More promising is the bottom-up approach, which is the interaction of Ba²⁺ and SO₄²⁻ ions in a liquid environment. Direct precipitation is the simplest method; however, it does not allow control of the particle size. Microemulsions, microreactors membrane dispersion, as well as spinning disc reactors are used to overcome drawbacks of direct precipitation and allow control of particle size and shape. This is ensured mainly by intensive controlled micromixing of the precursors with concentrations close to saturated ones. The present review focuses on recent advances in the production of barium sulfate nanoparticles using various approaches, as well as their advantages and limitations. The issues of scaling up the techniques are also considered, and promising methods for obtaining BaSO₄ nanoparticles are also discussed

Ketegenov, T., Kamunur, K., Batkal, A., Gani, D., & Nadirov, R. (2022). Recent Advances in the Preparation of Barium Sulfate Nanoparticles: A Mini-Review. ChemEngineering, 6(2), 30.

doi.org/10.3390/chemengineering6020030

2.

Enhancing Synthetic Zinc Ferrite Hydrochloric Acid Leaching by Using Isopropanol as a Solvent.

Mining, Metallurgy & Exploration (2022), 39(4), 1743-1751.

Doi.org/10.1007/s42461-022-00648-3

Zinc ferrite (ZnFe₂O₄) is a by-product of non-ferrous metal production and is considered a promising source of raw zinc. The most efficient way to extract zinc from its ferrite is via acidic extraction, specifically leaching by hydrochloric acid. A comparative study of synthetic zinc ferrite hydrochloric acid leaching in isopropanol, aqueous, and the mixed solvent was performed. Zinc ferrite was obtained by sintering a zinc and iron (III) oxide mixture. Crushed samples were subjected to leaching in 1 M HCl at 323, 333, and 353 K and pulp density of 1 g/100 Ml. The dissolution of zinc and iron into solution in organic media reached 77% at 353 K, while in an aqueous environment this value was 65%. The activation energy of 70.0 Kj/mol was found for the leaching process in an isopropanol environment, which is lower than that in an aqueous solution by 15%. The more efficient leaching effect of isopropanol is attributed to the lower dielectric constant of the alcohol which increases the affinity of chloride anions for zinc and iron cations at leaching.

Nadirov, R., & Karamyrzayev, G. (2022). Enhancing Synthetic Zinc Ferrite Hydrochloric Acid Leaching by Using Isopropanol as a Solvent. Mining, Metallurgy & Exploration, 39(4), 1743-1751.

Doi.org/10.1007/s42461-022-00648-3

3.

Selective Ozone-Assisted Acid Leaching of Copper from Copper Smelter Slag by Using Isopropanol as a Solvent

Minerals (2022), 12(8), 1047.

doi.org/10.3390/min12081047

Copper content in copper smelter slag exceeds that in copper ores, which has attracted increasing interest to recover copper from this by-product of pyrometallurgical copper production. The isopropanol-sulfuric acid-ozone system has been tested under different conditions to extract this metal from copper smelter slag containing chalcopyrite as a copper mineral. Isopropanol as a solvent played a key role in increasing the copper recovery to 87% after 5 h of leaching, while the use of an aqueous solution of sulfuric acid allowed only 13% of copper to be recovered. Iron extraction under these conditions was only 10%. The role of ozone was spectroscopically proven to oxidize ferrous ions to form ferric ions, which are effective oxidizers of chalcopyrite. The presence of copper in solution in the form of cuprous (Cu⁺) ions was proven electrochemically. The increased copper extraction in the solution was caused by the stabilization of cuprous ions by isopropanol. The limiting stage of the process was the chemical reaction on the chalcopyrite surface with the activation energy of 73.4 Kj mol⁻¹.

Nadirov, R., & Karamyrzayev, G. (2022). Selective Ozone-Assisted Acid Leaching of Copper from Copper Smelter Slag by Using Isopropanol as a Solvent. Minerals, 12(8), 1047.

doi.org/10.3390/min12081047

4.

Freshly Milled Quartz Particles Obtained from River Sand as an Efficient Natural Demulsifier for Crude Oil Emulsions

Processes (2022), 10(5), 811.

doi.org/10.3390/pr10050811

Saline water necessarily contained in crude oil forms complex and stable water-in-oil (w/o) emulsions with oil. Due to the negative impact of this emulsion on the oil’s transportation and refining, special materials are added to help break the emulsion and separate water. Herein, a comparative study of the demulsifying ability concerning w/o emulsion of the original and freshly milled quartz (FMQ) particles isolated from river sand was carried out. The effect of quartz with a mesh size of 75 μm on reducing emulsion stability was investigated using rheological measurements, interfacial tension measurements, demulsification tests, as well as routine methods for characterizing solid and liquid materials. With the addition of 3 wt% FMQ, 97% demulsification efficiency was achieved after 100 min of settling, against 140 min for the original quartz. The role of milling quartz is to increase the ability of water to adhere and thus locally increase the Ph value; this results in a reduction in the stability of the emulsion and its destruction. The prolonging effect of quartz milling lasted about 2.5–3.0 h, after which the demulsifying ability of milled quartz became comparable to that of the starting material.

Nadirov, K., Zhantasov, M., Nadirova, Z., Otarbaev, N., Bimbetova, G., & Nadirov, R. (2022). Freshly Milled Quartz Particles Obtained from River Sand as an Efficient Natural Demulsifier for Crude Oil Emulsions. Processes, 10(5), 811.

doi.org/10.3390/pr10050811

5.

Dissolution of Chalcopyrite in Presence of Chelating Agent and Hydrogen Peroxide

Transactions of the Indian Institute of Metals (2022), 75(1), 273-280.

Doi.org/10.1007/s12666-021-02426-z

Chelating agents (e.g., EDTA, titriplex III, etc.) are very important salts as they can take a complex form with metal ions. This study investigated usage of titriplex III in presence of hydrogen peroxide for metal extraction from chalcopyrite concentrate under various conditions such as conventional leaching, mechanical activation and ultrasound leaching. The results show that both titriplex and hydrogen peroxide are required for metal extraction from chalcopyrite concentrate. However, mechanical activation is an important parameter for increasing metal extraction, so that copper extraction increases to 83% from 47% after 30 min of grinding chalcopyrite by a high-energy grinding system. Metal extraction efficiency is improved by application of ultrasound to the leaching process. It is possible to obtain copper and iron extraction as 93% and 65%, respectively, under the following leaching conditions: mechanical activation time of 30 min, titriplex concentration of 100 g L⁻¹, H₂O₂ concentration of 2 mol L⁻¹, ultrasound power of 10%, leaching time of 90 min, leaching temperature of 45 °C and liquid–solid ratio of 25 Ml g⁻¹.

