The project examines the fundamental problems of the relationship between the stability, activity and selectivity of various types of catalytic systems based on transition metals in the catalysis of reactions of polyfunctional organic substances. At the stages of the 2014-2016 project, results were obtained that may change the understanding of the principles of functioning of certain types of metal-complex catalysts and heterogeneous-catalytic systems. It was found that Nickel, palladium, and platinum complexes widely used in catalysis with N-heterocyclic carbenes (NHC), which were generally considered very stable, can be rapidly destroyed during catalytic reactions with the breaking of the metal-NHC bond. These processes, usually considered undesirable and leading to loss of catalytic activity, play a key role in generating active centers and can significantly affect the activity and selectivity of catalytic systems. Unusual dependences of activity and selectivity of a number of new heterogeneous catalysts associated with changes in the state of active centers during catalytic transformations were found. The obtained results show the feasibility of revising the views on the relationship between the stability, activity and selectivity of some widely used catalytic systems based on transition metals. In the 2017 project, a comprehensive study of the detected phenomena is planned in order to obtain new fundamental knowledge about the mutual transformations of active particles in catalytic systems based on transition metals. The research covers homogeneous, nano - and heterogeneous catalysis of various types of catalysts, including metal complexes with N-heterocyclic carbenes, new heterogeneous systems with a complex hierarchical structure synthesized by electrochemical dispersion and oxidation of metals, as well as heterogeneous catalysts of industrial processes.
It is proposed to identify new mechanisms of catalytic reactions, ways of formation and degradation of active centers, patterns of influence of the nature of active centers on selectivity. It is planned that the 2017-2018 research will result in new approaches to managing the selectivity of metal-catalyzed reactions and methods for activating and stabilizing catalytic systems, as well as new effective catalysts, including catalytic systems with "switchable" selectivity. The developed approaches and catalysts will be tested in the synthesis of polyfunctional organic substances (functionally substituted heterocycles, carbocycles and acyclic Regents), as well as in the process of processing renewable plant raw materials into liquid motor fuels by gasification and Fischer-Tropsch synthesis.

Results for 2017:

