Annotation of the results obtained in 2022
Direction 1. NiCu/LaCeOx systems with the La/Ce molar ratios of 9/1 and 1/1 were studied in ethanol steam conversion. In a series of bulk catalysts based on LaCeOx, the NiCu-LaCeOx (9:1) catalyst is most active, and 98% ethanol conversion is observed already at 600 °C, the maximum H2 yield is ~60%, the H2/CO2 ratio is 7. According to the method developed, the catalysts with the Ni-LaCeOx/SBA-15 composition and NiCu-LaCeOx/SBA-15 modified with copper with the La/Ce ratios of 9/1 and 1/1 were prepared and characterized. An increase in the La/Ce ratio leads to an increase in the dispersion of NiO particles (CSR is 6-8 nm) in the catalysts. The La2O3 deposited on the SBA-15 surface is X-ray amorphous, and interacts with the SBA-15 to form surface lanthanum silicates, which leads to an increase in the wall thickness (LAXRS). For all LaCeOx-based catalysts, both the strength of the main sites and the amount of adsorbed CO2 increase. At close CH4 and CO2 conversion values as well as H2/CO for the catalysts studied, the Ni-LaCeOx/SBA-15 (9:1) composition system is more stable in the DRM reaction and undergoes less carbonation (1 wt.%/6h). The Cu addition to catalysts leads to a decrease in the conversion of reagents and H2/CO in the DRM process due to the accumulation of the carbon deposition products. Direction 2. Based on the study of the individual stages of the cascade HMF transformation in water and a mixture of DMSO-H2O (1:3) in the presence of NaHCO3 using the HMF, DFF, HMFCA and FFCA as reagents, for Pd and Au suspensions the main routes of HMF transformation on monometallic NPs were established, the rate constants of individual stages were determined. For bimetallic xAu100-xPd suspensions of nanoparticles obtained by pulsed laser ablation, a synergistic effect was observed leading to a significant increase in the conversion of hydroxymethylfurfural (HMF) and the yield of furandicarboxylic acid during the HMF oxidation and manifested in the high activity of AuyPd1-y alloy particles in the oxidation of both carbonyl and OH groups in the substrate molecule due to the formation of the Au-Pd interface in the NP alloy. The mechanism of substrate oxidation has been confirmed using quantum-chemical calculations. Comparison of the properties of Pd-Bi and Au-Ag NP with the corresponding hybrids based on the UiO-66 in the oxidation with O2 of glycerol and propylene glycol in water without alkali additives showed the advantages of the latter. Comparison of the hybrid samples with mechanical mixtures of Pd-Bi or Au-Ag dispersions and the corresponding amount of MOF in the oxidation of polyols allowed us to establish the key role of the size of bimetal NPs, their composition, spatial location in the MOF structure in the immediate vicinity of redox and acid sites. The specific porosity of UiO-66 had a critical effect on the activity and selectivity in glycerol conversion into MK. The stability of the bimetallic systems under neutral conditions of the catalytic process was shown. Direction 3. A technique for the chemical synthesis of bismuth titanates-silicates of various stoichiometry has been developed, which allows obtaining heterostructures of various types. A method to synthesize heterostructures and doped systems based on dark ablative TiO2 and p-type additives (Cu, Co, Ni) has been developed. With the introduction of Me<1%wt, using co-deposition in a mixture of ablative particles, TiO2 is mainly doped with the appearance of defective levels in the forbidden zone and an increase in the Ti3+ fraction. Cu has been determined as the optimal dopant of transition metals. The catalytic activity of variants of the Cu-TiO2 system has been determined. It is shown that the creation of a type II heterojunction during the formation of the ablative Cu2O-TiO2 composite significantly increases the activity of the catalyst approaching the activity of the Pt-doped systems. Due to the combined irradiation, the efficiency of H2 extraction is further increased by 20-30% for dark TiO2. Direction 4. It has been established that the activity and stability of the catalysts in the process of low–temperature oxidation of CO are determined by the well-developed structure of cryptomelane (Fe–OMS-2, Si/Ce-OMS-2) as well as the Cu compounds formed during the preparation on the catalyst surface (heat treatment at 300 °C), which affect the amount of available atomic oxygen. The most promising catalysts in low–temperature CO oxidation are 1%Pd+Cu/Fe-OMS–2–300 and 1%Pd+Cu/Fe-OMS–2–450 and Cu/Ce-OMS–2-300, Cu/Ce–OMS-2–450 and 1%Pd/Ce–OMS-2 and Cu–OMS-2. The interaction of two metals, one of which is transitional (Cu), and the second one is Pd, with the preservation of the OMS-2 structure or partial destruction of the OMS-2 structure and the presence of transition/rare earth metals (Cu/Ce) on the catalyst surface are the main parameters in the selection of catalysts for a low-temperature CO oxidation process that proceeds stably in the presence of water vapor. List of publications for the reporting period: 1. Kharlamova T.S., Verkhov V.A., Kulchakovskaya E.V., Svetlichnyi V.A., Cadete Santos Aires F.J., Bargiela P., Vodyankina O.V. Effect of metal-doping (Me = Fe, Ce, Sn) on phase composition, structural peculiarities, and CO oxidation catalytic activity of cryptomelane- type MnO2, Journal of Alloys and Compounds (2022 г.) WOS SCOPUS Q1 2. Torbina V., Ten S., Vodyankina O. Effect of organic linker substituent on catalytic activity of UiO-66 metal-organic framework in selective oxidation of propylene glycol: homolytic versus heterolytic activation of hydrogen peroxide, Materials Today Chemistry (2022 г.) WOS SCOPUS Q1 3. Shabalina A.V., Golubovskaya A.G., Fakhrutdinova E.D., Kulinich S.A., Vodyankina O.V., Svetlichyi V.A. Phase and structural thermal evolution of Bi-Si-O catalysts obtained via laser ablation, Nanomaterials (2022 г.) WOS SCOPUS Q1 4. Dorofeeva N.V., Kharlamova T.S., La Parola V., Liotta L.F., Vodyankina O.V. Carbon dioxide reforming of methane on Ni-containing La2O3 and La2O3–Mn2O3 catalysts: The effect of the preparation method, Reports of the Russian Academy of Sciences. Chemistry, Materials Sciences (2022) WOS SCOPUS 5. Shabalina A.V., Gotovtseva E.Yu., Belik Yu.A., Kuzmin S.M., Kharlamova T.S., Kulinich S.A., Svetlichnyi V.A., Vodyankina O.V. Electrochemical Study of Semiconductor Properties for Bismuth Silicate-Based Photocatalysts Obtained via Hydro/Solvothermal Approach, Materials (2022 г.) WOS SCOPUS 6. Fakhrutdinova E., Reutova O., Maliy L., Kharlamova T., Vodyankina O., Svetlichnyi V. Laser-based Synthesis of TiO2-Pt Photocatalysts for Hydrogen Generation, Materials (2022 г.) WOS SCOPUS 7. Kulchakovskaya E.V., Dotsenko S.S., Liotta L.F., La Parola V., Galanov S.I., Sidorova O.I., Vodyankina O.V. Synergistic Effect in Ag/Fe–MnO2 Catalysts for Ethanol Oxidation, Catalysts (2022 г.) WOS SCOPUS 8. Fakhrutdinova E.D., Egorova L.S., Svetlichnyi V.A. Laser Assisted Synthesis of Bismuth Titanate Bi12TiO20 for Application in Photocatalysis, Известия Российской Академии Наук. Серия физическая (2022 г.) SCOPUS RSCI 9. Reutova O.A., Svetlichnyi V.A. Photocatalytic Properties of Zinc Oxide Nanopowders Obtained via Nano- and Picosecond Laser Ablation in Air., Proceedings of the Russian Academy of Sciences. Physical Series (2022) SCOPUS RSCI Information resources on the Internet that are dedicated to the project: 1. News on the TSU website "Two special prizes and three gold medals were won by TSU at the Hi-Tech exhibition" https://news.tsu.ru/news/dva-spetspriza-i-tri-zolotykh-medali-zavoeval-tgu-/?sphrase_id=386694 2. News on the TSU website "Professor of Chemistry department edits a scientific collection on "green" energy" https://news.tsu.ru/news/professor-khf-redaktiruet-nauchnyy-sbornik-o-zelen/?sphrase_id=386694 3. News on the TSU website "October 11-14 – school-conference for young scientists "Catalysis: from science to industry" https://news.tsu.ru/calendarofevents/vii_mezhdunarodnaya_nauchnaya_shkola_konferentsiya_molodykh_uchenykh_kataliz_ot_nauki_k_promyshlenno/ ? sphrase_id=386694 4. News on the TSU website "Leading and young scientists from six countries discussed new topics in catalysis" https://news.tsu.ru/news/vedushchie-i-molodye-uchenye-iz-shesti-stran-obsudili-novye-temy-v-katalize/

 

Publications

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Annotation of the results obtained in 2019
A report on the results of the first year of the project: The main works carried out within the first year were as follows: Direction 1 - the methods to prepare the main types of catalytic systems within the project were developed and optimized, including those to obtain individual and binary oxide supports based on oxides of La, Ce, and Mn (La2O3; CeO2; MnOx; La2O3-CeO2; La2O3-MnOx; CeO2-MnOx) as well as to synthesize Ni-containing catalysts on the basis thereof. The methods are based on citric approach using additives (ammonia and ethylene glycol). The wetness impregnation was used to produce the Ni-containing catalysts. The studies of structure, chemical and phase composition, main physical-chemical properties of the obtained complex supports and catalytic materials on the basis thereof (additive nature, pH, temperatures of ripening, drying and calcination) were carried out using the methods of XRD, low-temperature N2 sorption, X-ray fluorescence, TEM HR, TGA, IR spectroscopy, Raman spectroscopy, H2-TPR etc. The catalytic properties of the samples prepared were studied in the reaction of the dry reforming of methane. The example of La2O3 preparation shows that the introduction of additives at the stage of synthesis (ammonia and ethylene glycol) determines the structure of the oxide surface that affects the distribution and phase composition of the Ni-containing particles of precursors after the impregnation by the solution of active component (the formation of NiO or LaNiO3 is observed). The impregnation with the Ni salt of the La2O3 support prepared by modified and traditional citric approaches leads to the formation of NiO. The method of La2O3 synthesis utilizing ethylene glycol yields LaNiO3. The use of the additives at the preparation of support results in better dispersion of NiO and LaNiO3 nanoparticles (NPs) in the catalyst. For the case of double oxide supports La2O3-CeO2 and La2O3-MnOx, the formation of defect nanocrystalline perovskite phases LaCeO3 or LaMnO3 with the particle sizes of 10-20 nm was typical. For the CeO2-MnO2 system, the CeO2 and Mn2O3 phases are formed at the Ce/Mn=1:1. The sizes of nanoparticles of Ni-containing precursors (NiO and LaNiO3) and their interaction with the surface of oxide support are determined by the effect of additive at the stage of support synthesis. The distribution of Ni NPs on the surface of the prereduced catalysts depends on the composition and structure of the oxide supports. For Ni/La2O3, the size of Ni NPs after reductive treatment is 8-15 nm. The introduction of NH3 results in the formation of Ni NPs of 5-10 nm. For the case of Ni/CeO2, the Ni NPs with the sizes of 5 nm and large aggregates of 100-200 nm are formed. For the case of Ni/La2O3-CeO2, the uneven coverage of the support surface by Ni NPs is observed. The nanocrystalline La2O3-CeO2 support contains the parts of surface enriched with CeO2 besides the LaCeO3 phase. This results in an uneven distribution of Ni NPs as in the case of individual LaCeO3 phase. For the samples of the series 2 (LaMnO3 and Ni/LaMnО3) the citric method is shown to allow providing the even distribution of the components at the stage of synthesis and crystallization of LaMnO3 with a minimal content of Mn2O3. This minimal Mn2O3 content in the support (XRD, Raman spectroscopy) allows introducing Ni that yields NiO particles and solid solution LaMn1-xNixO3. The increase of the Mn2O3 content in the support leads to the active component distribution in the sample as NiO particles strongly bound to the support surface. The catalytic tests of Ni-containing catalysts were carried out in the dry reforming of methane. High activity of Ni catalysts prepared over La-containing supports was shown. Under the testing conditions, the long-term stability and high activity were typical for Ni/La2O3-CeO2 and Ni/La2O3-MnOx, and are provided due to the resistance of Ni particles towards sintering as well as minimization of the carbon deposition process due to the presence of cerium and manganese oxides. Direction 2. The methods were created to prepare hybrid materials based on the metal-organic frameworks Cr-MIL-101, UiO-66 and UiO-67 with the immobilized bimetallic Ag-Me (Me=Pd, Au, Bi) nanoparticles; the method to prepare suspensions of bimetallic Ag-Me (Me=Pd, Au, Bi) particles using laser ablation. The characterization of the prepared materials by a complex of physical-chemical methods was carried out. The peculiarities of the effect of synthesis method on the size of nanoparticles, composition, and distribution of components in hybrid systems Ag-Me@MOF were revealed. It was shown that the ratio of volumes of two immiscible solvents determines the distribution of the metal nanoparticles inside the porous space of the MOFs and on the surface as well as influences on the formation of metal nanoparticles with the sizes above 3-5 nm. The application of the optimized impregnation technique