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China Geology 2024年第1期7卷 63-79页

作者： Viktor Antipin Valentina Makrygina Larisa Kushch Nataliya Sheptyakova Vinogradov institute of Geochemistry SB RAS664033 IrkutskRussia

The detailed description of two granite complexes in the Olkhon subterrane is given.The Early Paleozoic Sharanur complex was formed by granitization of gneisses of the Olkhon series.It includes migmatites,granite-gneisses,granites and pegmatites of normal alkalinity;they belong to the type of syncollisional granites.The Middle Paleozoic Aya granite complex includes mother Aya massif of amazonite-bearing granites and several types of rare-metal pegmatites.They have elevated alkalinity,low of Ba,Sr,and high LILE and HFSE elements contents.The Aya pegmatites lie in northwest cracks of stretching and associated with the rise of the territory under the influence of the North Asian plume.These cracks and pegmatites mark the beginning of a new intraplate geodynamic setting.Two geochemical types are distinguished among the pegmatites of this complex.These are amazonite pegmatites of Li-F type with Ta mineralization and complex type pegmatite with Be-Rb-Nb-Ta and Li-F mineralization(the Ilixin vein).The Tashkiney pegmatite vein is similar to Ilixin,but lies in the gneisses of the Olkhon series.It shows high concentrations of Be,Nb,Ta,as well as W,Sn,but lacks Li and F,due to a greater depth and higher temperature of the melt crystallization of this pegmatite.

关键词： Pegmatite Geochemistry Submantle plume Magmatism Caledonian collision Middle Paleozoic intraplate setting Be-Rb-Nb-Ta-Li-F mineralization Olkhon region Russia

Highly Defective Dark TiO_(2) Modified with Pt: Effects of Precursor Nature and Preparation Method on Photocatalytic Properties

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Transactions of Tianjin University 2024年第2期30卷 198-209页

作者： E.D.Fakhrutdinova O.A.Reutova T.A.Bugrova I.Yu.Ovsyuk L.S.Kibis O.A.Stonkus D.B.Vasilchenko O.V.Vodyankina V.A.Svetlychnyi National Research Tomsk State University TomskRussia 634050 Novosibirsk State University NovosibirskRussia 630090 Boreskov institute of Catalysis NovosibirskRussia 630090 nikolaev institute of inorganic chemistry NovosibirskRussia 630090

The study focused on the modification with platinum of dark defective titania obtained via pulsed laser ablation. Both the method of Pt introduction and the nature of the Pt precursor were varied. All samples exhibited similar phase compositions, specific surface areas, and Pt contents. High-resolution transmission electron microscopy coupled with pulsed CO adsorption revealed increased dispersity when photoreduction and the hydroxonitrate complex (Me _(4) N) _(2) [Pt _(2) (OH) _(2) (NO _(3) ) _(8) ] were used. The sample featured a high content of single-atom species and subnano-sized Pt clusters. The X-ray photoelectron spectroscopy results showed that the photoreduction method facilitated the appearance of a larger number of Pt ^(2+) states, which appeared owing to the strong metal-support interaction (SMSI) eff ect of the transfer of electron density from the electron-saturated defects on the TiO _(2) surface to Pt ^(4+) . In the hydrogen evolution reaction, samples with a significant fraction of the Pt ^(2+) ionic component, capable of generating short-lived Pt^(0) single-atom sites under irradiation due to the SMSI eff ect, exhibited the highest photocatalytic activity. The 0.5Pt(C)/TiO_(2) -Ph sample exhibited the highest hydrogen yield with a quantum efficiency of 0.53, retaining its activity even after 8 h of operation.

关键词： Dark(black)TiO_(2) Pulsed laser ablation Platinum reduction method Precursor type Photocatalysis Hydrogen evolution reaction

Catalytic co-combustion of biomass and brown coal in a fluidized bed:Economic and environmental benefits

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Journal of Environmental Sciences 2024年第6期140卷 24-36页

作者： Yury V.Dubinin Nikolay A.Yazykov Petr M.Yeletsky Roman B.Tabakaev Aleksandra I.Belyanovskaya Vadim A.Yakovlev Federal Research Center Boreskov institute of Catalysis sb ras Lavrentiev Ave.5Novosibirsk630090Russia University of Tyumen Volodarskogo str.6Tyumen625003Russia

The work is devoted to the study of combustion of brown coal,pine sawdust,and their mixtures in a fluidized bed of catalyst at 600-750℃.It is shown that an increase in the content of sawdust in a mixture with brown coal leads to an increase in the burnout degree of solid fuel from 94.4%to 99.9%,while the emission of greenhouse gases in the form of CO_(2)CO and NOxis reduced(CO_(2)from the biomass is not included in the balance).The high content of alkaline earth metal oxides(CaO and MgO)in the mineral part of brown coal,sawdust,and their mixtures eliminates the emission of sulfur oxides and the slagging of heat-exchange surfaces during the combustion in a fluidized bed of catalyst.The optimal temperature,when the highest burnout degree of the above fuels is achieved in the combustion is 750℃.It is also shown that the increase in temperature and the content of sawdust in the composition of the fuel mixtures has a positive effect on the economic and environmental process indicators.

