DEPARTMENT OF FREE RADICALS
The founder and head of the department in 1970-2008:
Honorary Director of the Institute, academician of the National Academy of Sciences of Ukraine, the foreign member of the Russian Academy of Sciences, Professor, Doctor of Sciences in Chemistry,
L.V. Pisarzhevsky Institute of Physical Chemistryof the National Academy of Sciences of Ukraine,
03028, Kyiv-28, Nauki avenue, 31, tel. (44) 525-66-67, fax: (44) 525-62-16
Head of the department:
academician of the National Academy of Sciences of Ukraine, Professor, Doctor of Sciences in Chemistry,
L.V. Pisarzhevsky Institute of Physical Chemistry of the National Academy of Sciences of Ukraine,
03028, Kyiv-28, Nauky avenue, 31, tel. (44) 525-11-90 (44) 525-66-71, fax: (44) 525-62-16
The department of free radicals was founded in 1970 on the basis of the department of chemical structure and reactivity (up to 1934 - department of electrochemistry, 1934-1963 - department of isotopes), headed by the outstanding physical chemist – the Hero of Socialist Labor, academician of the AS of the Ukrainian SSR O.I. Brodsky (1895-1969). In 1970-2008 the department was headed by academician of the NAS of Ukraine V.D. Pohodenko. Since its existence the main works were devoted to the study of electronic structure and properties of free radicals and ion-radicals of different classes, influence of their structure on magnetic resonance and spectral characteristics, kinetics and mechanism of reactions involving such particles, determination of the regularirites of their electrochemical and photochemical performance. The main results of these scientific studies are summarized in the monographs: V.D. Pohodenko "Phenoxyl radicals" (Kyiv, Naukova Dumka, 1969), V.D. Pohodenko, A.A. Beloded, V.G. Koshechko "Oxidation-reduction reactions of free radicals" (Kyiv, Naukova Dumka, 1978); V.D. Pohodenko, L.S. Dehtyarev, V.G. Koshechko, V.S. Kuts "Problems of chemistry of free radicals"(Kyiv, Naukova Dumka, 1984) and several review articles.
Since the mid of 80's the department has begun researches in the field of physical chemistry of conducting polymers - polycongugated cation- and anion-radicals, whose unique properties, including electrophysical, electrooptical etc., stipulated interest in them as objects of modern molecular materials. Along with conducting polymers, during the last time one of the research areas of the department is physics and chemistry of two-dimensional structures - graphene, graphene oxide, MoS2 etc and also functional nanocomposites based thereon.
Main research directions
Development of scientific principles of physical chemistry of organic conducting polymers and various nanocomposite materials based thereon: development of chemical, electro-, mechano- and sonochemical methods for preparation of such materials with a complex of functional properties; study of physical-chemical, electrochemical, electrophysical, photochemical properties of these materials, their spectral and magnetic resonance characteristics; investigation of relationship between composition, structure and properties of such systems for targeted regulation of their functional characteristics.
Physical chemistry of two-dimensional structures - graphene, graphene oxide, MoS2 etc and also functional nanocomposites based thereon.
The most important recent results
A number of the original chemical, mechanochemical, electrochemical and other methods for preparation of new conductive organic polymers (COP) based on polyaniline, polypyrrole, polythiophenes, polyphenylenvinylene etc. was elaborated, the details of the chemical and electrochemical doping/dedoping of COP were clarified, the search of new dopants of COP was made, the influence of the nature of the organic solvent on physicochemical properties of the COP was studied, their physicochemical, electrochemical, electrophysical, photochemical properties, magnetic resonance and spectral characteristics were investigated.
Luminescent nanocomposites based on poly[2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV) and MCM-41
Novel methods for creating nanostructured COP and their original nanocomposites with various inorganic compounds which possess attractive physicochemical, electrophysical and optical properties – advanced materials for use in chemical power sources, fuel cells, supercapacitors, light emitting diodes, sensors etc – were elaborated; possibility of purposeful control of functional properties of such materials by structuring COP at nanoscale level was substantiated. In particular, a fundamentally new hybrid ternary host-guest nanocomposites based on layered transition metal oxides, where macromolecules of polymers with different types of conductivity - electronic and ionic - are simultaneously located in the interlayer space of the nanoparticles of the inorganic component were developed. It was found that mechanochemically prepared host-guest nanocomposites based on COP and transition metal oxides significantly exceed analogous core-shell nanocomposites in stability of charge-discharge cycling in lithium batteries due to pillaring layers of the oxide with macromolecules of the conducting polymer.