from two immiscible solvents allows obtaining the immobilized bimetallic AgPd nanoparticles in the MOFs in the whole range of Ag/Me ratios that is confirmed by the data of low-temperature N2 sorption, XRD, and TEM HR. It was shown that the electronic state of Ag in hybrid materials Ag-Me@MOF depended on the nature of the second component and its distribution in the MOF structure. The UV-vis DR method showed that the introduction of Pd or Bi resulted in the decreasing of the intensity of the band of Ag plasmon resonance connected with the strong electronic interaction between the components. The samples AgAu@UiO-66 contained bimetallic nanoparticles with the core-shell structure. The role of acid sites of metal-organic frameworks (MOFs) used as heterogeneous catalysts in oxidative liquid-phase transformations of basic molecules formed during the processing of biorenewable feedstock was studied on the example of catalytic oxidation of propylene glycol (PG) into hydroxyacetone using tret-butylhydroperoxide as an oxidant on the Cr-MIL-101 catalyst. The studies of the effect of solvent nature (using protic and aprotic solvents) on the catalytic properties in PG selective oxidation into hydroxyacetone were carried out. It was stated that in the case of aprotic solvents, the effectiveness of the use of oxidant, PG conversion and the product yield were significantly higher as compared to those with protic solvents. The reason for this is the interaction of the solvent molecules with the active sites as well as intermolecular interation in the solution. The molecules of protic solvent are capable of competitive adsorption over Cr sites of the catalyst that leads to the reduction of their availability for the reagents. The initial rate of PG oxidation decreases linearly with the increasing of the diameter of molecule of protic solvent. The highest selectivity towards hydroxyacetone was obtained in those solvents where the initial rates of PG oxidation were the lowest ones. Direction 3. The solvothermal method to prepare materials based on bismuth silicates as well as mechanochemical activation to prepare bismuth silicates with the Bi/Si ratio of 2/1, 12/1 and ¾ under soft conditions. For the solvothermal method (STO), the use of ethylene glycol (EG) as a solvent for Bi(NO3)3*5H2O leads to the formation of the strongly bound chelate complex that does not completely decompose under the STO conditions (12 h, 180 °C) and results in the appearance of the α- and β-Bi2O3. The STO method allows synthesizing the composition based on bismuth silicates with high specific surface area due to (1) the formation of the resin during the STO from polyethylene glycol oligomers that stabilizes the particles of the initial phases of bismuth silicate, (2) the strong adsorption of the EG molecules on the surface of bismuth oxohydroxide particles using the precipitation method with NaOH from the solution of bismuth nitrate in the EG. The effect of the nature of Si precursor was established: The synthesized materials were X-ray amorphous, contained the nuclei of the silicate phases Bi2SiO5 or Bi12SiO20 that depended on the nature of the Si precursor. The sample synthesized from water solution after the stage of hydrothermal treatment was crystalline and comprised Bi2SiO5 and Bi12SiO20 (96 and 4 wt.%, respectively). Thus, the formation and distribution of the particles of the main phases depended on the ripening conditions at the stage of the STO/HTT. Based on the results obtained, a facile and ecofriendly method of soft synthesis of bismuth silicates with different composition was developed using solvent-free mechanochemical activation without the long temperature treatments at elevated temperatures that is not accompanied by the formation of toxic gases as a result of precursor decomposition. The interaction between α-Bi2O3 and SiO2·nH2O to yield γ-Bi12SiO20 and Bi2SiO5 phases at mechanical treatment was shown to occur rapidly and proceeded without the mixture amorphisation that indicated the opportunity of their formation via the plastically deformed or topotaxic mechanisms. At the same time, the formation of Bi4Si3O12 during the mechanochemical synthesis did not occur. The mechanical treatment of the corresponding stoichiometric mixture of α-Bi2O3 and silica results in the formation of the mixture of metastable Bi2SiO5 and unreacted silica. The formation of Bi4Si3O12 takes place as a result of solid phase reaction between the formed Bi2SiO5 and unreacting silica under the action of subsequent thermal treatment at moderate temperatures (450–500 °C). It was shown that when there is no interaction of the components in the mixture during the mechanical treatment, the mechanical activation of the mixture facilitates the solid-phase reaction between them under the subsequent thermal treatment. This is connected with the uniform distribution of the particles of components in the activated mixture accompanied by the decreasing of their size, formation of fresh contact surface and generation of structural defects. The photocatalytic properties of bismuth silicates prepared by different methods were studied. The high photocatalytic activity of a number of materials prepared by STO followed by thermal treatment as well as post-treatment by laser ablation was shown in degradation of organic dyes, including phenol. The electrochemical studies of semiconducting properties of materials were carried out, the type of conductivity was determined, and the location of the band gap edges was estimated. It was shown that the bismuth silicate samples are promising materials for the photoelectrochemical processes, including hydrogen production by water splitting. Direction 4. The conditions were optimized to prepare the catalysts based on MnO2 with the OMS-2 structure modified by the additives of Fe, Sn or Ce with variation of Mn/M molar ratio (20/1 and 10/1). The studies of structure, chemical and phase composition, main physical-chemical and catalytic properties of the synthesized MnO2 catalysts with the OMS-2 structure that were unmodified or modified at the preparation stage by cations of Fe, Sn and Ce were carried out using XRD, low-temperature N2 sorption, X-ray fluorescence, XPR, SEM, TEM HR, TGA, Raman spectroscopy, H2-TPR, etc. It was shown that the distribution of the modifying cations in the OMS-2 structure differs significantly. The Sn-containing sites are localized on the surface of anisotropic MnO2 particles in the subsurface layer with the distortion of the initial crystalline OMS-2 structure, while Fe3+ cations are evenly distributed on the surface and in the bulk of crystals. The Ce-containing modifier forms nanoparticles of oxide