关键词： Co-combustion Fluidized catalyst bed Biomass Coal Economic effect Environmental impact

Hydrochar and synthetic natural gas co-production for a full circular economy implementation via hydrothermal carbonization and methanation:An economic approach

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Journal of Environmental Sciences 2024年第6期140卷 69-78页

作者： Judith González-Arias Guillermo Torres-Sempere Miriam González-Castaño Francisco MBaena-Moreno Tomás RReina inorganic chemistry Department and Materials Sciences institute University of Seville-CSICSevilleSpain Materials Sciences institute(ICMSE) CSIC-University of SevilleSevilleSpain Department of chemistry and Chemical Engineering Chalmers University of TechnologyGothenburgSE 41296Sweden

Herein we study the economic performance of hydrochar and synthetic natural gas coproduction from olive tree pruning.The process entails a combination of hydrothermal carbonization and methanation.In a previous work,we evidenced that standalone hydrochar production via HTC results unprofitable.Hence,we propose a step forward on the process design by implementing a methanation,adding value to the gas effluent in an attempt to boost the overall process techno-economic aspects.Three different plant capacities were analyzed(312.5,625 and 1250 kg/hr).The baseline scenarios showed that,under the current circumstances,our circular economy strategy in unprofitable.An analysis of the revenues shows that hydrochar selling price have a high impact on NPV and subsidies for renewable coal production could help to boost the profitability of the process.On the contrary,the analysis for natural gas prices reveals that prices 8 times higher than the current ones in Spain must be achieved to reach profitability.This seems unlikely even under the presence of a strong subsidy scheme.The costs analysis suggests that a remarkable electricity cost reduction or electricity consumption of the HTC stage could be a potential strategy to reach profitability scenarios.Furthermore,significant reduction of green hydrogen production costs is deemed instrumental to improve the economic performance of the process.These results show the formidable techno-economic challenge that our society faces in the path towards circular economy societies.

关键词： Hydrothermal carbonization CO_(2)waste valorization Methanation Profitability analysis

Surface reconstruction and structural transformation of twodimensional Ni-Fe MOFs for oxygen evolution in seawater media

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Nano Research 2024年第4期17卷 2429-2437页

作者： Liyuan Xiao Xue Bai Jingyi Han Tianmi Tang Siyu Chen Hui Qi Changmin Hou Fuquan Bai Zhenlu Wang Jingqi Guan institute of Physical chemistry College of ChemistryJilin UniversityChangchun 130021China The Second Hospital of Jilin University Changchun 130021China State Key Laboratory of inorganic Synthesis and Preparative chemistry College of ChemistryJilin UniversityChangchun 130012China Laboratory of Theoretical and Computational chemistry Institute of Theoretical ChemistryCollege of ChemistryChangchun 130023China

As a four-electron transfer reaction,oxygen evolution reaction(OER)is limited by large overpotential and slow kinetics.Here,we in-situ synthesized two-dimensional(2D)Ni-Fe metal-organic framework nanosheets on nickel foam(NixFe-TPA/NF,TPA=terephthalic acid)for oxygen evolution in alkaline and alkaline seawater electrolytes.In 1 M KOH,Ni3Fe-TPA/NF shows a low overpotential(η10)of 189 mV at 10 mA·cm^(-2) and an ultra-low overpotential of only 260 mV at 500 mA·cm^(-2).In alkaline seawater,Ni3Fe-TPA/NF still provides impressive OER performance,with anη10 of 265 mV.In-situ Raman characterization results show that the phase transition occurs during the OER,and Ni3FeOOH with more oxygen vacancies is in-situ formed,reducing the OER energy barrier.Density functional theory(DFT)reveals that the synergy between Ni and Fe reduces the energy barrier and accelerates the rate-determining step.In addition,the ultra-thin 2D sheet structure and the close combination of Ni3FeOOH and highly conductive NF support ensure the high catalytic OER activity.Therefore,the surface reconstruction and structural modification strategy can be used to design and prepare high-performance OER electrocatalysts for energy-related applications.