Ternary hybrid guest-host nanocomposites as cathode materials for lithium batteries
Nanocomposite electrocatalysts of oxygen reduction based on conducting polyaniline and polypyrrole were created, which are capable to operate stably in different electrolytes due to complex and mutual influence of catalytic activity of various components (conducting polymer, heteropolyacids, transition metal oxide, nanoscaled platinum or palladium, enzyme) that shows opportunities for their use in hydrogen-oxygen fuel and metal-air cells.
Scientific approaches were elaborated and new class of luminescent hybrid nanocomposites based on semiconducting conjugated polymers of polyphenylenevinylene type and mesoporous metal oxides (silica, titanium, etc.) were prepared, in which the control of interchain interaction in conjugated polymer is possible. The confinement effect of inorganic matrix enables purposeful regulation of photoluminescent properties of such materials.
A number of new materials based on COP for sensor systems were obtained; the mechanism of the interaction with them of various organic and inorganic analytes was studied; first multichannel arrays of miniature chemoresitive polymer sensors based on the system of raster electrodes with sensitive layers of COP that can separate polar and nonpolar/low-polarity organic solvents were created.
The effective mechanochemical methods of producing graphene, directly from graphite, and graphene oxide with varying degrees of oxidation in the absence of aggressive environments were worked out.
Atomic force micrographs of mechanochemically obtained graphene oxide (a) and graphene (b) particles
The department realizes joint researches with a number of scientific centers of Ukraine (Institute of Semiconductor Physics of the NAS of Ukraine, Institute of Physics of the NAS of Ukraine, Institute of Biochemistry of the NAS of Ukraine, Institute of Molecular Biology and Genetics of the NAS of Ukraine, Shevchenko Kyiv National University etc.)
The department maintains close exchange of scientific information, discussion of various scientific fields with scientists from Frumkin Institute of Physical Chemistry and Electrochemistry of the RAS, the Institute of Organic Chemistry of the RAS, the Institute of Chemical Physics of the RAS, the Institute of Problems of Chemical Physics of the RAS and several other institutes of the RAS and with several research institutions in Western countries: Spain (the Institute of Materials Science, Barcelona), France (d'Angers University, Anger), the Great Britain (the Institute of Bioscience and Technology, Cranfield University, Bedfordshire) and others.
Jointly with the electro-organic reactions laboratory of the Institute the department successfully conducted joint researches in the framework of PECO with leading research centers in France, Great Britain, Germany, Spain, Portugal, Italy, the Netherlands, Belgium, Hungary, Czech Republic and Russia in 1995-1997 (grant ERBCIPDCT940617 "Selective Processes and Catalysis including small molecules"); the project INTAS-Ukraine 95-0214 «Fundamentals of converting of atmospheric oxygen chemical energy into electrical energy using conducting polymers and other promising catalysts" - in 1997-2000 (with scientists from Germany, Switzerland, Austria, Russia and Ukraine), the project of The Scientific and Technology Center in Ukraine (STCU) (STCU grant 2045 "Creating power sources based on new conductive composite polymer materials and electrolytes") - in 2004-2007. In 2006-2007 the department had carried out the joint project of the NAS of Ukraine and CNRF (France) "Mechanochemistry of conducting polymers and hybrid nanocomposites," green" synthesis, physical-chemical properties, applications" (with d'Angers University researchers, Anger, France). In collaboration with the electric-organic reactions laboratory of the Institute together with scientists from France (Paris University XII), Portugal (University of Coimbra), Northern Ireland (Belfast Queens University), Italy (University of Milan, University of Venice) and other countries in 2003-2009, the coordinated basic research was conducted in the framework of the international project "Green Organic Electrochemistry" of European Program COST-29. From 2012 the department carries out researches within the joint project of the NAS of Ukraine and RFBR (Russia) "Physical-chemical basis for the creation of hybrid nano graphene and interpolymer complexes of conducting polymers of different functions "(in cooperation with the scientists from A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of the RAS).
On a commercial basis in 1996-1997, the department conducted research work on specific application of the conducting polymers on demand of Thomas De La Rue Limited (UK), and carried out research work jointly with the electro-organic reactions laboratory of the Institute on creation of new nanocomposite materials for lithium batteries on demand of General Motors Corporation (USA) in 2007, the results of which were the subject of the U.S. patent (O.Yu. Posudievsky, O.A. Kozarenko, V.S. Dyadyun, V.G. Koshechko, S.W. Jorgensen, V.D. Pokhodenko. Hybrid two- and three-component host-guest nanocomposites and method for manufacturing the same. US Patent No. 8,148,455 B2.).