phase on the MnO2 crystal surface as well as decorates the edges of the anisotropic NPs preventing their aggregation. For the Ce-containing catalysts, the formation of the pyrolusite in the amount of up to 30% along with the target OMS-2 phase is typical. The effect of Mn7+/Mn2+ molar ratio at the stage of precursor precipitation on the phase composition of Ce-OMS-2 catalysts was stated. It was shown that the Mn7+/Mn2+ ratio up to 2.85 allows synthesizing the composite materials where OMS-2 is the major phase. It was stated that the catalytic activity of the prepared materials in CO oxidation increased in a raw: OMS-2 < Sn-OMS-2 (20/1) < Fe-OMS-2 (20/1) < Ce-OMS-2 (20/1). The experimental activation energy in CO oxidation was determined. For the Ce-OMS-2 (20/1) the Еа = 46 kJ/mol, while for other catalysts the Ea varies in the range of 65-115 kJ/mol. Based on the results of testing of the catalytic properties in the process of formaldehyde oxidation it was stated that the highest activity wass shown by the catalyst Fe-OMS-2 (20/1): Т 50% = 175 оС, 100 % СО conversion at 190 оС. The selectivity towards СО2 comprised 100%, the formation of esters or any other products was not observed for all catalyst studied. The synthesized materials are promising to prepare highly active catalysts for total oxidation of organic compounds. List of publications for the first year of the project: 1. Dotsenko S.S., Verkhov V.A., Svetlichnyi V.A., Liotta L.F., La Parola V., Izaak T.I., Vodyankina O.V. Oxidative dehydrogenation of ethanol by modified OMS-2 catalysts Catalysis Today (2019 г.), Q1 2. Torbina V., Salaev M., Vodyankina O. Effect of solvent nature on propylene glycol oxidation with tert-butyl hydroperoxide over metal–organic framework Cr-MIL-101 RSC Advances (2019 г.), Q1 3. Galanov S., Sidorova O., Magaev O. Dependence of the preparation method on the phase composition and particle size of the binary NiO–ZrO2 system oxides IOP Conference Series: Materials Science and Engineering (2019 г.) 4. Svetlichnyi V.A. , Belik Y.A., Vodyankin A.A., Fakhrutdinova E.D., Vodyankina O.V. Laser fragmentation of photocatalyst particles based on bismuth silicates Proceedings of SPIE - The International Society for Optical Engineering (2019 г.) 5. Ten S., Gavrilenko E.A., Svetlichnyi V.A., Vodyankina O.V. Ag-Pd nanoparticles prepared by laser ablation for selective oxidation of propylene glycol to lactic acid IOP Conf. Series: Materials Science and Engineering (2019 г.) Information sources on the Internet devoted to the project: 1. News portal of the National Research Tomsk State University “Laboratory of catalytic research develops new catalysts for resource-saving energetics”, http://www.tsu.ru/news/lki-razrabotaet-novye-katalizatory-dlya-resursosbe/?sphrase_id=234639 2. News of Siberian science “TSU develops new catalysts for resource-saving energetics”, http://www.sib-science.info/ru/heis/novye-11032019 3. Youth information agency "World", “Tomsk Region: Chemistss at TSU develop the catalysts for resource-saving energetics”, http://xn--80apbncz.xn--p1ai/nauka/46486

 

Publications

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Annotation of the results obtained in 2020
Direction 1 The approaches to prepare and synthesize the new Ni-containing catalytic materials based on ordered mesoporous SBA-15 support modified with mono- (CeO2, La2O3) and binary (CeO2-La2O3, La2O3-MnOx, CeO2-MnOx (molar ratio Ce/Mn = 0.25, 1 and 9)) nanodispersed particles were developed. The nanoparticles of modifiers based on binary oxides, preliminarily introduced into the porous structure of the SBA-15, were found to possess a significant effect on the distribution and sizes of nanoparticles of precursors of Ni-containing phases, reducing their size from 18 nm (for unmodified SBA-15) to up to 7.5 nm for NiO in the CeO2-MnOx/SBA-15 (Ce/Mn = 9). With an increase in Сe/Mn ratio (from 0.25 to 9) and subsequent NiO deposition, an increase in the defectiveness of the crystal lattice of the modifier nanoparticles was observed due to the incorporation of MnOx and/or NiO into the CeO2 structure (change in the lattice parameter d111 (CeO2)). The MnOx addition to CeO2 strongly affected the size of NiO crystals: for Ni/CeO2-MnOx/SBA-15 catalysts, the CSR size of NiO varied from 7.5 to 11.4 nm depending on the Ce/Mn ratio. The catalytic activity of the composites Ni/CeO2-MnOx/SBA-15 (with different Ce/Mn ratios), Ni/La2O3-MnOx/SBA-15, Ni/La2O3/SBA-15 was investigated in the course of dry reforming of methane. The gradient catalytic DRM test in the temperature range of 400-800 °C showed the highest conversions of CH4 and CO2 for the Ni/CeO2-MnOx/SBA-15 sample with Ce/Mn=9. For this sample, stable conversions of CH4 and CO2 were also observed (the long-term stability tests at 650 °C for 24 and 80 h). The introduction of Mnn+ cations into the CeO2 structure led to an increase in the interaction of nanoparticles of the active component with the support, an increase in the concentration of oxygen vacancies in the support structure and, consequently, to a decrease in the sintering of the active component and a significant decrease in the amount of carbon deposits (according to the TGA data, the weight losses of the spent sample after 24 h and 80 h of catalytic testing were 0.0 and 18.9 wt%, respectively). Thus, the use of ordered mesoporous SBA-15 modified with defective Ce1–xMnxO2–δ nanoparticles made it possible to stabilize metallic Ni nanoparticles with the size of 5 nm, which provided high catalytic activity in the DRM reaction into synthesis gas for at least 80 h with a minimal surface coke deposition. Direction 2 The catalytic properties of a number of hybrid materials, namely, AgPd@UiO-66 and AgBi@UiO-66 for the oxidation of propylene glycol (PG), Au and AuAg NPs and hybrid materials Pd@UiO-66, AgPd@UiO-66 and AgBi@UiO-66 for glycerol oxidation reaction as well as various Pd, PdAu, PdAg, Au and AuAg catalysts (both supported and in the form of NPs) for the 5-hydroxymethylfurfural (HMF) oxidation, were studied. It was shown that the use of hybrid catalytic systems based on HSO3-UiO-66 was promising for the cascade glycerol conversion to lactic acid in a neutral medium. It was shown that the hybrid materials Pd@HSO3-UiO-66 and PdBi@HSO3-UiO-66 were catalytically active in glycerol oxidative transformations. By using the example of PdBi@HSO3-UiO-66 hybrid materials with the Pd/Bi=90/10 ratio and the total metal content of 2.5 wt%, it was shown that realization of the reaction at oxygen pressure of 3 atm and 100 oC provided the glycerol conversion to lactic acid (LA) in a neutral medium with high selectivity (up to 80%). For bimetallic Au1-xAgx