DEPARTMENT OF PHOTOCHEMISTRY
The Department Head– Kuchmiy Stepan Yaroslavovych
Doctor of Chemistry, Professor
Brief summary of the Department of Photochemistry
The department of photochemistry was organized in 1934 and headed by Prof. Borys Yakovych Dain (department head till 1971) – a student of L. V. Pisarzhevskii- Academician of the USSR Academy of Sciences. B.Ya. Dain initiated experimental studies of the photoinduced electron transfer which is a fundamental primary step in the natural photosynthesis and many photochemical redox-reactions. These studies were continued in the works of the Dain’s pupils – Yosyp Yosypovych Dilung (Nominee of the State Award of Ukraine in the field of Science and Technology and L.V. Pisarzhevsksii Award of the National Academy of Sciences of Ukraine, Doctor of Sciences, Professor, Head of the Department of photochemistry in 1971–1993), who studied the photoinduced electron transfer phenomena in the systems based on chlorophil, dyes and aromatic chromophores, and Anatoliy Ivanovych Kryukov (Nominee of the L.V. Pisarzhevsksii Award of the National Academy of Sciences of Ukraine, Doctor of Sciences, Professor, Head of the Laboratory of photochemistry of coordination compounds, later – Laboratory of the photocatalytic reactions, 1974–1993), who established a vital role of the photoinduced electron transfer in the photochemistry of metal complexes and in photocatalysis, both homogeneous, with the participation of coordination compounds, and in heterogeneous, in the presence of semiconductor crystallites.
• fundamental and applied aspects of photophysical, photochemical and photocatalytic processes in light-sensitive systems comprising novel materials – nanometer semiconductor crystals, graphene oxide and reduced graphene oxide, various nanosized heterostructures and composites;
• new ways to efficient materials for photo- and electroluminescence, photovoltaics, non-linear optical materials based on polymer materials, semiconductor and metal nanocrystals, and dyes;
• development of light-sensitive materials for applications in printing, electronic and other industries.
Recent most important result
Principles of rational design of efficient photocatalytic systems based on semiconductor crystals, electron transfer mediators, sensitizers and secondary catalysts were formulated. Data on origins of the quantum size effects in highly disperse semiconductors and their influence on the photophysical, photochemical and photocatalytic properties of semiconductor nanocrystals and nanostructures were summarized. Fundamentals of a new trend in the semiconductor photochemistry named nanophotocatalysis were created. Common features and principal differences between classic semiconductor photocatalysis and nanophotocatalysis were analysed and shown to originate from spatial exciton confinement in semiconductor nanocrystals. New methods of synthesis of ultra-small (with the size around 2 nm) quantum dots of cadmium chalcogenides – CdS, CdSe, CdSxSe1–x, CdTe stabilized by amino-groups-rich polyelectrolytes were developed. The quantum dots exhibit photoluminescence in the visible spectral region (400–650 nm) with the relative quantum yields of up to 15–20 %. Feasibility of utilization of ultra-small CdS quantum dots as white-light emitting electroluminescent (EL) components of LED at an applied voltage of 5–6 V was shown.
а) Normalized absorption and photoluminescence spectra of ultra-small CdS, CdSe, and CdTe quantum dots. Photo: photoluminescence of a film with CdS quantum dots excited by UV light. (b) EL spectrum of CdS quantum dots incorporated in a four-layer model LED (ITO – conductive transparent glass, PEDOT:PSS – a conjugated polymer with the p-type conductivity, Ca-Al – a metal layer with the n-type conductivity.
New electrochemical and photocatalytic methods were applied to prepare ITO/ZnO/CdS heterostructures exhibiting a much higher photoelectrochemical activity than similar films produced by conventional methods.
Scanning electron microscopy images of electrodeposited ITO/ZnO film (a,b). (c) Photos of ITO/ZnO/CdS films produces by the conventional SILAR (Successive Ion Layer Adsorption and Deposition) method and original photocatalytic CdS deposition method (Photo) developed in the Department of photochemistry. (d) Chronoamperograms registered in aqueous 0.1 M Na2S solutions for ITO/ZnO/CdS-SILAR ITO/ZnO/CdS-Photo.
Illumination of colloidal graphene oxide (GO) by UV light was found to yield partially reduced GO. The heterostructures of GO and partially reduced GO with Ag nanoparticles produced under illumination with visible light were shown to be efficient electrocatalysts of methanol and formaldehyde oxidation by O2. Ultrasound-assisted interaction between colloidal GO and partially reduced GO sheets with graphite and multi-wall carbon nanotubes was found to yield stable aqueous dispersions, where the amount of graphite microparticles and nanotubes is the higher the deeper is the preliminary photoreduction of GO. Photochemical activity of colloidal GO as a photoinitiator of acrylamide polymerization under illumination at λ < 420 nm was reported for the first time.
(а) Atomic force microphotograph of a GO sheet on a Si surface. (b) Energy of the electron transition in colloidal GO (Ebg) as a function of exposure to UV light. Inset: photographs of colloidal GO before (left) and after (right) illumination. (c, d) Scanning electron microphotograph of graphite microparticles (c) and carbon nanotubes (d) dispersed in water by photochemically reduced GO.
New photocurable polymerization compositions were developed that found applications in technologies of protective masks for printed electronic plates production, UV-light curable varnishes and protective coating for printing industry.
Institute of Chemical Kinetics and Combustion of Siberian Branch of Russian Academy of Sciences, Novosibirsk State University, Novosibirsk, Russia (Doctor of Sciences, Professor Victor F. Plyusnin);
Belorussian State University, Faculty of Chemistry, Minsk, Belorussia (Doctor of Sciences, Professor Eugene A. Streltsov);
University of Southampton, Faculty of Engineering and the Environment, Southampton, United Kingdom (Doctor of Sciences Dmitriy V. Bavykin);
Chemnitz University of Technology, Chemnitz, Deutschland (Doctor of Sciences, Professor Dietrich R.T. Zahn).