Turan, M. D., Silva, J. P., Sarı, Z. A., Nadirov, R., & Toro, N. (2022). Dissolution of Chalcopyrite in Presence of Chelating Agent and Hydrogen Peroxide. Transactions of the Indian Institute of Metals, 75(1), 273-280.

Doi.org/10.1007/s12666-021-02426-z

6.

Selective Hydrochloric Acid Leaching of Zinc, Lead and Silver from Mechanically Activated Zinc Plant Residue

Russian Journal of Non-Ferrous Metals (2022), 63(5), 490-499.

Doi.org/10.3103/S1067821222050108

Abstract—A solid waste from zinc production, zinc plant residue (ZPR) is a valuable resource for the recovery

of zinc (Zn), lead (Pb), and silver (Ag). However, the ferritic structure of ZPR makes it difficult to leach these

metals. Here, in order to increase the reactivity of the ZPR, mechanical activation using a high-energy ball

mill was used. The sample mechanically activated for 15 min was subjected to two-stage leaching with the

hydrochloric acid (HCl) solution. At the 1^st stage, 74% of Zn was recovered from mechanically activated ZPR

sample into the solution under the following conditions: 1 M HCl, 120 min leaching duration, liquid-to-solid

ratio (L : S) of 4, the temperature of 25°C, and a rotation speed of 600 rpm. At the 2^nd stage, 56% of Pb and

53% of Ag were recovered from the leaching residue, under the following optimized conditions: 8 M HCl,

120 min leaching duration, liquid-to-solid ratio (L : S) of 20, the temperature of 25°C, and a rotation speed

of 600 rpm. Сonceptual flow-diagram of the zinc, lead and silver selective recovery from ZPR is proposed

herein.

M. Deniz Turan, Shoeleh Assemi, Rashid K. Nadirov, Galymzhan A. Karamyrzayev, Omirserik Baigenzhenov, Norman Toro (2022). Selective Hydrochloric Acid Leaching of Zinc, Lead and Silver from Mechanically Activated Zinc Plant Residue. Russian Journal of Non-Ferrous Metals, 63(5), 490-499.

Doi.org/10.3103/S1067821222050108

7.

Catalytic Decomposition of Methane to Hydrogen over Al₂O₃Supported Mono- and Bimetallic Catalysts

Bulletin of Chemical Reaction Engineering & Catalysis, 17 (1), 1-12 (doi:10.9767/bcrec.17.1.12174.1-12)

This article discusses the decomposition of methane in the temperature range 550-800°C on low-percentage monometallic (Ni/γ-Al₂O₃, Co/γ-Al₂O₃) and bimetallic (Ni-Co/γ-Al₂O₃) catalysts. It is shown that the bimetallic cata-lyst is more active in the decomposition of methane to hydrogen than monometallic ones. At a reaction tempera-ture of 600°C, the highest methane conversion is 81%, and the highest hydrogen yield of 51% is formed on Ni-Co/γ-Al₂O₃. A complex of physicochemical methods (Scanning Electron Microscope (SEM), X-ray Diffraction (XRD), Temperature Programmed Reduction (TPR-H2), etc.) established that the addition of cobalt oxide to the composi-tion of Ni/γ-Al₂O₃leads to the formation of surface bimetallic Ni-Co alloys, while the dispersion of particles haracte-es and the reducibility of the catalyst is facilitated, which provides an increase in the concentration of metal parti-cles – active centers, which can be the reason for an increase in the catalytic properties of a bimetallic catalyst in comparison with monometallic ones. © 2022 Diponegoro University. All rights reserved.

Ergazieva, G. E., Makayeva, N., Shaimerden, Z., Soloviev, S. O., Telbayeva, М., Akkazin, Е., Ahmetova, F. (2022). Catalytic Decomposition of Methane to Hydrogen over Al2O3 Supported Mono- and Bimetallic Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 17 (1), 1-12 (doi:10.9767/bcrec.17.1.12174.1-12) 

8.

Electrochemical synthesis of Fe-containing composite for decomposition of methane into Cox-free hydrogen and nano-carbon

Chem. Pap. (2022). https://doi.org/10.1007/s11696-022-02420-9

Decomposition of methane is the most efficient method for obtaining pure hydrogen. As catalysts for decomposition of methane, in this work, Ni-foam and Ni–Fe composites obtained by the electrochemical method were used for the first time. Thin iron films were electrochemically grown by potential cycling on the Ni-foam surface. The obtained catalysts were tested for decomposition of methane in the temperature range of 650–850 °C and characterized using XRD, RAMAN, SEM, TGA/DTA, H₂-TPR and BET analysis of specific surface area and pore size. The effect of cycles (75, 150, and 250) of iron deposition on Ni-foam on its activity in methane decomposition was studied. It has been determined that the highest catalytic activity is observed for the composite, where the iron deposition cycle on nickel foam is 150. The Ni-Fe150 catalyst showed an initial methane conversion of 91% at a temperature of 850 °C, which increased from 60 min to 96.7% and from 180 min to 98.6%, and was stable for 540 min, while the hydrogen yield was 76%. It has been stated that graphite-like carbon is formed on all catalysts, and the largest amount (32%) is formed on Ni-Fe150. The data obtained in the work indicate that the increase in the activity of Ni-Fe150 in the decomposition of methane is associated with the formation of a Ni–Fe alloy and an increase in the reducibility of iron cations in the composition of the Ni–Fe alloy. In addition, the formation of graphite-like carbon with a high defectiveness on the surface of the Ni-Fe150 catalyst promotes the decomposition of methane in areas not covered with carbon.