The project aims to develop three complementary areas in the field of catalysis: (i) homogeneous catalysis by metal complexes with N-heterocyclic carbenes (m/NHC complexes) and other organic ligands; (ii) development of a new methodology for the synthesis of heterogeneous catalysts with a complex hierarchical structure by electrochemical dispersion and oxidation of metals; (iii) development of effective heterogeneous catalysts for the Fischer-Tropsch process and technologies for the synthesis of hydrocarbons from CO and H2. (i) in the course of research at the previous stage of the project, a new mechanism of catalysis by Pd/NHC complexes was discovered, in which the cleavage of the metal-NHC bond plays a key role in the generation of active centers. Therefore, at the current stage, a comprehensive study of transformations of m/NHC complexes (M = Pd, Pt, Ni, Ru) under conditions of catalytic processes has been performed and the main reactions of complex decay have been determined. In particular, new reactions have been found that occur both with and without breaking the M-NHC bond. These reactions are important for metal complex catalysis, as they significantly affect the activity, performance and stability of catalytic systems, and can also significantly affect the selectivity of reactions. As a result of the study of PD/NHC complex transformations in the process of catalysis of Mizoroki-Heka, Suzuki-Miyaura, Sonogashira, and arylation of ketones, it was found that the main reactions of the decay of complexes with a metal-NHC bond break are R-NHC combination, H-NHC combination, O-NHC combination, and protolysis. The decay of R-NHC and H-NHC combination complexes is observed during the catalysis of all the studied carbon-carbon bond formation reactions. For the first time, it was found that aliphatic amines, often used as bases, can cause rapid decomposition of complexes by the H-NHC combination reaction under typical catalytic processes, acting as hydride ion donors. It is shown for the first time that the reaction of Pd-PEPSI complexes or their platinum analogues with amines is accompanied by the formation of more stable, but less catalytically active bis-NHC complexes Pd(II) or Pt(II). O-NHC the combination of M/NHC complexes is a new reaction that was discovered and investigated during the current project. It was found that this reaction has a General character for m(II)/NHC complexes and consists in the formation of azole-2(5)-ones and m(0) nanoparticles when acting on complexes of strong oxygen-containing bases (alcohols, hydroxides, and alkali metal carbonates). For the first time, the protolysis of widely used Pd-PEPSI complexes in catalysis was experimentally investigated. Protolysis is accompanied by rapid cleavage of the pyridine ligand to form bridge-type bionuclear complexes, which, when heated with acids, undergo splitting of the Pd-NHC bond and form azolic salts and palladium salts. It is shown experimentally that the effect of metal/NHC complex decay processes on the activity of catalytic systems depends significantly on the mechanism of the catalyzed reaction. The breakdown of the M-NHC bond leads to deactivation of the catalytic system during molecular M/NHC catalysis (for example, in Pd-catalyzed arylation of ketones), and, on the contrary, to activation of the system during NHC-free catalysis (for example, in the Mizoroki Heck reaction). The results obtained can be used to create more efficient catalytic systems based on M/NHC complexes. (ii) synthesis methods and new electrocatalytic materials have been Developed — Pd/C, Rh/C, Pt-Rh/C, PtIr/C, Pt/SnOx-C, as well as ZnO-based photocatalysts with a complex hierarchical structure. These methods are based on electrochemical dispersion of the corresponding metals under conditions of non-stationary electrolysis (using alternating pulse current) and provide wide opportunities for varying the composition and structure of the resulting materials by changing the composition of the electrodes and the electrolyte, the mode of electrolysis. The influence of the composition of electrolytes, the parameters of electrolysis and post-treatment on the rate of formation and structural organization of the resulting materials is studied. It is shown that when the current density increases from 0.2 to 2.4 A / cm2 and the current duty cycle increases from 10 to 25%, the rate of nanoparticle formation increases by 4-5 times for d-metals and 5-10 times for p-metals. The influence of parameters of non-stationary electrolysis and post - treatment on the activity of heterogeneous-catalytic systems obtained in the reactions of electro-oxidation of CO, MeOH, EtOH, electrochemical hydrogenation of butene and butindiol, and photo-oxidation of organic dyes is studied. It was found that the introduction Of RH and Ir additives can significantly reduce the overvoltage of electrochemical oxidation of CO, MeOH, EtOH on platinum catalysts. The use of hybrid SnOx-C carriers obtained under conditions of non-stationary electrolysis can significantly increase the activity and stability of platinum catalysts in comparison with catalysts on monocarbon carriers. The resulting catalytic materials can be used in fuel cells and in devices designed to purify water from organic pollutants. (iii) experimental studies of the Fischer-Tropsch synthesis process on aluminum oxide-promoted Co / SiO2 catalysts at high pressures (2-8 MPa) in a tube reactor in the temperature range of 185-225 °C. New data on the combined effect of pressure and temperature on the selectivity of C5+ hydrocarbon formation during continuous continuous (up to 1000 h) operation of the catalyst were obtained. It was found that selectivity for C5+ hydrocarbons decreases with increasing temperature in the range of 2-4 MPa, but increases at pressures of 4-8 MPa. Conditions were found that provide maximum performance for C5 + hydrocarbons. For the first time, data on changes in the composition and structural characteristics of Co/SiO2 catalysts promoted by aluminum oxide during long-term (1000 h) continuous operation at pressures of 4-8 MPa were obtained. It was found that during the operation of the catalyst, the specific surface area is reduced by 60-70% due to the accumulation of carbon and high-molecular hydrocarbons that clog the carrier pores. High-temperature regeneration of catalysts allows to restore the specific surface area to the original level. The results obtained can be used to intensify the synthesis of hydrocarbons. Methods for the synthesis of new bifunctional cobalt catalysts on carriers with high acidity and including aluminum oxide and aluminosilicates (zeolites) have been developed. A special feature of bifunctional catalysts is the ability to catalyze the isomerization of linear hydrocarbons into branched ones, which can be used for single-stage synthesis of high-octane motor fuels from CO and H2. The efficiency of the obtained catalysts in the synthesis of branched hydrocarbons will be studied at the next stage of the project.