Scientific staff of the department
Posudievsky Oleg Yuliyovych, Candidate of Science in Chemistry, Senior Research Scientist, tel. (44) 525-66-72, e-mail: email@example.com, firstname.lastname@example.org
Konoshchuk Natalia Volodymyrivna, Candidate of Science in Chemistry, Research Scientist, tel. (44) 525-67-51, e-mail: email@example.com
Kozarenko Olga Andriivna, Candidate of Science in Chemistry, Research Scientist, tel. (44) 525-75-77, e-mail: firstname.lastname@example.org
Hyzhny Vasil Opanasovych, Candidate of Science in Chemistry, Tel. (44) 525-75-77
List of selected publications
Нанокомпозиційні каталізатори на основі електропровідних полімерів для паливних елементів / Я.І. Курись, О.С. Додон, В.Г. Кошечко, В.Д. Походенко // Фундаментальні проблеми водневої енергетики / за ред. В.Д. Походенка, В.В. Скорохода, Ю.М. Солоніна. – Київ, “КІМ”. – 2010. – С. 385-408.
O.Yu. Posudievsky, O.A. Goncharuk, R. Barillé, V.D. Pokhodenko. Structure–property relationship in mechanochemically prepared polyaniline // Synth. Met. – 2010. – v.160. – №5-6. – Р.462–467.
O.Yu. Posudievsky, O.A. Goncharuk, V.D. Pokhodenko. Mechanochemical preparation of conducting polymers and oligomers // Synth. Met. – 2010. – v.160. – №1. – P.47–51.
O.Yu. Posudievsky, O.A. Kozarenko. Effect of monomer/oxidant mole ratio on polymerization mechanism, conductivity and spectral characteristics of mechanochemically prepared polypyrrole // Polym. Chem. – 2011. – Vol. 2, №1. – P. 216–220.
O.Yu. Posudievsky, N.V. Konoschuk, A.L. Kukla, A.S. Pavluchenko, Yu.M. Shirshov, V.D. Pokhodenko. Comparative analysis of sensor responses of thin conducting polymer films to organic solvent vapors // Sensors and Actuators B. – 2011. – Vol. 151, № 2. – P. 351–359.
Н.В. Конощук, В.Д. Походенко. Влияние гетерополикислот типа кеггина на перенос заряда в гибридных нанокомпозитах TiO2/органический сопряженный полимер (MEH-PPV) // Теорет. и эксперим. химия.- 2011.- Т. 47, №3.- С. 161-167.
O.Yu. Posudievsky, O.A. Kozarenko, V.S. Dyadyun, S.W. Jorgensen, J.A. Spearot, V.G. Koshechko, V.D. Pokhodenko. Characteristics of mechanochemically prepared host-guest hybrid nanocomposites of vanadium oxide and conducting polymers // J. Power Sources. – 2011. – Vol. 196, № 6. – P. 3331–3341.
O.Yu. Posudievsky, O.A. Kozarenko, V.S. Dyadyun, S.W. Jorgensen, J.A. Spearot, V.G. Koshechko, V.D. Pokhodenko. Effect of host–guest versus core–shell structure on electrochemical characteristics of vanadium oxide/polypyrrole nanocomposites // Electrochim. Acta. – 2011. – Vol. 58. – P. 442–448.
Я.И. Курысь, Е.С. Додон, Е.А. Уставицкая, В.Г. Кошечко, В.Д. Походенко. Электрокаталитические свойства нанокомпозитов на основе электропроводящих полимеров и диоксида титана в процессе восстановления кислорода // Электрохимия. – 2012.- Т. 38, № 11.
O.Yu. Posudievsky, O.A. Khazieieva, V.G. Koshechko, V.D. Pokhodenko. Preparation of graphene oxide by solvent-free mechanochemical oxidation of graphite // J. Mater. Chem. – 2012. – Vol. 22. – P. 12465.
O.Yu. Posudievsky, O.A. Kozarenko, V.S. Dyadyun, V.G. Koshechko, S.W. Jorgensen, V.D. Pokhodenko. Hybrid two- and three-component host-guest nanocomposites and method for manufacturing the same. US Patent No. 8,148,455 B2.
Scientific-Technical developments of the Department
Wide assortment of conducting metal-free organic polymers in powders, solutions and films with different functional application.
Nanostructured functional materials based on the organic conducting polymers and their composites for chemical power sources, ultracapacitors, optoelectronics, sensor and other applications.
New aprotic organic electrolytes for lithium chemical power sources with improved performance.