Yergaziyeva, G., Makayeva, N., Abdisattar, A. et al. Electrochemical synthesis of Fe-containing composite for decomposition of methane into Cox-free hydrogen and nano-carbon. Chem. Pap. (2022). https://doi.org/10.1007/s11696-022-02420-9 

9.

Comparative Study of Physicochemical Characteristics and Catalytic Activity of Copper Oxide over Synthetic Silicon Oxide and Silicon Oxide from Rice Husk in Non-Oxidative Dehydrogenation of Ethanol

ChemEngineering 2022, 6(5), 74; https://doi.org/10.3390/chemengineering6050074

The article presents the results of comparative research on the physicochemical characteristics and catalytic activity of copper oxide supported on synthetic SiO2 and SiO2 (RH) from rice husk. SiO2 (RH) is more hydrophobic compared to SiO2, which leads to the concentration of copper oxide on its surface in the form of a “crust”, which is very important in the synthesis of low-percentage catalysts. According to SEM, XRD, and TPR-H2, the use of SiO2 (RH) as a carrier leads to an increase in the dispersion of copper oxide particles, which is the active center of ethanol dehydrogenation.

Mambetova, M.; Yergaziyeva, G.; Dossumov, K.; Askaruly, K.; Azat, S.; Bexeitova, K.; Anissova, M.; Baizhomartov, B. Comparative Study of Physicochemical Characteristics and Catalytic Activity of Copper Oxide over Synthetic Silicon Oxide and Silicon Oxide from Rice Husk in Non-Oxidative Dehydrogenation of Ethanol. ChemEngineering 2022, 6, 74. https://doi.org/10.3390/chemengineering6050074

Effect of Preparation Method on the Activity of Fe2O3-NiO/γ-Al2O3 Catalyst in Decomposition of Methane

(2022) Eurasian Chemico-Technological Journal, 24 (3), pp. 221 – 227.

DOI 10.18321/ectj1435

The effect of method preparation on the activity of Fe2O3-NiO/γ-Al2O3 catalyst was investigated in process decomposition of methane. Fe2O3-NiO/γ-Al2O3 catalyst was prepared by impregnation and solution combustion methods. The samples were characterized by X-ray phase analysis (XRD), temperature-programmed hydrogen reduction (TPR-H2), BET and Raman spectroscopy. It has been shown that the method of preparation plays an important role in regulating the textural and morphological properties of catalysts and provides a difference in their catalytic activity. The synthesis of the Fe2O3-NiO/γ-Al2O3 catalyst by the solution combustion method, in comparison with the capillary impregnation method, leads to the formation of a large amount of FeNi and FeAl2O4 solid solutions, which ensured good catalytic activity at high temperatures. The Fe2O3-NiO/γ-Al2O3 catalyst synthesized by the solution combustion method demonstrated good activity with a hydrogen yield of 52% within 150 min of the reaction without any deactivation. According to the results of Raman spectroscopy, graphene-like carbon was obtained on the surface of the catalysts. On the catalyst of Fe2O3-NiO/γ-Al2O3 (СI) synthesized by capillary impregnation, 4‒5 layer graphene on Fe2O3-NiO/γ-Al2O3 (SC)-6-7 layer graphene is formed

Yergaziyeva G., Makayeva N., Anissova M., Dossumov K., Mambetova M., Shaimerden Z., Niyazbaeva A., Akkazin E. Effect of Preparation Method on the Activity of Fe2O3-NiO/γ-Al2O3 Catalyst in Decomposition of Methane

(2022) Eurasian Chemico-Technological Journal, 24 (3), pp. 221 – 227.

DOI: 10.18321/ectj1435

10.

Test trials of a process to produce briquettes from coal mining waste

At the present time, coal production wastes up to 2 % of fine fraction, which has adverse impact on the environment. On the other hand, coal fines can be a feedstock to obtain different products of chemical processing—benzines, oils, briquettes, etc. For this reason, it is necessary to develop dedicated technologies to utilize fine waste in manufacture of products having high added value. The experimental results demonstrate usability of wheat bran as a binder in coal waste briquetting. It is found how the binder and the briquetting conditions influence the physical and mechanical properties and combustion characteristics of coal briquettes. The optimized coal briquetting conditions are: carbonization of feedstock, use of binder in quantity of 25–30 mass%, briquetting pressure of 4 Mpa. Thus, the authors have analyzed the influence of the briquetting conditions on the properties of coal briquettes, and have tested the earlier developed approaches to transformation of Oi-Karagai coal fines into a target product of high added value.

Kamunur, K., Ketegenov, T., Kalugin, S., Karagulanova, A., Zhaksibaev, M., The role of the alkaline promoter on the formation of strength and burning of coal briquettes //

South African Journal of Chemical Engineering, 2022, 42, P. 156–161

https://doi.org/10.1016/j.sajce.2022.08.009

11.

The role of the alkaline promoter on the formation of strength and burning of coal briquettes

Coal fines formed in the process of coal mining are of no commercial value and accumulate in dumps, harming the environment. At the same time, they can be used as a source of low-smoke fuel used by the population for domestic needs. To create such a product, it is necessary to solve many technical problems related to selecting binders for coal, providing mechanical strength, and initiating the combustion process of coal briquettes. This study presents the results of obtaining briquette fuel from fine particles of brown coal. Low-temperature pyrolysis determined the qualitative and quantitative composition of volatile components and proposed a mechanism for forming a porous structure of coal after thermal exposure. A composition of a mixture of caustic soda and grain processing waste was used as a binder for the production of briquettes. The mechanism of the formation of adhesive properties of the binder material is explained, and the optimal concentration of sodium hydroxide in it is determined. The positive role of caustic soda as a catalyst for the burning of briquettes is shown, and the activation energy of the burning process is calculated. 

K. Kamunur, T. Ketegenov, S. Kalugin, A. Karagulanova, M. Zhaksibaev, The role of the alkaline promoter on the formation of strength and burning of coal briquettes, South African Journal of Chemical Engineering, Volume 42, 2022, Pages 156-161, ISSN 1026-9185, https://doi.org/10.1016/j.sajce.2022.08.009.

12.