Publications:

1. Aleksenko K. N., Ivanenko S. S., Vasilenko A. A., Sulima S. I., Bakun V. G. Investigation of structural parameters of promoted Co-catalysts on a silicate carrier engineering Bulletin of the don, - (year of publication-2017).

2. Astakhov A.V., Suponitsky K. Yu., Chernyshev V. M. Trimethylchlorosilane promoted synthesis of 1,2,4-triazolopyrimidines via condensation of 1-substituted 3,5-diamino-1,2,4-triazoles with pentane-2,4-diones Mendeleev Communications, — (year of publication — 2018).

3. Astakhov A.V., khazipov O. V., Chernenko A. Yu., Pasyukov D. V., Kashin A. S., Gordeev E. G., Khrustalev V. N., Chernyshev V. M., Ananikov V. P. A New Mode of Operation of Pd-NHC Systems Studied in a Catalytic Mizoroki–Heck Reaction Organometallics, 36, 10, 1981-1992 (year of publication — 2017).

4. Gordeev E. G., Eremin D. B., Chernyshev V. M., Ananikov V. P. Influence of R–NHC Coupling on the Outcome of R–X Oxidative Addition to Pd/NHC Complexes (R = Me, Ph, Vinyl, Ethynyl) Organometallics, Organometallics, Article ASAP DOI: 10.1021/acs.organomet.7b00669 (year of publication — 2017).

5. Krasnyakova T. V., Nikitenko D. V., Khomutova E. V., Mitchenko S. A. Catalytic Hydrochlorination of Acetylene on PdCl2 / with Supported Catalysts: Kinetic Isotopic Effect of HCl/DCl, Stereoselectivity, and Mechanism Kinetics and Catalysis, 58, 5, 533-540 (year of publication — 2017).

6. Kuriganova A. B., Leontiev I. N., Smirnova N. V. PtIr / C catalysts for solid polymer fuel cells obtained by electrochemical dispersion method Russian Journal of Electrochemistry, — (year of publication — 2018).

7. Novikova K., Kuriganova A., Leontiev I., Gerasimova E., Maslova O., Rakhmatullin A., Smirnova N., Dobrovolsky Yu. Influence of Carbon Support on Catalytic Layer Performance of Proton Exchange Membrane Fuel Cells Electrocatalysis, Electrocatalysis (2017). https://doi.org/10.1007/s12678-017-0416-4 (year of publication-2017).

8. Savostyanov A. P., Narochny G. B., Yakovenko R. E., Mitchenko S. A., Zubkov I. N. Enhancement of the Fischer-Tropsch Process for Producing Long-Chain Hydrocarbons on a Cobalt-Alumina-Silica Gel Catalyst Petroleum Chemistry, 58, 1, 81-89 (year of publication — 2018).

9. Savostyanov A. P., Yakovenko R. E., Narochny G. B, Sulima S. I., Bakun V. G., Soromotin V. N., Mitchenko S. A. "Unexpected increase in C5+ selectivity at temperature rise in high pressure Fischer-Tropsch synthesis over Co-Al2O3/SiO2 catalyst" Catalyst Communications, 99, 25-29 (year of publication — 2017).

10. Savostyanov A. P., Yakovenko R. E., Narochny G. B., Saliev A. N., Bakun V. G., Sulima S. and a Catalyst for the synthesis of hydrocarbons by the Fischer-Tropsch method and a method for its preparation -, RU 201615037 (year of publication—).

11. Sulima S. I., Bakun V. G., Yakovenko R. E., Shabelskaya N. P., Saliev A. N., Narochny G. B., Savostyanov A. P. Microstructure of a cobaltsilicagel catalyst in the presence of an Al2O3 additive Kinetics and catalysis — - (year of publication-2018).

12. Ulyankina A., Leontiev I., Maslova O., Alix M., Rakhmatullin A., Nevzorova N., Valeev R., yalovega G., Smirnova N. Copper oxides for energy storage application: Novel pulse alternating current synthesis Materials Science in Semiconductor Processing, 73, 111-116 (year of publication — 2018).

13. Ulyankina A. A., Leontiev I. N., Smirnova N. V. Morphology and properties of nanoscale zinc oxide obtained using alternating pulsed current engineering Bulletin of the don, - (year of publication-2017).