NPs obtained by laser ablation, a synergistic interaction between Ag and Au was established comprising the enhancement of oxidation sites on the surface of bimetallic Au1-xAgx NPs. The Ag addition led to an increase in the activity in glycerol oxidation, on the one hand, and a decrease in their aggregation stability under the reaction conditions, on the other hand. In this case, the selectivity towards LA for bimetallic Au1-xAgx NPs sharply decreased in favor of the formation of glyceric acid at small Ag amounts as well as the products of oxidative cleavage of the C-C bond with an increase in the Ag fraction. It was found that the most promising compositions in the cascade glycerol transformations in a neutral medium were Pd1-xBix systems, while bimetallic samples containing Ag (both Pd1-xAgx and Ag1-xBix) did not exhibit catalytic activity. Based on the data obtained, the most promising compositions for cascade HMF transformations in a neutral medium were Pd1-xAgx systems with a small Ag amount. The systems based on Au1-xAgx were characterized by high activity in the oxidative cleavage of the C–C bond. In the cascade PG transformations, the systems based on Pd1-xAgx with high silver content (Ag/Pd = 85/15) were found promising; it was shown that for the Pd1-xAgx@UiO-66 hybrid materials, the distribution of Pd1-xAgx particles in the UiO-66 matrix and their sizes were of importance. It was found that the UiO-66 modification with HSO3 groups promoted a strong increase in the selectivity towards LA during the cascade glycerol conversion over PdBi@HSO3-UiO-66, while the oxidative PG transformations over AgPd@UiO-66 and AgPd@HSO3-UiO-66 were practically unaffected by the –HSO3 introduction. The HSO3-, NH2-, NO2- and OH-modified samples of UiO-66 as the most promising MOF were synthesized using the original methods, the structure, chemical composition of the samples were confirmed by XRD, IR spectroscopy, and N2 adsorption. It is planned to study the catalytic properties of the hybrid materials synthesized on the basis of modified ligands in cascade transformations of platform molecules. Direction 3 Based on the results of quantum chemical calculations, the surfaces of β and γ- Bi2O3, Bi2SiO5, and Bi12SiO20 were constructed to be further used to model the interfaces between these phases. While for isostructural Bi12SiO20 and -Bi2O3, the surfaces (001) with a thickness of one unit cell were calculated, for β-Bi2O3 and Bi2SiO5 that did not coincide in the structural parameters, the supercells Bi2SiO5 (100) and β-Bi2O3 (001) with sizes of 2*2 and 3*3, respectively, were calculated to ensure the compatibility of the resulting structures. In addition, the influence of the spin-orbit interaction (SOC) on the electronic structure of the compounds under consideration was determined. Various options to create complex structures, composites, and doping, namely, joint synthesis, coprecipitation, impregnation, were implemented by laser ablation, and the properties of BSO-TiO2, BSO-TiO2, Pt/BSO materials obtained by different methods, as well as the effect of the annealing temperature, were studied and compared. It was established that the amorphous structure of the ablated bismuth silicate was stabilized in composites, and the effects of the structure on the optical properties were determined. The simulation of the obtained experimental spectra of electrochemical impedance was carried out, the models of equivalent electrical circuits for the semiconductor/solution interface were calculated. On the basis of the models developed, the assumptions were made regarding the mechanisms of processes occurring at the semiconductor/solution interface. The parameters were extracted from the obtained models that allow quantitatively characterizing the system. The photocatalytic activity of the materials synthesized on this basis, including oxides of titanium, bismuth, and bismuth silicates, obtained by various methods, and composites with various compositions was determined in the processes of hydrogen production, photocatalytic degradation of aqueous solutions of phenols and dyes. The efficiency (including in comparison with the materials synthesized at the previous stages), mechanisms of the decomposition of rhodamine B and phenol for different photocatalysts and excitation sources, decay rate constants, the effect of the excitation wavelength, and the BSO stability were determined. The compact unit to test the photocatalytic activity of the materials in the hydrogen decomposition reaction with the LED sources was developed, the tests were carried out and the opportunity to generate hydrogen on bismuth silicates from aqueous methanol solutions was shown. A rather good efficiency was transitionally achieved for the catalysts based on titanium dioxide. Direction 4 The catalysts based on manganese dioxide with a cryptomelane structure modified with iron and with additions of Pd in the amount of 1, 2, 3 %wt. by varying the nature of the Pd precursor and/or Ag 1–5 %wt. were prepared. The studies of the stability in CO oxidation for modified catalysts showed that the sample OMS-2, unmodified with transition metals, gradually decreased its activity after 100 h of testing (36,000 h-1 and О2/СО=8/1), and under conditions of 36,000 h-1 and О2/СО=21/1 its activity sharply decreased after 25 h of testing, while the modified Fe-, Sn-, Ce-OMS-2 catalysts retained their activity for at least 100 h. The Fe- and Sn-containing catalysts showed almost the same activity, which decreased slightly during the first hours of testing, after which it reached a stable 85–86%. The most active catalyst was Ce-OMS-2, for which the highest conversion was obtained at a lower temperature, which increased by 11% during the testing. The introduction of 1 wt.% Pd made it possible to significantly increase the activity of the iron-modified OMS-2 in CO oxidation; the experimentally determined Ea values decreased from 44 to up to 27 kJ/mol. The catalytic properties of the synthesized OMS-2 samples modified with Fe3+ in the ratio Mn/M of 20/1, with additions of Ag and/or Pd, were determined in the oxidation of ethanol and formaldehyde. The synergistic Fe–Mn–Ag effect was achieved in the case of the Fe-OMS-2 (20/1)+Ag catalyst in the selective oxidation of ethanol. The introduction of 5 mol.% Fe into MnO2 with the OMS-2 structure made it possible to obtain a catalyst in which the Fe cations were well dispersed without the formation of separate phases. The subsequent Ag deposition on Fe-OMS-2 (20/1) and OMS-2 resulted in a sample with high content of adsorbed oxygen species on the surface (XPS data), which played a key role and led to the production of catalysts with high activity (T80=150-155 °C) and selectivity (93%) towards acetaldehyde. The introduction of Pd and/or Ag additives into the iron-modified OMS-2 led to an increase in the activity of the catalyst in the total oxidation of formaldehyde: the addition of 1 wt.