Mechanisms for Ultrafine Copper Powders Electrolytes Production in the Presence of Titanium Ions 

Copper (Cu) powder production, in a sulfuric acid (H₂SO₄) solution with titanium (Ti) ions, was studied by electrolysis, using Cu anodes. It was empirically proven that this process occurs by three different stage-based mechanisms that depend on the electrolyte composition and electrolysis conditions. The first mechanism occurs in a H₂SO₄ solution with Cu²⁺ ions and Ti⁴⁺ (tetravalent ions). Cu²⁺ are cathodically reduced, forming Cu powder (CP), since the process occurs at current densities (J) lower than the limiting one. So, part of the current that would be consumed by the hydrogen ions (H⁺) reduction reaction is spent to reduce Ti⁴⁺, which results in Ti³⁺ (trivalent ions). These, in the cathode space, reduce Cu²⁺, which, simultaneously, regenerates Ti⁴⁺. Then, these diffuse and are again reduced at the cathode, and Ti³⁺ are formed, reducing Cu²⁺, in a cyclic process that

further increases CP production current efficiency (CE) at the near-cathode space, forming more dispersed particles. The second mechanism occurs in a H₂SO₄ solution with only Ti⁴⁺. During the electrochemical circuit current flow, the Cu anode is oxidized to form Cu²⁺, and Ti⁴⁺ are reduced to Ti³⁺, on the cathode surface. Then, Cu²⁺ and Ti³⁺, by diffusing the solution volume and meeting in the inter-electrode space, chemically interact with each other, due to the red-ox (reduction-oxidation) potential difference, forming a dispersed CP and Ti⁴⁺. These diffuse one more time, and are again reduced to Ti³⁺. These processes are cyclically repeated, i.e., Ti⁴⁺ work as catalyst. The third mechanism takes place in H₂SO₄ with Ti³⁺. When the current flows through the electrolyte, the Cu anode is oxidized, forming Cu²⁺, which are immediately reduced in the anode by Ti³⁺, producing CP. Ti⁴⁺ are formed due to the red-ox reaction diffusion to the cathode, being reduced to Ti³⁺ on its surface, which again interact with Cu, producing CP on the anode. Since, in all mechanisms (except the first), CP is not directly produced on The cathode surface, but in the inter-electrode space, further growth of Cu particles does not occur. Thus, CP particles of spherical shape, with sizes from 0.01 to 0.1 μm, are formed, with a CE from 95.2 to 99.1%, under optimal conditions. 

Bayeshov, А., Bayeshova, А., Abduvaliyeva, U., Buketova, A.

Portugaliae Electrochimica Acta, 2022, 40(5), стр. 373–381

https://doi.org/10.4152/pea.2022400505

13.

Recovery of “Hard-to-Recover” Selenate Ions in Sulfuric Acid Solutions during Polarization of Titanium Electrodes by Industrial Alternating Current 

The article is devoted to the study of selenium (VI) reduction processes in sulfuric acid solutions when titanium electrodes are polarized by alternating current of industrial frequency (50 Hz). It was found that selenate ion reduction occurs on the surface of titanium electrodes in the cathode half-cycle of alternating current (practically at the cathode) by reaction: SeO₂⁻⁴+ 6e + 8H⁺ → Se + 4H₂O. In addition, the recovery is carried out by titanium (III) ions: 6Ti³⁺ SeO₂⁻⁴+ 8H⁺ → Se + 6Ti⁴⁺ + 4H₂O. It has been established that titanium (III) ions are products of dissolution of titanium during polarization by alternating current, so they can be formed by reaction: 2Ti + 6H⁺ → 2Ti³⁺ + 3H₂. Reduction in selenate ions during polarization by alternating current can also occur due to the cementation reaction with titanium: 3Ti + 2SeO₂⁻⁴ + 16H⁺ → 2Se + 8H₂O + 3Ti⁴⁺. It was shown for the first time that the selenate ion is reduced to form a dispersed selenium powder with a high current efficiency. Depending on the conditions, both amorphous and crystalline selenium modifications are produced. 

Abduali Bayeshov, Azhar Bayeshova, Khairulla Zhanbekov, Madina Zhubanys and Pakhchan Naguman

Inorganics 2022, 10(6), 72

https://doi.org/10.3390/inorganics10060072

Production of Copper Powders by Alternating Current Polarization of a Copper–Titanium Electrode Pair

The possibility of obtaining copper powders using alternating current of industrial frequency is shown. The electrochemical circuit consisted of two cells connected in parallel. A copper–titanium electrode pair was installed in each cell. The electrolyte was an aqueous solution containing copper(II) sulfate. In cell 1, during electrolysis, the copper electrode dissolves in the positive half-cycle with the formation of Cu2+, which are reduced on the titanium electrode to Cu0 in the form of a dispersed powder. In cell 2 in this half-cycle, the electrolysis does not occur. When the direction of the current is changed, electrolysis occurs only in cell 2. It was found that when the current density changes in the range of 10–75 kA m–2, the current efficiency of Cu0 in each cell increases from 31 to 85.2%. When the concentration of Cu2+ varies within 5–10 g L–1, the current efficiency of Cu0 in each cell increases to 84.2%. As a result of the process, ultrafine copper powders are formed. Scanning electron microscopy has shown that the average particle size of copper powders does not exceed 1 µm.

Bayeshova A. A. K. Bayeshova, A. N. Zhylysbayeva, A. S. Kadirbayeva, R. N. Nurdillayeva. Russian Journal of Applied Chemistry. – 2022. - Vol. 95. - No.5. – Р.685–688/ 10.1134/S1070427222050081 

Synthesis and Growth of Rare Earth Borates NaSrR(BO₃)₂ (R = Ho–Lu, Y, Sc)

NaSrR(BO₃)₂ (R = Ho-Lu, Y, Sc) compounds were obtained for the first time. Their structures exhibit disordered positions of Sr²⁺ and Na⁺ atoms while RO6 polyhedra are connected through the BO3 groups. Large distances between R atoms and high transparency in the range of 250-900 nm make them promising for phosphor applications. A pathway to obtain single crystals was shown by growing NaSrY(BO₃)₂ and NaSrYb(BO₃)₂ by the top seeded solution growth method with Na₂O-B₂O₃-NaF flux.