关键词： density functional theory(DFT)calculation Ni3FeOOH oxygen evolution reaction seawater electrolysis surface reconstruction

Antibacterial HA-coatings on bioresorbable Mg alloy

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Journal of Magnesium and Alloys 2024年第5期12卷 1965-1985页

作者： K.V.Nadaraia D.V.Mashtalyar M.A.Piatkova A.I.Pleshkova I.M.Imshinetskiy M.S.Gerasimenko E.A.Belov V.V.Kumeiko D.N.Kozyrev K.A.Fomenko V.V.Mostovaya B.R.Torpanov A.R.Biktimirov I.S.Osmushko S.L.Sinebryukhov S.V.Gnedenkov institute of chemistry FEB ras Far Eastern Federal University A.V.Zhirmunsky National Scientific Center of Marine Biology FEB ras Regional Clinical Dermatovenerological Dispensary NMIC “Treatment and Rehabilitation Center”

In this study, a calcium-phosphate coating was formed on a Mg-Mn-Ce alloy by the plasma electrolytic oxidation(PEO). The antibiotic vancomycin, widely used in the treatment of infections caused by Staphylococcus aureus(S. aureus), was impregnated into the coating.Samples with vancomycin showed high bactericidal activity against S. aureus. The mechanical and electrochemical properties of the formed coatings were studied, as well as in vitro cytotoxicity tests and in vivo tests on mature male rats were performed. According to SEM,EDS, XRD and XPS data, coatings had a developed morphology and contained hydroxyapatite, which indicates high biocompatibility.The analysis of roughness of coatings without and with vancomycin did not reveal any differences, confirming the high roughness of the samples. During electrochemical tests, an increase in corrosion resistance by more than two times after the application of PEO coatings was revealed. According to the results of an in vivo study, after 28 days of the implantation of samples with calcium phosphate PEO coating and vancomycin, no signs of inflammation were observed, while an inflammatory reaction developed in the area of implantation of bare alloy,followed by encapsulation. Antibiotic release tests from the coatings show a sharp decrease in the concentration of the released antibiotic on day 7 and then a gradual decrease until day 28. Throughout the experiment, no significant deviations in the condition and behavior of the animals were observed; clinical tests did not reveal a systemic toxic reaction.

关键词： Bioactive coatings Biocompatibility Mg alloy Plasma electrolytic oxidation Hydroxyapatite Vancomycin

Analysis of the discrete contact characteristics based on the Greenwood-Williamson model and the localization principle

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Friction 2024年第5期12卷 1042-1056页

作者： Anastasiya A.YAKOVENKO Irina G.GORYACHEVA Ishlinsky institute for Problems in Mechanics ras Moscow119526Russia

The contact of a rigid body with nominally flat rough surface and an elastic half-space is considered.To solve the contact problem,the Greenwood-Williamson statistical model and the localization principle are used.The developed contact model allows us to investigate the surface approach and the real contact area with taking into account the asperities interaction.It is shown that the mutual influence of asperities changes not only contact characteristics at the macroscale,but also the contact pressure distribution at the microscale.As follows from the results,the inclusion in the contact model of the effect of the mutual influence of asperities is especially significant for studying the real contact area,as well as the contact characteristics at high applied loads.The results calculated according to the proposed approach are in a good agreement with the experimentally observed effects,i.e.,the real contact area saturation and the additional compliance exhaustion.

关键词： surface roughness elasticity Greenwood-Williamson model localization principle asperity interaction

Study of asphaltene reaggregation in toluene/heptane mixture by dynamic and static light scattering

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Petroleum Research 2024年第1期9卷 48-54页

作者： Vladimir N.Kuryakov Oil and Gas Research institute of ras(OGRI ras) Gubkina Str.3119333MoscowRussian Federation

This paper presents the study of the effect of multiple ultrasonic impacts on submicron asphaltene aggregates in a toluene/heptane solution,conducted with dynamic light scattering technique.The objects of the study were four samples of asphaltenes obtained from four different oils.For all samples,the change in the average size of the asphaltene submicron aggregates with time was measured after the addition of a precipitant(heptane)to a solution of asphaltenes in toluene at an amount above the threshold concentration.Asphaltene aggregates formed in solution after the addition of the precipitant and were subjected to ultrasonic treatment,which led to the destruction of the asphaltene aggregates.Aggregation of destroyed asphaltenes was observed.The kinetics of this aggregation were similar to the kinetics of aggregation of asphaltenes after the addition of a precipitant.Multiple iterations of asphaltene aggregate destruction in the sample led to a significant change in the kinetics of aggregation:the growth of aggregates slowed and stabilized at a size of approximately 200 nm and 30 nm for the different studied samples.