14. Ulyankina A. A., Smirnova N. V. on the mechanism of electrochemical formation of nanodisperse copper oxides under the action of alternating pulsed current Fundamental research — - (year of publication-2017).

15. Faddeev N. A., Kuriganova A. B., Leontiev I. N., Smirnova N. V. Electrocatalytic properties of Rh/C and Pt-Rh/C catalysts obtained by electrochemical dispersion electrochemistry — (year of publication-2018).

16. khazipov O. V., Krasnyakova T. V., Nikitenko D. V., Merzlikina M. A., Khomutova E. V., Mitchenko S. A. Successful alkylation of PtII by RI to form bis-organoplatinum (IV) derivatives as key steps for cross-electrophile coupling Journal of Organometallic chemistry, — (year of publication — 2018).

17. Chernenko A. Yu., Astakhov A.V., Pasyukov D. V., Dorovatovsky P. V., Zubavichus Ya. V., Khrustalev V. N., Chernyshev V. M. Pd-PEPSI complexes based on 1,2,4-triazol-5-ylidene ligands – effective catalysts for the Suzuki-Miyaura reaction proceedings of the Academy of Sciences. Chemical series., — (year of publication-2018).

18. Chernenko A. Yu., Pasyukov D. V., Astakhov A.V., Tafeenko V. A., Chernyshev V. M. Reactions of Pd-PEPSI complexes with proton acids Izvestiya Akademii Nauk. Chemical series., — (year of publication-2018).

19. Chernenko A. Yu., Pasyukov D. V., Soliev S. B., Astakhov A.V., Chernyshev V. M. Influence of substituents on the regioselectivity of the 5-alkylamino-3-R-1,2,4-triazole acylation reaction.proceedings of higher educational institutions. North Caucasus region. Series: technical Sciences, — (year of publication-2018).

20. Yakovenko R. E., Saliev A. N., Zubkov I. N., Soromotin V. N., Narochny G. B., Savostyanov A. P. Processing of coal and natural organic Substances into synthetic hydrocarbons. Part 6. Influence of the preparation method on the properties of a cobalt-containing catalyst for direct synthesis of motor fuels from CO and H2 proceedings of higher educational institutions. North Caucasus region. Series: technical Sciences, — (year of publication-2018).

Results for 2018:

According to the work plan, the research was carried out in three directions: (i) homogeneous catalysis by metal complexes with N-heterocyclic carbenes (m/NHC complexes) and other organic ligands; (ii) development of a new methodology for the synthesis of heterogeneous catalysts with a complex hierarchical structure by electrochemical dispersion and oxidation of metals; (iii) development of effective heterogeneous catalysts for the Fischer-Tropsch process and technologies for the synthesis of hydrocarbons from CO and H2. (i) at the previous stage of the project, the importance of reducing elimination reactions of NHC ligands by H-NHC, C-NHC and O-NHC combinations for activation and deactivation of m/NHC catalytic systems (M = Pd, Pt, Ni) was established. At the current stage of the project, the study of the new reaction of the O-NHC combination, as well as the General ability of the m/NHC complexes [M = Pd(0) Cu(I) Ag(I), Au(I), Pd(II), Pt(II), Ru(II), Au(III), Pt (IV)] undergo reduction elimination reactions of NHC ligands by combination with heteroatom-containing reagents. This new family of reactions is called "X-NHC combination reactions". It is established that the processes of X-NHC combination are typical for metals in the degree of oxidation II-IV and are implemented in catalytic systems during M/NHC catalysis of C-C, C-S and C-N bond formation reactions (cross-combination and C-H functionalization reactions in the presence of strong bases, thiolation of halides, hydrothyolation of alkynes, Buchwald-Hartwig amination). It is shown that X-NHC combination reactions are one of the important reasons for deactivation of M/NHC catalysts in the case of molecular M/NHC catalysis, although they can also be used to generate catalytically active m (0) forms of metals. The S (Se)-NHC combination is realized when PD/NHC, Ni/NHC, and Pt/NHC complexes interact with thiols and selenols. The main products of the S-NHC combination are polysulfides of metals of variable composition, salts of alkylthio - and arylthioazoles, and azolthions. The formation of azoltiones as the main products of NHC-ligand transformation suggests that the reaction is complex and is accompanied by cleavage of C-S thiol bonds. A method for stabilization of active molecular forms of Pd/NHC in reactions proceeding by the "molecular" mechanism of M/NHC catalysis in the presence of strong bases has been developed, based on the use of imidazole NHC ligands modified by NH-acid substituents with volume 2,6-dialkyl-substituted aryl groups at NHC nitrogen atoms. It is assumed that the NH-group of the substituent is deprotonated in the main medium and, due to positive inductive and resonant effects, significantly stabilizes the metal-NHC bond. Bulk N-aryl substituents sterically prevent the decay of complexes along the path of H-NHC and R-NHC combinations, and also contribute to the targeted reduction elimination of coordinated reagents. The influence of reduction elimination reactions of NHC ligands on the activation/deactivation of catalytic systems under different catalysis mechanisms, as well as on the selectivity of catalytic reactions, is studied. New approaches to activation of Ni/NHC systems by o-NHC combination of bis-NHC Nickel complexes in Suzuki-Miyaura reactions and reducing dehalogenation of aryl halides are proposed. Based on the available Ni/NHC complexes, a new efficient catalytic system for biaryl synthesis has been developed. (ii). A new methodology for the synthesis of multicomponent oxide materials with a complex hierarchical structure based on electrochemical dispersion and oxidation of metals (Sn, Co, Zn, Al, Ti) under the conditions of electrolysis using pulsed alternating current has been developed. The influence of current, temperature, and electrolyte composition parameters on the formation rate, composition, and structure of oxide materials is studied. The resulting oxide materials have been studied as potential components of lithium-ion battery electrodes, supercapacitors and fuel cells, as well as catalysts for photocatalytic water purification systems from organic pollutants. It is established that Co3O4-CoOOH obtained by electrochemical synthesis can be used as an effective anode material for lithium-ion batteries. The specific capacity of this material in the anode of a lithium-ion battery (electrolyte — 1M LiPF6 in a mixture of ethylene carbonate/dimethyl carbonate) reaches 1361 mAh/g at a current density of 45 A/g, which corresponds to the highest indicators of similar materials described in the literature. This material can also be used as part of supercapacitor electrodes — its specific capacity is 330 F / g at a current density of 10 A / g (the electrolyte is 1 M KOH). It is shown that ZnOx, SnOx-ZnOx and TiOx oxides can be used as effective photocatalysts for photodegradation of organic impurities in aqueous solutions. (iii) a comprehensive study of the single-reactor synthesis of liquid motor fuels from CO and H2 in the combined Fischer-Tropsch process, isomerization and hydrocracking of hydrocarbons on Bifunctional co/SiO2-Al2O3-ZSM-5 cobalt-silicate catalysts was Performed. It was found that the catalysts obtained by mechanical mixing of the Co-Al2O3/SiO2 catalyst with zeolite ZSM-5 and boehmite (so-called composite catalysts) have significantly higher selectivity for branched hydrocarbons compared to the catalysts obtained by impregnation of pre-formed SiO2-Al2O3-ZSM-5 carriers with cobalt nitrate (impregnation catalysts). An atypical change in the selectivity of composite catalysts for C5+ hydrocarbons was found depending on temperature and pressure — at a pressure of 2.0 MPa with an increase in temperature in the range of 230 — 250 °C, the selectivity for C5+ increases, while at a pressure of 4.0 MPa and higher, it decreases. A new highly efficient bifunctional Co/SiO2-Al2O3-ZSM-5 catalyst for the synthesis of liquid motor fuels from CO and H2 has been developed. The technological parameters of synthesis are optimized to ensure stable operation of the catalyst for a long time and high performance for hydrocarbon fractions suitable for use as gasoline and diesel. A laboratory complex for the synthesis of liquid hydrocarbons, mainly motor fuel fractions, from carbon-containing raw materials of plant origin – pine sawdust has been developed. The complex consists of a biomass gasification unit, a synthesis gas treatment unit, a Fischer-Tropsch synthesis unit, isomerization and hydrocracking of hydrocarbons, and a product separation unit. In the reactor for the synthesis of hydrocarbons used kabeltelevision bifunctional catalyst. The developed complex provides the possibility of synthesis of 0.1636 kg of liquid hydrocarbons from 1 kg of dry sawdust. The degree of utilization of biomass carbon is ~58%. The complex makes it possible to obtain a gasoline fraction (~56% of the total amount of liquid hydrocarbons) with an octane number of at least 92 and a diesel fraction (~32% of the total amount of liquid hydrocarbons) with a cetane number of 51. The developed process opens up opportunities for creating mobile modular installations for processing waste from woodworking and agricultural industries into liquid motor fuels.