Kuznetsov A.B., Kokh K.A., Sagatov N., Gavryushkin P.N., Molokeev M.S., Svetlichnyi V.A., Lapin I.N., Kononova N.G., Shevchenko V.S., Bolatov A., Uralbekov B., Goreiavcheva A.A., Kokh A.E. Synthesis and Growth of Rare Earth Borates NaSrR(BO₃)₂ (R = Ho–Lu, Y, Sc). Inorganic Chemistry, V.61, Is.19, p.7497-7505, 2022. 10.1021/acs.inorgchem.2c00596

Single-phase CZTSe via isothermal recrystallization in a KI-KCl flux

(2022) CrystEngComm, 24 (12), pp. 2291 - 2296.

10.1039/d1ce01653a

A facile, two-step procedure was developed to prepare a pure CZTSe (Cu2ZnSnSe4) phase from elemental Cu, Zn, Sn, and Se with the addition of a KI-KCl mixture. During the first step, the mixture charge was reacted at 1000 °C to convert all the metals to selenides. Next, the extracted charge was powdered and again heated to 750 °C to obtain homogeneous grains of CZTSe with a size of 30-100 microns. The main intermediate phase during the synthesis of Cu2SnSe3 was found to dissolve Zn up to 11.5 at% and, without Raman spectroscopy data, this phase could be easily confused with CZTSe because they are not optically distinguishable. On the other hand, the deviation of the Zn content in CZTSe does not exceed ±0.5 at%

Bakhadur A.M., Uralbekov B.M., Atuchin V.V., Mukherjee S., Kokh K.A. Single-phase CZTSe via isothermal recrystallization in a KI-KCl flux

(2022) CrystEngComm, 24 (12), pp. 2291 - 2296.

DOI: 10.1039/d1ce01653a

15.

Effect of mineral fertilisers application on the transfer of natural radionuclides from soil to radish (Raphanus sativus L.)

DOI: 10.1016/j.jenvrad.2022.106863 

Non-controlled usage of mineral fertilisers in agriculture land of Kazakhstan is a concerning issue, due to possible contamination of the soil by radionuclides. Pot experiment of growing of R. sativus with application of mineral fertilisers was carried out under natural conditions. Two commonly used mineral fertilisers, mono-potassium phosphate and ammonium nitrate, were chosen in the frame of current research to determine the impact of mineral haracteri on transfer of natural radionuclides from soil to R. sativus edible part. For this goal, the activity concentrations of natural radionuclides U-234, U-238, Th-230, Th-232 and Ra-226, were determined in both R. sativus edible part and the investigated soil by using alpha-particle spectrometry. The highest activity concentrations were found for R. sativus edible part growing on soil that was haracteri by mono-potassium phosphate and were equal to 174 ± 17, 134 ± 15, 62 ± 4, 15 ± 2 and 2.8 ± 0.6 Bq/kg for U-234, U-238, Th-230, Th-232 and Ra-226, respectively. The results of soil-to- R. sativus edible part transfer factor for different radionuclides varied depending on the mineral haracteri used. For evaluation of impact during consumption of R. sativus edible part by a population of Kazakhstan, annual effective ingestion dose and excess lifetime cancer risk were determined. The highest annual effective ingestion dose was found for R. sativus edible part cultivated in mono-potassium phosphate-fertilised soil and was equal to 4.4 μSv year^-1.

Nursapina NA, Shynybek BA, Matveyeva IV, Nazarkulova SN, Štrok M, Benedik L, Ponomarenko OI. Effect of mineral fertilisers application on the transfer of natural radionuclides from soil to radish (Raphanus sativus L.). J Environ Radioact. 2022 Jun;247:106863. Doi: 10.1016/j.jenvrad.2022.106863.

16.

Uranium isotopes in food and effect on health of Southern Kazakhstan citizens

DOI: 10.1016/j.jenvrad.2022.106863

Natural uranium isotopes were determined in food products of the Kyzylorda region in Kazakhstan. This region is haracterized by the influence of the uranium industry, as up to 15% of the world uranium reserves are concentrated in this part of Kazakhstan and the adjacent territory of Kyrgyzstan. The food products most consumed by locals were selected for this survey. Special attention was paid to the analysis of edible and non-edible parts of food products and the assessment of a possible increase in risk due to consumption of non-edible parts. The highest content of uranium, of 80.2 mu g/kg, was found in the edible part of the carrot. The highest activity concentrations of uranium isotopes are found in carrot, potato and onion, as edible parts of these vegetables are grown in the soil. All estimated cancer risks for uranium isotopes range from 10(-14) to 10(-12), which are insignificant values.

Nursapina, N., Diyarov, A., Matveyeva, I., Nazarkulova, S., Ponomarenko, O. (2022) Uranium isotopes in food and effect on health of Southern Kazakhstan citizens. Food Additives and Contaminants: Part B Surveillance, V.15, Is1., P.56-61, 2022.   https://doi.org/10.1080/19393210.2021.2010810

17.

DMSO- mediated solvothermal synthesis of S/AgX (X = Cl, Br) microstructures and study of their photocatalytic and biological activity

Microstructures with different content of sulfur (S) and silver halides (AgX, X = Cl, Br) were obtained by DMSO-mediated solvothermal synthesis with using of two methods: 1) precipitation of S at room temperature and 2) precipitation of S with water. The XRD and Raman analysis has shown the presence of S and AgX phases. The SEM analysis have displayed that S/AgX microstructures are represented by agglomerates of S with irregular form with 25-50 mu m in size, which are mostly covered by spherical particles of AgX with size range from 0.7 to 2 mu m. These results were proved by TEM elemental mapping. TEM analysis also showed the presence of the dense micron-sized aggregates of particles from 5 to 100 nm with highly developed system of dense intergrain boundaries for S/AgCl sample, while S/AgBr sample was represented by large aggregates of crystalline particles and an amorphous matrix. Obtained microstructures exhibited low specific surface area. XPS revealed the presence of metallic silver on the surface of all samples due to partial photoreduction. Its content was much higher when sulfur was precipitated at laboratory temperature. According to TGA-DSC analysis the actual composition of the microstructures corresponds to the desired content. The samples with the highest content of AgX were able to degrade from 70 to 90 % of molecules of Orange II, after 180 min of visible light irradiation. Up to 5 cycles, almost similar photocatalytic activity could be retained for all the samples. The majority of the samples exhibited antimicrobial activity, namely they were active in suppression of the S. aureus ATCC 6538-P, E. coli ATCC 8739, C.albicans ATCC 10231, P.aeruginosa ATCC 9027, Erwinia amylovora, S. aureus ATCC BAA-39 and E. coli ATCC BAA-196 strains.