Scientific staff of the department
Rayevska Oleksandra Yevgenivna, Senior researcher, candidate of sciences. Тel.: +38 (044) 525 02 70, fax: + 38 (044) 525 02 70, e-mail: firstname.lastname@example.org.
Shvalagin Vitaly Vasylyovych, Researcher, candidate of sciences. Tel.: +38 (044) 525 02 70, fax: + 38 (044) 525 02 70, e-mail: email@example.com
Stroyuk A.L., Kryukov A.I., Kuchmiy S.Ya., Pokhodenko V.D. Semiconductor photocatalytic systems for molecular hydrogen production using visible light // Theoret. Experim. Chem. – 2009. – 45, № 4. – P. 209-233.
Stroyuk O.L., Dzhagan V.M., Shvalagin V.V., Kuchmiy S.Ya. Size-Dependent Optical Properties of Colloidal ZnO Nanoparticles Charged by Photoexcitation // J. Phys. Chem. C. – 2010. – 114, N 1. – P. 220-225.
Stroyuk O.L., Rayevska O.Ye., Kozytskiy A.V., Kuchmiy S.Ya. Electron energy factors in photocatalytic methylviologen reduction in the presence of semiconductor nanocrystals // J. Photochem. Photobiol. A. – 2010. – 210, N 2-3. – P. 209-214.
Stroyuk O.L., Kuchmiy S.Ya., Kryukov A.I., Pokhodenko V.D. Semiconductor catalysis and photocatalysis on the nanoscale. – Nova Science Publishers, Inc., New York. - 2010. – 183 р.
Rayevskaya A.E., Stroyuk A.L., Grodzyuk G.Ya., Kuchmiy S.Ya., Dzhagan V.N., Plyusnin V.F., Grivin V.P. Dynamics of radiative recombination of charge carriers in CdS nanoparticles stabilized by polyethyleneimine // Theoret. Experim. Chem. – 2010. – 46, № 5. – P. 273-278.
Rayevska O.E., Grodzyuk G.Ya., Dzhagan V.M., Stroyuk O.L., Kuchmiy S.Ya., Plyusnin V.F., Grivin V.P., Valakh M.Ya. Synthesis and characterization of white-emitting CdS quantum dots stabilized with polyethylenimine // J. Phys. Chem. C. – 2010. – v. 114, N 51. – P. 22478-22486.
Bavykin D.V., Kulak A.N., Shvalagin V.V., Andryushina N.S., Stroyuk A.L. Photocatalytic properties of rutile nanoparticles obtained via low temperature route from titanate nanotubes // J. Photochem. Photobiol. A. – 2011. – v. 218, N 2-3. – P. 231-238.
Grodzyuk G.Ya., Rayevskaya A.E., Stroyuk A.L., Kuchmii S.Ya., Vortman M.Ya., Lemeshko V.N., Shevchenko V.V., Chertopalov S.V., Kolomzarov Yu.V., Sorokin V.M. Optical and electroluminescent characteristics of CdS nanoparticles stabilized by guanidine-containing dendrimers // Theoret. Experim. Chem. – 2011. – 47, № 6. – P. 361-66.
Stroyuk A.L., Andryushina N.S., Shcherban’ N.D., Il’in V.G., Efanov V.S., Yanchuk I.B., Kuchmii S.Ya., Pokhodenko V.D. Photochemical reduction of graphene oxide in colloidal solution // Theoret. Experim. Chem. – 2012. – 48, № 1. – P. 2-13.
A.V. Yakovenko, P.L. Stroyuk, V.V. Pavlishchuk Size-dependent photoinduced interactions between ZnO nanocrystals and a nitronyl nitroxide radical Nit(o-OH)Ph // Photochem. Photobiol. Sci. - 2013. - Vol. 12, P. 356–362. doi: 10.1039/c2pp25272d.
А.Е. Раевская, Г.Я. Гродзюк, А.Л. Строюк, С.Я. Кучмий, В.Ф. Плюснин Влияние температуры на оптические свойства наночастиц CdS, стабилизированных полиэтиленимином // Теорет. эксперим. химия. – 2012. – 48, № 2, – С. 95-101.
Borkovska L.V., Korsunska N.O., Stara T.R., Dzhagan V.M., Stroyuk O.L., Raevska O.Ye., Kryshtab T.G. Modification by thermal annealing of the luminescent characteristics of CdSe quantum dots in gelatin films // Phys. Status solidi (C). – 2012. - 9. – N 8-9. – P. 1779-1782.
Kositskiy A.V., Stroyuk A.L., Kuchmy S.Ya., Skorik N.A., Moskalyuk V.O. Morphology, photochemical and photocatalytic properties of nanocrystalline zinc oxide films // Theoret. Experim. Chem. – 2012. – 48, № 5. – P. 331-337.
O.L. Stroyuk, O.Ye. Rayvska, V.V. Shvalagin, S.Ya. Kuchmiy, D.V. Bavykin, E.A. Streltsov, S.K. Poznyak Gelatin-templated mesoporous titania for photocatalytic air treatment and application in metal chalcogenide nanoparticle-sensitized solar cells // Photochem. Photobiol. Sci. - 2013. - DOI: 10.1039/c2pp25196e.
Technical products of the department
Photocurable composition for production of printing plates with regeneration of sieve material – “PHOTOCOM – ТS”.
Photocurable composition for protective masks of printing plates – “МАSКОPHОТ – ТP".