关键词： Asphaltenes Aggregation Sonication Dynamic light scattering Re-aggregation Colloidal stability Resins

Expanded Porphyrin Exhibiting Off-Centered Out-of-Plane Coordination to Dysprosium

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CCS chemistry 2024年第7期6卷 1731-1738页

作者： Dmitry I.Nazarov Jorge Labella Alexey V.Kuzmin Maxim A.Faraonov Evgenii N.Ivanov Salavat S.Khasanov Tomas Torres Mikhail K.Islyaikin Dmitri V.Konarev Federal Research Center of Problems of Chemical Physics and Medicinal chemistry ras 142432 Chernogolovka Department of Organic chemistry Universidad Autonoma de Madrid28049 Madrid institute of Solid-State Physics ras 142432 Chernogolovka Research institute of Macroheterocycles Ivanovo State University of Chemistry and Technology15300 Ivanovo G.A.Krestov institute of Solution chemistry of the Russian Academy of Sciences 153045 Ivanovo institute for Advanced Research in Chemical Sciences Universidad Autonoma de Madrid28049 Madrid IMDEA-Nanociencia 28049 Madrid

The complexation of high-spin lanthanides to porphyrinoids is a powerful strategy for the development of advanced molecular magnets.In this context,the use of expanded porphyrinoids remains elusive since their coordination chemistry is challenging to control.Herein,taking inspiration from on-surface chemistry,we explored the coordination of Dy^(3+)to a six-membered porphyrinoid,namely,the hemihexaphyrazine H3Hhp.Remarkably,we observed the selective formation of a mono-nuclear off-centered,out-of-plane H_(2)Hhp-Dy^(3+)complex when performing the complexation under reductive conditions.During this reaction,the oxidation state of the macrocycle did not change.Employing X-ray diffraction analysis,we found that the coordination number of Dy in this complex was 8.The macrocycle cocrystallized with decamethylcobaltocene(Cp_(2)^(*)Co)molecules,giving rise to a wellordered solid-state packing,governed byπ-πinteractions.As a result of this organization,a small magnetic coupling between the neighboring molecules was observed.All in all,this work provides key insights into the coordination of magnetically active metals with expanded porphyrinoids,thus motivating the development of advanced spintronic devices.

关键词： porphyrins dysprosium macrocycle coordination chemistry magnetism

Nickel-based cerium zirconate inorganic complex structures for CO_(2)valorisation via dry reforming of methane

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Journal of Environmental Sciences 2024年第6期140卷 12-23页

作者： Juan Luis Martín-Espejo Loukia-Pantzechroula Merkouri Jesús Gándara-Loe José Antonio Odriozola Tomas Ramirez Reina Laura Pastor-Pérez Department of inorganic chemistry and Material Sciences institute of Seville University of Seville-CSICSeville 41092Spain Department of Chemical and Process Engineering University of SurreyGuildford GU27XHUnited Kingdom

The increasing anthropogenic emissions of greenhouse gases(GHG)is encouraging extensive research in CO_(2)utilisation.Dry reforming of methane(DRM)depicts a viable strategy to convert both CO_(2)and CH4into syngas,a worthwhile chemical intermediate.Among the different active phases for DRM,the use of nickel as catalyst is economically favourable,but typically deactivates due to sintering and carbon deposition.The stabilisation of Ni at different loadings in cerium zirconate inorganic complex structures is investigated in this work as strategy to develop robust Ni-based DRM catalysts.XRD and TPR-H2analyses confirmed the existence of different phases according to the Ni loading in these materials.Besides,superficial Ni is observed as well as the existence of a CeNiO_(3)perovskite structure.The catalytic activity was tested,proving that 10 wt.%Ni loading is the optimum which maximises conversion.This catalyst was also tested in long-term stability experiments at 600and 800℃in order to study the potential deactivation issues at two different temperatures.At 600℃,carbon formation is the main cause of catalytic deactivation,whereas a robust stability is shown at 800℃,observing no sintering of the active phase evidencing the success of this strategy rendering a new family of economically appealing CO_(2)and biogas mixtures upgrading catalysts.

关键词： CO_(2)conversion Dry reforming of methane Nickel catalysts Pyrochlore Cerium zirconate