Khan, N., Balaz, M., Burkitbayev, M., Tatykayev, B., Shalabayev, Z., Nemkayeva, R., Jumagaziyeva, A., Niyazbayeva, A., Rakhimbek, I., Beldeubayev, A., Urakaev, F. DMSO- mediated solvothermal synthesis of S/AgX (X = Cl, Br) microstructures and study of their photocatalytic and biological activity. Applied surface science, V.601., 2022. DOI10.1016/j.apsusc.2022.154122

18.

Sustainable Synthesis of Cadmium Sulfide, with Applicability in Photocatalysis, Hydrogen Production, and as an Antibacterial Agent, Using Two Mechanochemical Protocols

CdS nanoparticles were successfully synthesized using cadmium acetate and sodium sulfide as Cd and S precursors, respectively. The effect of using sodium thiosulfate as an additional sulfur precursor was also investigated (combined milling). The samples were characterized by XRD, Raman spectroscopy, XPS, UV-Vis spectroscopy, PL spectroscopy, DLS, and TEM. Photocatalytic activities of both CdS samples were compared. The photocatalytic activity of CdS, which is produced by combined milling, was superior to that of CdS, and was obtained by an acetate route in the degradation of Orange II under visible light irradiation. Better results for CdS prepared using a combined approach were also evidenced in photocatalytic experiments on hydrogen generation. The antibacterial potential of mechanochemically prepared CdS nanocrystals was also tested on reference strains of E. coli and S. aureus. Susceptibility tests included a 24-h toxicity test, a disk diffusion assay, and respiration monitoring. Bacterial growth was not completely inhibited by the presence of neither nanomaterial in the growth environment. However, the experiments have confirmed that the nanoparticles have some capability to inhibit bacterial growth during the logarithmic growth phase, with a more substantial effect coming from CdS nanoparticles prepared in the absence of sodium thiosulfate. The present research demonstrated the solvent-free, facile, and sustainable character of mechanochemical synthesis to produce semiconductor nanocrystals with multidisciplinary application.

Shalabayev, Z.; Baláž, M.; Khan, N.; Nurlan, Y.; Augustyniak, A.; Daneu, N.; Tatykayev, B.; Dutková, E.; Burashev, G.; Casas-Luna, M.; Džunda, R.; Bureš, R.; Čelko, L.; Ilin, A.; Burkitbayev, M. Sustainable Synthesis of Cadmium Sulfide, with Applicability in Photocatalysis, Hydrogen Production, and as an Antibacterial Agent, Using Two Mechanochemical Protocols. Nanomaterials 2022, 12, 1250. https://doi.org/10.3390/nano12081250

19.

Mechanochemical synthesis of non-stoichiometric copper sulfide Cu1.8S applicable as a photocatalyst and antibacterial agent and synthesis scalability verification

DOI 10.1039/d2fd00082b 

An effort to prepare different non-stoichiometric CuxSy compounds starting from elemental precursors using mechanochemistry was made in this study. However, out of the 7 stoichiometries tested, it was only possible to obtain three phases: covellite CuS, chalcocite Cu2S and digenite Cu1.8S and their mixtures. To obtain the digenite phase with the highest purity, the Cu : S stoichiometric ratio needed to be fixed at 1.6 : 1. The reaction between copper and sulfur was completed within a second range, however, milling was performed for up to 15 minutes until the equilibrium in phase composition between digenite and covellite was reached. The possibility of preparing the product in a 300 g batch by eccentric vibratory milling in 30 minutes was successfully verified at the end. The estimated crystallite sizes for the digenite Cu1.8S obtained via lab-scale and scalable experiments were around 12 and 17 nm, respectively. The obtained products were found to be efficient photocatalysts under visible light irradiation in the presence of hydrogen peroxide, being capable of the complete degradation of the Methyl Orange dye in a concentration of 10 mg L−1 in 2 hours. Finally, the antibacterial potential of both lab-scale and large-scale industrial products was proven and, regardless of the manufacturing scale, the nanoparticles retained their properties against bacterial cells

Baláž M., Augustyniak A., Tatykayev B., Shalabayev Z., Burashev G., Dutková E., Daneu N., Briančin J., Balážová Ľ., Tkáčiková Ľ., Stahorský M., Achimovičová M., Baláž P. Mechanochemical synthesis of non-stoichiometric copper sulfide Cu1.8S applicable as a photocatalyst and antibacterial agent and synthesis scalability verification

(2022) Faraday Discussions, 241, pp. 367 – 386. DOI: 10.1039/d2fd00082b

20.

Photoluminescence

Quenching

Concentration and

Quantum Yield in

(Y_1–xPr_x)₂O₂Se Solid

Solutions

Abstract—(Y_1–xPr_x)₂O₂Se solid solutions with х = 0.004, 0.008, 0.010, 0.012, and 0.020 have been prepared from oxides by ampule synthesis. We have measured their excitation spectra at λ_em = 514 nm and their photoluminescence and quantum yield spectra at λ_ex = 463 nm (T = 300 K). Comparing their emission intensities at wavelengths of 514 (³P₀ → ³H₄ transition) and 670 nm (³P₀ → ³F₂ transition), we have determined the optimal dopant concentration (x = 0.01), at which the quantum yield has a maximum, reaching 3% 

Tarasenko, M.S., Ryadun, A.A., Orazov, Z.K. et al. The Concentration Quenching of Photoluminescence and the Quantum Yield in (Y_1–xPr_x)₂O₂Se Solid Solutions. Inorg Mater 57, 830–834 (2021). https://doi.org/10.1134/S002016852108015X 

21.

Transformation of teacher training in a rapidly evolving digital environment

DOI: 10.1007/s10639-021-10749-z

The purpose of the study is to consider the problem of digital competence of rising teachers and provide recommendations for its improvement. The study generally describes the widespread use of digital tools in the classroom, namely the current situation, barriers and prospects associated with it. The research was conducted using a digital questionnaire that was sent to respondents by e-mail. 