% Pd to 3 wt.% Ag led to a significant increase in the activity of such a catalyst in the formaldehyde oxidation: T50 = 114 °C, T90 = 126 °C (120,000 h-1), an increase in the Pd content up to 2 wt. %/2 wt.% Ag in Fe-OMS-2 (20/1) was accompanied by the activity increase (T50 = 79 °C, T90 = 88 °C) in the formaldehyde oxidation to CO2. List of publications for the reported period: 1. Yu. Belik, T. Kharlamova, A. Vodyankin, V. Svetlichnyi, O. Vodyankina, Mechanical activation for soft synthesis of bismuth silicates Ceramics International (2020 г.) WOS SCOPUS Q1 2. O.Yu. Vodorezova, I.N. Lapin, T. I. Izaak, Formation of the open-cell foam structures in tetraethoxysilane-based gelling systems, J. Sol-Gel Sci.Technol (2020 г.) WOS SCOPUS Q2 3. S. Galanov, O. Sidorova, O. Magaev, The MnOx-Al2O3 catalysts in the reaction of С1-С3 hydrocarbons deep oxidation IOP Publishing (2020 г.) SCOPUS 4. V. A. Svetlichnyi, E. D. Fakhrutdinova, T. S. Nazarova, S. A. Kulinich, O.V. Vodyankina, Comparative Study of Bismuth Composites Obtained via Pulsed Laser Ablation in a Liquid and in Air for Photocatalytic Application. Solid State Phenomena (2020 г.) WOS SCOPUS Q3 5. Sergey Ten, Viktoriia V. Torbina, Vladimir I. Zaikovskii, Sergei A. Kulinich, Olga V. Vodyankina, Bimetallic AgPd/UiO-66 Hybrid Catalysts for Propylene Glycol Oxidation into Lactic Acid, Materials (2020 г.) WOS SCOPUS Q2 6. E. D. Fakhrutdinova, A.V. Shabalina, M.A. Gerasimova, A. L. Nemoykina, O.V. Vodyankina, V.A. Svetlichnyi, Highly Defective Dark Nano Titanium Dioxide: Preparation via Pulsed Laser Ablation and Application, Materials (2020 г.) WOS SCOPUS Q2 7. M. Grabchenko, G. Pantaleo, F. Puleo, O. Vodyankina, L.F. Liotta, Ni/La2O3 catalysts for dry reforming of methane: Effect of La2O3 synthesis conditions on the structural properties and catalytic performances International Journal of Hydrogen Energy (2021 г.) WOS SCOPUS Q1 8. A.A. Vodyankin, Yu.A. Belik, V.I. Zaikovskii, O.V. Vodyankina, Investigating the influence of silver state on electronic properties of Ag/Ag2O/TiO2 heterojunctions prepared by photodeposition Journal of Photochemistry & Photobiology A: Chemistry (2021 г.) WOS SCOPUS Q1 9. K. L. Timofeev, O. Vodyankina, Selective oxidation of bio-based platform molecules and its conversion products over metal nanoparticle catalysts: A review, Reaction Chemistry & Engineering (2021 г.) WOS SCOPUS Q1 Information sources devoted to the project on the Internet: News on the website of National Research Tomsk State University: “In TSU, chemists from different countries discuss the prospects of development of catalysis”, http://www.tsu.ru/news/v-tgu-khimiki-iz-raznykh-stran-obsudyat-perspektiv/ News on the website of National Research Tomsk State University: “TSU and ECTC participate in international exhibition and forum “Khimia”, http://www.tsu.ru/short_news/tgu-i-ikhtts-primut-uchastie-v-mezhdunarodnoy-vystavke-i-forume-khimiya/ News on the website of the laboratory of new materials and promising technologies of SPTI TSU: “Researcher of the Lab, Elena Fakhrutdinova, represented the results on the development of photocatalysts based on bismuth silicate for ecology and green energetics”, http://amtlab.ru News on the website of the laboratory of new materials and promising technologies of SPTI TSU: “Anastasia Shabalina participated in the XI International conference “Modern methods in theoretical and experimental electrochemistry”, http://amtlab.ru News on the website of National Research Tomsk State University: “TSU presented 20 developments on national exhibition VUZPROMEXPO-2020” List of TSU exhibits represented at the VUZPROMEXPO-2020 Exhibition. DIGITAL CATALOGUE http://www.tsu.ru/upload/iblock/%D0%9F%D0%B5%D1%80%D0%B5%D1%87%D0%B5%D0%BD%D1%8C%20%D0%B4%D0%B5%D0%BC%D0%BE%D0%BD%D1%81%D1%82%D1%80%D0%B8%D1%80%D1%83%D0%B5%D0%BC%D1%8B%D1%85%20%D1%8D%D0%BA%D1%81%D0%BF%D0%BE%D0%BD%D0%B0%D1%82%D0%BE%D0%B2%20%D0%A2%D0%93%D0%A3%20%D0%BD%D0%B0%20%D0%92%D1%83%D0%B7%D0%BF%D1%80%D0%BE%D0%BC%D1%8D%D0%BA%D1%81%D0%BF%D0%BE%202020.pdf

 

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Annotation of the results obtained in 2021
Direction 1. The methods have been developed to promote nickel-containing (10 wt% Ni) supported catalysts based on La2O3-CeO2 and CeO2-MnOx double oxides with Cu and Ag additives. The samples of Cu- or Ag-promoted (1.0 mol% with respect to Ni) Ni-containing catalysts based on La2O3-CeO2 (LaCe) and CeO2-MnOx (CeMn) double oxides were prepared with La/Ce, Ce/Mn molar ratios of 1/1, 9/1: Ni-Cu/LaCe (1:1), Ni-Cu/LaCe (9:1); Ni-Cu/CeMn (1:1), Ni-Cu/(9:1); Ni-Ag/LaCe (1:1), Ni-Ag/LaCe (9:1); Ni-Ag(NH3)/LaCe (9:1), Ag(NH3)-Ni/LaCe (9:1), and differed in La/Ce ratio in the support, the nature of the Ag precursor (AgNO3, [Ag(NH3)2]NO3) and the order of introduction of the supported components; Ni-Ag/CeMn (1:1) and Ni-Ag/CeMn (9:1) with different Ce/Mn ratios in the support. For the Cu-promoted samples, the promoter distribution in the structure of mixed phases Ce1-xy-zLaxNiyCuzO2 with a fluorite structure and LaNi1-xCuxO3 with a perovskite structure for Ni-Cu/LaCe (1:1) and Ni-Cu/LaCe (9:1), respectively, and the formation of mixed phases Ni1-xCuxMn2O4 with a spinel structure and Ce1-x-yMnxCuyO2 with a fluorite structure in Ni-Cu/CeMn (1:1) and Ni-Cu/CeMn (9:1) samples, respectively, were established. For the Ag-promoted samples, the silver distribution was revealed predominantly on the surface of the oxide catalyst precursors. The formation of more dispersed particles of metallic Ni in the catalysts promoted with Cu and Ag compared with the corresponding unpromoted samples was established by XRD. The silver introduction promoted a decrease in the Ni reduction temperature (according to H2-TPR data), while the copper addition had practically no effect on the reduction process. Among the studied samples, the highest catalytic activity in the reaction of dry reforming of methane was characteristic of the Ni-Cu/LaCe (1:1) catalyst, the CO2 and CH4 conversions were higher than for the corresponding unmodified sample, and under the experimental conditions approached the equilibrium values, while the H2/CO ratio at 600-900 °C was above 0.9. An increase in the La content in the support for the Ni-Cu/LaCe sample (9:1) was accompanied by a decrease in the initial activity as well as in the H2/CO ratio; under the isothermal conditions, this catalyst run in with time approaching the stationary