Publications:

1. - Article on a joint project of scientists of IOH RAS and NPI was included in the five most cited works of ACS journal Official website of the Zelinsky Institute of organic chemistry of the Russian Academy of Sciences, Moscow,July 31, 2018, news section of the Zelinsky Institute of organic chemistry of the Russian Academy of Sciences (year of publication—).

2 — - Two articles by Russian scientists are included in the shortlist of the most widely read articles of the American chemical society Official website of the Zelinsky Institute of organic chemistry of the Russian Academy of Sciences, Moscow, February 18, 2018, news section of the Zelinsky Institute of organic chemistry of the Russian Academy of Sciences (year of publication—).

3. - scientists from Novocherkassk came up with how to create oil in an hour TV channel "DON 24", Rostov-on-don, April 10, 2018, column "Education", material of the correspondent of the TV channel "DON 24" Yevgenia Slinkina (year of publication — ).

4. - Grant RPF 14-23-00078 "New catalytic systems and processes of selective synthesis and processing of polyfunctional organic substances" Official website of the South Russian state Polytechnic University (NPI) named after M. I. Platov, Novocherkassk, section "Science and innovation", ongoing projects and programs (year of publication — ).

5. Aleksenko K. N., Ivanenko S. S., Vasilenko A. A., Yagmurov V. Yu., Chistyakova N. S., Karabanov A.V. Investigation of the effect of Zr and Mn promoters on the properties of cobalt catalysts of Fischer-Tropsch synthesis Engineering Bulletin of the don, Number 4, http://ivdon.ru/ru/magazine/archive/n4y2018/5323 (year of publication-2018).

6. Eliseev O. L., Savostyanov A. P., Sulima S. I., Lapidus A. L. Recent development in heavy paraffin synthesis from CO and H2 Mendeleev Communications, 28 (4), p. 345-351 (year of publication — 2018).

7. Eremin D. B., Boyko D. A., borkovskaya E. V., Khrustalev V. N., Chernyshev V. M., Ananikov V. P. Ten-fold boost of catalytic performance in thiol–yne click reaction enabled by a palladium diketonate complex with a hexafluoroacetylacetonate ligand Catalyst Science & Technology, 8 (12), p. 3073-3080 (year of publication — 2018).

8. Ilyin V. B., Narochny G. B., Yakovenko R. E., Zubenko A. F., Savostyanov A. A. Processing of coal and natural organic substances into synthetic hydrocarbons. Part 7. Production of motor fraction hydrocarbons from pine wood Izvestiya vuzov. SEV. - Kavk. region. Technical Sciences, — (year of publication-2019).

9. Kuriganova A. B., Leontiev I. N., Avramenko M. V., Smirnova N. V. The Investigation of Structural, Micro-structural and Electrochemical Characteristics of Pt/SnOx-C Electrocatalysts Prepared via the Electrochemical Dispersion of Tin and Platinum proceedings of higher educational institutions. Series "Chemistry and chemical technology", — (year of publication-2019).

10. Kuriganova A. B., Smirnova N. V. Electrocatalytic systems Pt/SnOx-C with different morphology of tin oxide Engineering Bulletin of the don, Number 4, http://ivdon.ru/ru/magazine/archive/n4y2018/5341 (year of publication-2018).