V. Shurygin, R Ryskaliyeva, E. Dolzhich, S. Dmitrichenkova, A.Ilyin

Transformation of teacher training in a rapidly evolving digital environment

Education and Information Technologies

2022 | Journal article

DOI: 10.1007/s10639-021-10749-z

22.

Properties of CuFeS₂/TiO₂ Nanocomposite Prepared by Mechanochemical Synthesis 

DOI: 10.3390/ma15196913

Abstract: CuFeS2/TiO2 nanocomposite has been prepared by a simple, low-cost mechanochemical route to assess its visible-light-driven photocatalytic efficiency in Methyl Orange azo dye decolorization. The structural and microstructural characterization was studied using X-ray diffraction and high-resolution transmission electron microscopy. The presence of both components in the composite and a partial anatase-to-rutile phase transformation was proven by X-ray diffraction. Both components exhibit crystallite size below 10 nm. The crystallite size of both phases in the range of 10– 20 nm was found and confirmed by TEM. Surface and morphological properties were characterized by scanning electron microscopy and nitrogen adsorption measurement. Scanning electron microscopy has shown that the nanoparticles are agglomerated into larger grains. The specific surface area of the nanocomposite was determined to be 21.2 m2· g−1. Optical properties using UVVis and photoluminescence spectroscopy were also investigated. CuFeS2/TiO2 nanocomposite exhibits strong absorption with the determined optical band gap 2.75 eV. Electron paramagnetic resonance analysis has found two types of paramagnetic ions in the nanocomposite. Mössbauer spectra showed the existence of antiferromagnetic and paramagnetic spin structure in the nanocomposite. The CuFeS2/TiO2 nanocomposite showed the highest discoloration activity with a MO conversion of ~ 74% after 120 min irradiation. This study has shown the possibility to prepare nanocomposite material with enhanced photocatalytic activity of decoloration of MO in the visible range by an environmentally friendly manner 

Erika Dutkova, Matej Baláž, Nina Daneu, Batukhan Tatykayev, et al. «Properties of CuFeS2/TiO2 Nanocomposite Prepared by Mechanochemical Synthesis." Materials 15, no. 19 (2022): 6913. DOI: 10.3390/ma15196913

23.

Peroxide Oxidative Desulfurization of the Gas Condensate from Karachaganak Field

(2022) Petroleum Chemistry, 62 (9), pp. 1081 – 1086.

DOI: 10.1134/S0965544122090080

Oxidative desulfurization of the gas condensate from Karachaganak field (Kazakhstan) was carried out. The influence of the oxidation conditions on the residual sulfur content in the gas condensate was examined. It was found that oxidation at a temperature of 60°C in the presence of hydrogen peroxide, as well as of sodium molybdate as a catalyst, affords a 91% decrease in the total sulfur content in the gas condensate. The oxidative desulfurization process was shown to have no significant effect on the physicochemical characteristics of the gas condensate

Muktaly D., Myltykbaeva Z.K., Akopyan A.V., Smaiyl M.B. Peroxide Oxidative Desulfurization of the Gas Condensate from Karachaganak Field

(2022) Petroleum Chemistry, 62 (9), pp. 1081 – 1086.

DOI: 10.1134/S0965544122090080

24.

Thermal methods of solid fuel processing: review

(2022) Oil Shale, 39 (3), pp. 217 - 240.

DOI: 10.3176/oil.2022.3.04

A review of literature data on the processing of solid types of combustible fossils into liquid fuels and chemical products has been carried out. The reserves of solid fossil fuels far exceed the natural resources of oil and gas, so the development of methods for processing solid fossil fuels into chemical products and liquid fuels is an urgent task. The main methods of processing coal and oil shale (OS) are reduced to pyrolysis and supercritical gasification. Pyrolysis is preferred for processing oil shale into shale oil, and currently a promising method for processing coal is extraction with supercritical solvents such as water and CO2 at temperatures up to 900 °C and in some cases with the addition of a catalyst. For oil shale, the gasification process, like pyrolysis, is carried out under milder conditions, since the mineral part of oil shale contains trace elements that act as catalysts, and the structure of the organic part of oil shale is more similar in composition to oil.

Myltykbayeva Z.K., Yeshova Z.Т., Smaiyl М.B. Thermal methods of solid fuel processing: review

(2022) Oil Shale, 39 (3), pp. 217 - 240.

DOI: 10.3176/oil.2022.3.04

25.

Synthesis of polymer protected Pd–Ag/ZnO catalysts for phenylacetylene hydrogenation

(2022) Journal of Nanoparticle Research, 24 (12), art. no. 236.

DOI: 10.1007/s11051-022-05621-1

A simple and environmentally friendly method, based on sequential adsorption of polyacrylamide (PAM) and transition metal ions (Pd2+, Ag+) on zinc oxide precipitated from water solution, was used to synthesize supported mono- and bimetallic catalysts with various Pd:Ag ratios. The catalyst characterization results indicated that PAM and metal ions are completely adsorbed by zinc oxide, forming polymer-stabilized Pd and Ag nanoparticles of 1–3 nm in size, evenly distributed on the support surface. The catalysts were studied in the hydrogenation of phenylacetylene under mild conditions (0.1 MPa, 40 °C). Although Ag-free 1%Pd-PAM/ZnO catalyst presents an interesting catalytic performance (in terms of activity, selectivity, and stability), among PAM-modified catalysts the optimal was 1%Pd–Ag(3:1)-PAM/ZnO, presenting a selectivity to styrene of 88% at 91% conversion of phenylacetylene. For comparison, similar Pd–Ag (3:1) bimetallic catalysts modified with polysaccharides, such as pectin (Pec), chitosan (Chit), and 2-hydroxyethylcellulose (HEC), were studied in the hydrogenation process. The catalysts demonstrated nearly the same selectivity to styrene. The activity of the catalysts decreases in the following order: 1%Pd–Ag(3:1)-HEC/ZnO > 1%Pd–Ag(3:1)-PAM/ZnO > 1%Pd–Ag(3:1)-Pec/ZnO > 1%Pd–Ag(3:1)-Chit/ZnO.