state: at 650 °C, the stationary conversions were 60% for CO2 and 45% for CH4, the H2/CO ratio was 0.81. The Ni-Cu samples supported on Ce-Mn-O supports exhibited rather high activity at temperatures below 750 °C but gradually deactivated due to carbonization. The initial CO2 and CH4 conversions at 650 °C were 67% and 54%, respectively, and the H2/CO ratio was 0.89; after 6.5 h, the CO2 and CH4 conversions were reduced to up to 63% and 47%, and the H2/CO ratio was reduced to up to 0.81. An increase in the Mn content in the support led to a noticeable decrease in the initial activity for the Ni-Cu/CeMn (1:1) sample over the entire temperature range. It was found that regardless of the method and order of introduction, the silver addition led to a significant decrease in the activity of the DRM catalysts. The Ag inhibitory effect was associated with the suppression of the CH4 dissociative adsorption on the Ni1-xAgx particles formed. Direction 2. Modification of UiO-66 in hybrid 1%Pd-Ag/X-UiO-66 materials with NH2 and HSO3 groups is accompanied by a decrease in the HMF conversion in water. While keeping a sufficiently high HMF conversion (74.9%), a bimetallic 1%Pd,Ag@HSO3-UiO-66 sample in an alkaline medium showed the highest selectivity towards the target products, and a decrease in the amount of the by-products formed in the presence of NaOH was observed. During the HMF oxidation in the DMSO-water mixture in the presence of mild alkaline agent NaHCO3, an increase in the DMSO fraction led to the activity decrease for the 1%Pd-Ag/UiO-66 catalyst; however, the selectivity towards the target HMF oxidation products passed through a maximum for the DMSO/water ratio of 2/1. Based on the results of studying the HMF oxidation over 1%Pd-Ag/UiO-66 using the HPLC and NMR, it was found that the formation of the target product FDCA was possible only at pH>7 through the route HMF→HMFCA→FFCA→FDCA. It was found that when using the strong base NaOH, the main by-products of the catalytic HMF oxidation were those of hydration, oligomerization, and the Cannizzaro reaction of the carbonyl groups of the initial reagents and intermediates. In a neutral environment, the HMF oxidation to FDCA was hindered, while the slow HMF oxidation occurred through the route HMF-DFF-FFCA-FDCA. For the modified X-UiO-66 materials (X = -HSO3, -NO2, -NH2, -OH, -H), it was shown that the substituent had a large effect on the propylene glycol conversion in the presence of hydrogen peroxide as an oxidizing agent, with the hydroxyacetone being the main product (83%). The conversion was found to increase by a factor of 2 (up to 17.5%) while maintaining the selectivity towards hydroxyacetone (~82%). In the reaction of oxidative glycerol conversion, the presence of sulfate groups in the composition of Bi,Pd@UiO-66-HSO3 catalysts provided high selectivity towards C3 products (above 80%) in a neutral medium. The use of the water-acetonitrile mixture (1/1 mol.) as a solvent in the oxidative glycerol conversion inhibited the route to lactic acid formation. Direction 3. A method to synthesize the complex compositions of bismuth titanates-silicates Bi2Si1-xTixO5 (BST) has been developed. Based on the analysis of the lattice parameters, it was shown that in the structure of Bi2SiO5 (the main phase content was up to 95 %wt.), and there was a partial substitution of Ti atoms by those of Si. Based on the laser techniques (pulsed laser ablation, PLA), the individual oxides were synthesized by ablation of Ti, Bi, Zn, Sn, Mn, V, Pb metals in water, including the modification of dark TiO2 with Pt/Ag additives and the synthesis of the Ag/ZnO. For the first time, the complex oxides based on bismuth, BXO, where X = Si, Ti, Zn, Fe, V, including bismuth silicates of various stoichiometry, i.e. bismuth orthosilicate and sillenite, were synthesized using the PLA. Using the quantum chemistry methods, the structure and features of the electron density distribution at the interfaces were studied based on bismuth oxides and silicates, which can be considered the model systems, illustrating the process of formation and properties of the interface between the phases of bismuth oxide and silicate in the Bi-containing composites exhibiting activity in photocatalysis. The data were obtained characterizing the processes of formation and separation of the charges during the irradiation. The highest photocatalytic activity and stable photocurrent under soft UV irradiation (375 nm) were observed for the samples with improved structural properties (TiO2-400, Pt/TiO2-400, TiO2-600, BST-600), especially for those modified with platinum nanoparticles. A significant increase in the density of the generated photocurrent occurred in an alkaline medium and in the presence of electron donors (glycerol and ethanol) in the solution. The photocatalytic activity was determined for all materials synthesized at this stage, including the individual oxides of titanium, bismuth, iron, manganese, tin, lead, vanadium as well as for the complex oxides of ternary systems BXO, where X = Si, Ti, Zn, Fe, V in the process of decomposition of the rhodamine B dye and phenol under the action of LED with a wavelength of 375 nm. The most active systems were revealed, namely, zinc oxide, dark titania, and bismuth silicates. The zinc-based materials showed the best rhodamine B degradation characteristics. The BSO showed excellent results in the phenol photodegradation. Using the "traps", the role of active particles of a radical nature (h+,•O2, •OH) in the rhodamine B decomposition was established for titania, the rate constants were calculated, and the stability of bismuth silicate samples with stoichiometry Bi12SiO20 close to monophase with a small amount of phase impurity Bi2SiO5 was studied. Dark ablative titania and its platinized modification showed rather good results during the study of photocatalytic hydrogen generation. The optimal concentration of platinum during the modification was 0.25%mass. The studies were carried out using various sacrificial agents (methanol, glycerol) varying pH and excitation wavelength. The hydrogen generation was obtained upon irradiation with visible radiation. For the photocatalytic hydrogen production, a semi-automatic unit with an online analysis of the gaseous medium was designed and assembled. Direction 4. In the MnO2-based catalysts with the OMS-2 structure, modified with iron or cerium (Mn/Me = 20/1 mol.), Pd was introduced in the amount of 1–2 wt.% by the method of hydrolytic precipitation or wetness impregnation (varying the prereduction conditions: H2 at 95 °C or the addition of hydrazine) and/or Cu in the amount of 3-4 wt.