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Получение новых гомогенных и гетерогенных электро- и фотокатализаторов на основе клеточных комплексов клатрохелатов переходных металлов и гибридных систем с фотосенсибилизирующими фрагментами, а также клатрохелатсодержащих углеродных и оксидных материалов и гетерогенных прекатализаторов для получения водорода из воды как наиболее распространённого его источника, а также из водных растворов Н-кислот.
Molecular hydrogen and hydrogen-based energy based on its use are the promising alternative of carbonaceous raw materials since an increase of energy consumption in modern industry and transport, using the raw materials and increase emission of CO2-pollutants. If we have an appropriate source of H2, the use of hydrocarbons can be substantially decreased by using of water as practically unlimited source of H2 and sunlight-based energy for water splitting. The main goal of the present project is the evaluation of the new types of highly effective molecular electro- and photocatalysts, as well as precatalysts for hydrogen production, which are the biomimetic functional analogues of natural hydrogenases, and the hybrid organic-inorganic materials based on them. This project will be performed on the edges of chemistry and physics of the hybrid molecular structures and organic-inorganic materials, as well as of physical, organic, elementoorganic and coordination chemistry, solid-state chemistry and physics, photo- and electrochemistry, modern of materials science and hydrogen-based energy. Functionalized iron and cobalt clathrochelates (in particular, those immobilized on the surface of carbonaceous materials) are prospective functional models of natural hydrogenases, allowing to produse of H2 from water and an origin of their high electrocatalytic activity is one of the most important tasks. In the case of the homogeneous molecular electrocatalytic process, the formation of a metal(I)-containing clathrochelate intermediate with the interaction of H+ ions leads to the H2 formation. So, the reduction of the cobalt and iron(II) hexachloroclatrochelates possessing an electrocatalytic activity will be used for the preparation of metal(I) cage complexes. The reactions of the titled compounds with strong H-acids, causing a H2 evalution or not, will be studied. In the case of the heterogeneous catalytic H2 production, the above complexes are only precatalysts of the catalytically active metallic nanoparticals which will be detected using the synchrotron XPS and XANES methods. For the efficient immobilization of a surface of various carbonaceous materials the synthesis of mono- and disulfide cobalt(II) clathrochelate with the terminal functionalized phenanthrenyl group(s), as well as of the hexasulfide analogues with encapsulated Fe2+, Ru2+ and Co2+ ions will be prepared. Nucleophylic substitution of the hexachloroclathrochelate precursors with the appropriate amine will be used for preparation of the complexes with terminal polyaromatic groups, the molecules of which do not contain the sulfure atoms known as potent inhibitors of the catalytic activity. Metal(II) tris-perfluoro-α-benzildioximates with terminal phenanthrenyl groups will be obtained by template cross-linking of a tris-perfluoro-α-benzildioxime with phenanthrenyl-containing boronic acid. The various type of the tris-α-dioximate clathrochelates with apical terminal phenanthrenylgroups for their immobilization on carbonaceous materials will be synthesized using the analogous synthetic approach. The first hybrid clathrochelate precursor of the polynuclear photocatalytic systems with annelated electrocatalyticaly and photocatalytically active fragments will be prepared stepwise synthetic procedures including the template synthesis, transmetallation and coordination. Cage complexes with one and two photosensitizers macroheterocyclic fragment will be prepared by transmetallation of triethylantimony-capped macrobicyclic precursors. The porphyrinato- and phthalocyaninato-containing hybrid system will be obtained by coordination of the 4-pyridyl-terminated clathrochelate ligands, with will be initially synthesized by template condensation. The pyridyl-terminated porphyrinato- and phthalocyaninatoclathrochelates will be used as N-donor ligands for the synthesis of more complicated hybrid systems. Cage complexes with apical terminal polar group designed for their efficient immobilization on oxide (including TiO2) and ceramic material will be prepared by template cross-linking on a metal ion as a matrix using the functionalized boronic acids. Their analogues with terminal polar groups in the apical and ribbed substituents will be synthesized by nucleophilic substitution of the corresponding hexachloroclathrochelate precursors. The composition and structure of the new d-metal cage complexes and hybrid system based on them will be obtained using elemental analysis, IR, UV-vis and multinuclear NMR spectroscopy; MALDI-TOF and ESI- mass spectra as well as by the single crystal X-ray diffraction. The electro and photocatalytic systems immobilized on a working electrode and electrode materials, as well as the transformation of the clathrochelate electro- and photocatalysts on a surface in the course of electro- and photocatalytic H2 production will be studied using the synchrotron XPS and XANES methods. The redox characteristics of the clathrochelates obtained and the hybrid systems based on them will be studied using CV method. This method accompanied with GC detection will be used for the study of electro- and photocatalytic properties of the above cage complexes and hybrid systems (including those immobilized on the surface of a working electrode and electrode materials) in the reaction of H2 production from H+ ions and photocatalytic water splitting. The obtained results and the developed methods will be allowe to create highly efficient biomimetic electro- and photocatalytic systems which will determine of the wordwide level at the chemistry physico-chemical and (photo)electrochemistry of the compounds and systems of this type and in the various fields of the modern materials science and hydrogen-based energy as well. The potential of innovation of the presented project is determinated by the creation of a new generation of highly efficient and chemically robust electro- and photocatalysts for molecular hydrogen production from water splitting and aqueous solutions. Thus designed (pre)catalysts can be immobilized on electrode materials and, then, they can be used in industrial and semi-industrial hydrogen generators (water electrolyzers), fuel cells and other devices of hydrogen-based energy.
грант РФФИ |
# | Сроки | Название |
1 | 1 ноября 2018 г.-31 декабря 2019 г. | Природа высокой гидрогеназной активности клатрохелатов d-металлов и гибридных систем на их основе: получение (пре)катализаторов новых типов, их иммобилизация на углеродные и оксидные материалы и электро- и фотокаталитическое получение молекулярного водорода из воды и Н-кислот |
Результаты этапа: | ||
2 | 1 января 2020 г.-31 декабря 2020 г. | Природа высокой гидрогеназной активности клатрохелатов d-металлов и гибридных систем на их основе: получение (пре)катализаторов новых типов, их иммобилизация на углеродные и оксидные материалы и электро- и фотокаталитическое получение молекулярного водорода из воды и Н-кислот |
Результаты этапа: | ||
3 | 1 января 2021 г.-31 декабря 2021 г. | Природа высокой гидрогеназной активности клатрохелатов d-металлов и гибридных систем на их основе: получение (пре)катализаторов новых типов, их иммобилизация на углеродные и оксидные материалы и электро- и фотокаталитическое получение молекулярного водорода из воды и Н-кислот |
Результаты этапа: |
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