Zharmagambetova A., Auyezkhanova A., Talgatov E., Jumekeyeva A., Buharbayeva F., Akhmetova S., Myltykbayeva Z., Nieto J.M.L. Synthesis of polymer protected Pd–Ag/ZnO catalysts for phenylacetylene hydrogenation

(2022) Journal of Nanoparticle Research, 24 (12), art. no. 236.

DOI: 10.1007/s11051-022-05621-1

26.

V-Porphyrins Encapsulated or Supported on Siliceous Materials: Synthesis, Characterization, and Photoelectrochemical Properties

(2022) Materials, 15 (21), art. no. 7473.

DOI: 10.3390/ma15217473

Metalloporphyrin-containing mesoporous materials, named VTPP@SBA, were prepared via a simple anchoring of vanadyl porphyrin (5,10,15,20-Tetraphenyl-21H,23H-porphine vanadium(IV) oxide) through a SBA-15-type mesoporous material. For comparison, vanadyl porphyrin was also impregnated on SiO2 (VTPP/SiO2). The characterization results of catalysts by XRD, FTIR, DR-UV-vis, and EPR confirm the incorporation of vanadyl porphyrin within the mesoporous SBA-15. These catalysts have also been studied using electrochemical and photoelectrochemical methods. Impedance measurements confirmed that supporting the porphyrin in silica improved the electrical conductivity of samples. In fact, when using mesoporous silica, current densities associated with oxidation/reduction processes appreciably increased, implying an enhancement in charge transfer processes and, therefore, in electrochemical performance. All samples presented n-type semiconductivity and provided an interesting photoelectrocatalytic response upon illumination, especially silica-supported porphyrins. This is the first time that V-porphyrin-derived materials have been tested for photoelectrochemical applications, showing good potential for this use.

Myltykbayeva Z.K., Seysembekova A., Moreno B.M., Sánchez-Tovar R., Fernández-Domene R.M., Vidal-Moya A., Solsona B., López Nieto J.M. V-Porphyrins Encapsulated or Supported on Siliceous Materials: Synthesis, Characterization, and Photoelectrochemical Properties

(2022) Materials, 15 (21), art. no. 7473.

DOI: 10.3390/ma15217473

2023 

1

Evaluation of dissolved and acid-leachable trace element concentrations in relation to practical water quality standards in the Syr Darya, Aral Sea Basin, South Kazakhstan

(2023) Chemosphere, 313, 137465

10.1016/j.chemosphere.2022.137465

The Syr Darya is one of the major rivers supplying the Aral Sea with freshwater. Soviet programs aimed at maximizing agricultural productivity in the Syr Darya basin increased diversion of water drastically affecting its water quality with significant consequences to its suitability for irrigation, fisheries and other uses. While water quality standards for trace elements are typically measured in the dissolved phase, there is evidence that adsorbed phases may also be relevant. Here we report potentially available heavy metals and metalloid concentrations in the Syr Darya water through the treatment of unfiltered waters samples with dilute nitric acid. Significant differences were found for most studied elements (Mann-Whitney U Test, p < 0.05) between their dissolved and acid-leachable concentrations. For Sr and Se in both sampling campaigns, no significant differences were found between their dissolved and acid-leachable concentrations, indicating their low geochemical reactivity. Dissolved V concentrations and acid-leachable Ni and Zn were found to exceed Kazakhstan Maximum Permissible Concentrations (MPC) values for the protection of fishery water quality. Our study evaluates the importance of considering regulatory issues of measuring trace metal concentrations to assess the water suitability for fisheries and irrigation.

Satybaldiyev, Bagdat ;Ismailov, Baimurat; Nurpeisov Nurbek; Kenges, Kairat; Snow Daniel D.;Malakar, Arindam;Uralbekov Bolat (2023) Evaluation of dissolved and acid-leachable trace element concentrations in relation to practical water quality standards in the Syr Darya, Aral Sea Basin, South Kazakhstan. Chemosphere, 313, 137465.

2

Predicted aquatic and human health risks associated with the presence of metals in the Syr Darya and Shardara Reservoir, Kazakhstan

(2023) Science of the Total Environment, 859, 159827

10.1016/j.scitotenv.2022.159827

Due to the decline of the Aral Sea fishery and recent efforts to expand the fisheries sector in Kazakhstan for both local consumption and global export, there is a need to sustain other fisheries in the area, including the Shardara Reservoir, which lies in the Syr Darya basin. Metals are present in the Syr Darya; yet, their impacts on fishery and consumer health remain unclear. Thus, the objectives of this study were to evaluate: 1) the potential impacts of metals on Syr Darya basin fish and 2) the human health risks posed by consumption of Shardara Reservoir fish. The health of the fishery was assessed by comparing surface water metal concentrations to maximum permissible concentrations (MPCs), calculating water quality index (WQI) and degree of contamination (Cd) values, and evaluating gene expression biomarker responses in wild-caught roach (Rutilus rutilus). To assess the risk to consumers, metal concentrations in roach were used to calculate hazard quotients (HQs) and hazard indices (HIs). Water concentrations of Cu, Fe, Mn, Se, Sr and V exceeded MPCs and all sites were classified as highly polluted based upon WQI and Cd values. This, along with site-specific differences in the expression of genes associated with xenobiotic metabolism and oxidative stress in roach, indicates potential risks to the fishery. Though all HQs and HIs were below 1 indicating a lack of significant risk to consumers, Pb levels in roach exceeded MPCs for safe consumption indicating a potential risk. Given the potential risks to the fishery and consumers, the development of pollution monitoring and management programs are warranted. The work presented here provides initial monitoring data that can be used to aid such efforts and also underscores the need to identify environmental stressors that may thwart the anticipated growth of fisheries in this region

Allen D.S.; Kolok A.S.; Snow D.D.; Satybaldiyev B.; Uralbekov B.; Nystrom G.S.; Thornton Hampton L.M.; Bartelt-Hunt S.L.; Sellin Jeffries M.K. (2023) Predicted aquatic and human health risks associated with the presence of metals in the Syr Darya and Shardara Reservoir, Kazakhstan. Science of the Total Environment, 859, 159827.