% by impregnation according to the moisture capacity. The presence of palladium and/or copper and their oxides was not detected by the XRD, which indicated a high degree of dispersion of nanoparticles of the introduced components in the MnO2 catalysts. It was found by the TPR–H2 method that the chemisorption of CO molecules and the strength of the Mn–O bond had an important effect on the catalytic properties of the catalysts based on manganese oxides MnO2. The use of manganese sulfate as a precursor of Mn2+ ions led to a stronger Mn–O bonding and high degree of crystallization of anisotropic OMS-2 particles, which was confirmed by the TPR-H2, XRD and Raman data; however, these catalysts were characterized by low activity in the low-temperature CO oxidation. The results of studies of the combined effect of modifiers and nanoparticles of the introduced metals (Cu/Pd) on the catalytic properties of the samples in the presence of water vapor showed that the presence of 5%vol. water vapor in the reaction mixture led to a noticeable (by 50–100 °C) increase in the temperature at which the specified CO conversion was achieved for all samples modified with Fe, Sn, Ce, as compared with dry conditions. The observed initial activity of the samples under humid conditions in the isothermal mode changed in the following order: Ce–MnO2 (20/1) = Ce–MnO2 (10/1) = Fe–MnO2 (10/1) > Fe–MnO2(20/1) > Sn–MnO2(20/1) > Sn–MnO2(10/1) = MnO2. The modification had different effects on the activity of the samples in formaldehyde oxidation. For the Me–MnO2 (20/1) samples, the modification with Fe and Sn led to a noticeable shift in the temperature dependence of the formaldehyde conversion towards the low-temperature region, while the modification with Ce did not have a significant effect on the conversion. In general, the activity of the samples in the formaldehyde oxidation changed in the following order: Ce–MnO2(10/1) > Fe–MnO2(20/1)> Sn–MnO2(20/1) > Fe–MnO2(10/1) = Sn–MnO2(10/1) = Ce–MnO2(20/1) ≥ MnO2. The hydrazine introduction at the stage of Pd deposition ensured a stronger interaction of nanoclusters/ions of the Cu, Pd, Fe, Mn components with each other, which made it possible to achieve high catalytic activity in the low-temperature CO oxidation reaction. Activation in a flow of Н2 at 95 °С for 2 h led to a significant change in the catalyst structure, while the Pd deposited from the Pd(NO3)2 solution retained its stability during the CO oxidation. The catalysts 1Pd/Fe–OMS-2 and 3Cu–2Pd/Fe-OMS-2 (Pd deposited by hydrolytic deposition from H2PdCl4 using hydrazine) showed similar activity in stability testing under conditions of low-temperature CO oxidation in the presence of water vapor (25–30 h at T90 = 130 °C), however, a slight activity decrease was observed during the entire experiment. For 1Pd/Fe–OMS-2, the decrease may be associated with the gradual oxidation of Pd0 or Pdδ+ sites by molecular О2, and the amount of PdO oxide, which was less active in CO oxidation, became higher. For 3Cu–2Pd/Fe-OMS-2, the CuO formation seems to hinder the reoxidation of Pdδ+, which made the catalyst less stable. List of publications for the reporting period: 1. Grabchenko M., Pantaleo G., Puleo F., Kharlamova T.S., Zaikovskii V.I., Vodyankina O., Liotta L.F. Design of Ni-based catalysts supported over binary La-Ce oxides: Influence of La/Ce ratio on the catalytic performances in DRM, Catalysis Today (2021) WOS SCOPUS Q1 2. Grabchenko M.V., Dorofeeva N.V., Lapin I.N., La Parola V., Liotta L.F., Vodyankina O.V. Study of Nickel Catalysts Supported on MnOx–CeO2 Mixed Oxides in Dry Reforming of Methane, Kinetics and Catalysis (2021) WOS SCOPUS 3. Salaev M.A., Liotta L.F., Vodyankina O.V. Lanthanoid-containing Ni-based catalysts for dry reforming of methane: A review, International Journal of Hydrogen Energy (2022 г.) WOS SCOPUS Q1 4. Belik Yu.A., Vodyankin A.A., Fakhrutdinova E.D., Svetlichnyi V.A., Vodyankina O.V. Photoactive bismuth silicate catalysts: Role of preparation method, Journal of Photochemistry & Photobiology A: Chemistry (2022) WOS SCOPUS Q1 5. Shabalina A.V., Svetlichnyi V.A., Kulinich S.A. Green laser ablation-based synthesis of functional nanomaterials for generation, storage and detection of hydrogen, Current Opinion in Green and Sustainable Chemistry (2022) WOS SCOPUS Q1 6. Shabalina A.V., Fakhrutdinova E.D., Golubovskaya A.G., Kuzmin S.M., Koscheev S.V., Kulinich S.A., Svetlichnyi V.A., Vodyankina O.V. Laser-assisted preparation of highly-efficient photocatalytic nanomaterial based on bismuth silicate, Applied Surface Science (2022) WOS SCOPUS Q1 7. Golubovskaya A.G., Fakhrutdinova E.D., Svetlichnyi V.A. Bismuth silicates: preparation by pulsed laser ablation and photocatalytic activity, Proceedings of SPIE (2021) WOS SCOPUS 8. Fedorovich Z.P., Gerasimova M.A., Fakhrutdinova E.D., Svetlichnyi V.A. The influence of laser and thermal treatment on the optic properties of titania nanoparticles prepared by impulse laser ablation method Влияние лазерной и термической обработки на оптические свойства наночастиц диоксида титана, полученных методом импульсной лазерной абляции, Известия вузов. Физика (2021) WOS SCOPUS 9. Vodyankina O.V. Серебряные катализаторы для процессов парциального окисления спиртов, Катализ в промышленности (2022) SCOPUS 10. Kovaleva E.A., Vodyankina O.V., Svetlichnyi V.A. Interface features and electronic structure of Bi2SiO5/β-Bi2O3 heterojunction, Proceedings of SPIE (2021) WOS SCOPUS Information resources on the Internet devoted to the project: 1. TV channel "Russia" (Russia - 1). A news story about the photocatalytic production of hydrogen. Vesti-Tomsk. News (7.04.2021), https://www.youtube.com/watch?v=cf2d1zxIADE&t=677s. 2. State Internet Channel "Russia" "Obtaining hydrogen with the help of new catalysts" Hour of Science. Tomsk. News (18.04.2021), https://www.youtube.com/watch?v=46S5eWXGQCE 3. Official web site of Tomsk State University. The news title "Chemistry - ecology: Young scientists will help resource-saving energy". Tomsk State University News (13.09.2021), https://www.tsu.ru/news/khimiya-ekologii-molodye-uchenye-pomogut-resursosb/ 4. Official site of the Year of Science and Technology in Russia. The news title "At TSU, young scientists were told about environmentally friendly technologies." News of the Year of Science in Russia (13.09.2021), https://годнауки.рф/news/7561/ 5. Official site of Tomsk State University. The news title "Employees of the Chemistry department of TSU discussed the development of the science of catalysis at the congress in Kazan". News of Tomsk State University (05.10.2021), https://www.tsu.ru/freeformat/news/58425/?sphrase_id=363242

 

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