11. Kutovoy A. A., Shmanovskaya A. L., Aleksenko K. N., Vasilenko A. A., Ivanenko S. S., Yagmurov V. Yu., Sulima S. I. Influence of modifying additives on the properties of the deposited cobalt catalyst Engineering Bulletin of the don, Number 2, http://ivdon.ru/ru/magazine/archive/n1y2018/4816 (year of publication-2018).

12. Kutovoy A. A., Shmanovskaya A. L., Sulima S. I., Bakun V. G. Investigation of physical and chemical properties of promoted catalysts based on Co-Al2O3/SiO2 Engineering Bulletin of the don, Number 1, http://ivdon.ru/ru/magazine/archive/n1y2018/4652 (year of publication-2018).

13. Savostyanov A. P., Narochny G. B., Yakovenko R. E., Soromotin V. N., Zubkov I. N. Effect of Diffusion Limitations on the Fischer-Tropsch Synthesis of Long-Chain Hydrocarbons on a Cobalt-Alumina Silica Gel Catalyst Catalyst in Industry, 10 (3), p. 181-184 (year of publication — 2018).

14. Smirnova N. V., Kuriganova A. B., Faddeev N. A., Pudova L. S., Ulyankina A. A. Electrode materials based on tin dioxide for electrochemical applications Fundamental research, Vol. 12-2, pp. 323-327 (year of publication — 2018).

15. Ulyankina A. A., Kuriganova A. B., Smirnova N. V. Photocatalytic properties of SnO2-SnO nanocomposite acquired via PAC synthesis Mendeleev Communications, — (year of publication-2019).

16. Ulyankina A. A., Leontiev I. N., Avramenko M. V., Zhigunov D. M., Smirnova N. V. Large-scale synthesis of ZnO nanostructures by pulse electrochemical method and their photocatalytic properties Materials Science in Semiconductor Processing, 76, p.7-13 (year of publication — 2018).

17. khazipov O. V., Shevchenko M. A., Chernenko A. Yu., Astakhov A.V., Pasyukov D. V., Eremin D. B., Zubavichus Ya.V., Khrustalev V. N., Chernyshev V. M., Ananikov V. P. Fast and Slow Release of Catalytically Active Species in Metal/NHC Systems Induced by Aliphatic Amines Organometallics, 37 (9), pp 1483-1492 (year of publication — 2018).

18. Chernenko A. Yu., Pasyukov D. V., Ranniy G. S., Soliev S. B., Kutyrev V. V., Astakhov A.V., Chernyshev V. M. Theoretical and experimental study of prototropic tautomerism of C-amino-3(5) - R-1,2,4-triazoles Izvestiya vuzov. SEV. - Kavk. region. Technical Sciences, — (year of publication-2019).

19. Chernyshev V. M., khazipov O. V., Shevchenko M. A., Chernenko A. Yu., Astakhov A.V., Eremin D. B., Pasyukov D. V., Kashin A. S., Ananikov V. P. Revealing the unusual role of bases in activation/deactivation of catalytic systems: O–NHC coupling in M/NHC catalyst Chemical Science, 9 (25), p. 5564-5577 (year of publication — 2018).

20. Chernyshev V. M., Astakhov A.V., Chikunov I. E., Tyurin R. V., Eremin D. B., Ranniy G. S., Khrustalev V. N., Ananikov V. P. Pd and Pt Catalyst Poisoning in the Study of Reaction Mechanisms: What Does the Mercury Test Mean for Catalysis? ACS Catalysis, Vol. 9, Pp. 2984-2995 (year of publication-2019).

21. Chernysheva D., vlaik K., Leontiev I., Pudova L., Ivanov S., Avramenko M., Alix M., Rakhmatollin A., Maslova O., Band A., Smirnova N. Synthesis of Co3O4/CoOOH via electrochemical dispersion using a pulse alternating current method for lithium-ion batteries and supercapacitors Solid State Sciences, 86, p. 53-59 (year of publication — 2018).

22. Chikunov I. E., Ranniy G. S., Astakhov A.V., Tafeenko V. A., Chernysheva V. M. Mechanochemical synthesis of platinum(iv) complexes with N-heterocyclic carbenes proceedings of the Academy of Sciences. Chemical series, 67 (11), p. 2003-2009 (year of publication-2018).