Laboratory of technetium chemistry | A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences

Laboratory of technetium chemistry

Konstantin German

. Head of laboratory: Ph.D., Prof. of Sci.-edu. center professor GERMAN Konstantin Eduardovich

Phone: +7(495) 335-20-04
E-mail: guerman_k@mail.ru

People

PeretrukhinVF

. Principle scientific advisor Ph.D., Prof. PERETRUKHIN Vladimir Fedorovich

Phone: +7 495 333 85 22
E-mail: vperet@ipc.rssi.ru

SafonovAV

. Senior scientist Head of biotechnology and radioecology group Ph.D. SAFONOV Aleksey Vladimirovich

Phone: +7 495 335 20 04
E-mail: alexeysafonof@gmail.com

KopytinAV

. Leading scientific advisor Head of sensor materials group Ph.D. KOPYTIN Alexander Viktorovich

Phone: +7(495) 335-20-04
E-mail: ionix@igic.ras.ru

AfanasievAV

. Leading scientific advisor Nuclear technology and education Group Ph.D., Dc. AFANASIEV Andrey Viktorovich

Phone: +7(495) 335-20-04
E-mail: guerman_k@mail.ru

MarukAYa

. Jr. scientific advisor Technetium chemistry group Ph.D. MARUK Alesya Yakovlevna

Engineer – group of biotechnology and radioecology ALDABAEV Roman Alexandrovich

Phone: +7 495 335 20 04

. Jr. sci. advisor Technetium chemistry group Ph.D. KIRAKOSYAN Gayana Artavazdovna

. Jr. sci. advisor Technetium chemistry group Ph.D. TSEBRIKOVA Galina Sergeevna

Scientific research


Scientific directions of laboratory research

  • Fundamental and applied chemistry of technetium. Chemistry of technetium in nitrate solutions and the synthesis of new nitrogen-containing technetium complexes.
  • Synthesis of new compounds of technetium and rhenium for use in nuclear medicine.
  • Radiochemistry and electrochemistry of fission product elements Tc, Ru, Mo, etc. and actinides (Th-Cf), their behavior during irradiated fuel reprocessing, in radioactive wastes and in the environment.
  • Various types of matrices for Technetium long-term storage / disposal. Development of new promising materials for long-term immobilization of technetium.
    Reactor transmutation of technetium, target selection and process parameters.
  • Radioecology. Study of biogeochemical parameters of technetium and actinides migration in underground aquifers and surface water bodies with different salt content.
  • Fundamental aspects of radionuclide interaction with microorganism cells and the products of their metabolism, a biogenic effect onto sorption parameters in the geological environment.
  • Applied ecobiotechnology. Development of methods for bioremediation of contaminated underground aquifers (pertechnetate, uranyl, nitrate, chromate ions, heavy metals) using microbiological redox biobarrier technologies.

Laboratory assisted in the production of the scientific film Aggressive media – Acids – by Alexandra Govorchenko at the RT-2 and Nauka-2.0: https://www.youtube.com/watch?v=PCaHPTK7ukg

Scientific results

The main scientific results of laboratory research

FUNDAMENTAL CHEMISTRY AND TECHNOLOGY. During the years of the laboratory’s work, its staff developed synthesis techniques and obtained more than two hundred new compounds of technetium and rhenium. New classes of technetium compounds have been obtained, such as peroxides, polynuclear cluster halides, and others.

TRANSMUTATION TECHNOLOGY. Technetium, which is a radioactive waste, produces stable ruthenium upon neutron irradiation. This process, called transmutation of technetium, is in the stage of pilot-industrial development in different countries, including in Russia. When obtaining materials for the transmutation of technetium, it was necessary to develop and apply methods and materials that meet the requirements of high levels of recovery of Tc from waste and large coefficients of its purification from radioactive and stable impurities. At the same time, the inorganic materials used were to meet the tasks of minimizing radioactive waste and enhancing the radiochemical and fire-and-explosion safety of technological processes. The main materials for the preparation of transmutational targets are metallic technetium and its carbide, they are obtained by high-temperature technology, which is associated with the formation of a number of volatile / gaseous products. To obtain transmutational targets, a promising group of starting materials are new technetium compounds with tetraalkylammonium cations, and for extraction purification Tc-c with crown ethers and organophosphorus tripotanides. They make it possible to obtain a high yield and purity of the product, and minimize the irreversible loss of technetium, especially when combined synthetic methods with extractive methods of extraction and purification of the radioactive element – technetium. In this connection, the choice of this group of compounds – the tetraalkylammonium series and complexes with crown ethers and tripodands for conversion into metal and carbide – seems to be the most promising. In view of the absence of stable isotopes in Tc, the modeling of basic processes on a stable analog of technetium – rhenium is a common stage, therefore, in developing directional methods for the synthesis of new materials, along with the preparation of technetium compounds, preliminary methods for obtaining compounds and materials on rhenium compounds have been carried out. The available experience in the development of methods for the synthesis of new technetium compounds, the separation of technetium from radioactive waste, and the development of methods for obtaining targets for transmutation is reflected in the publications of the laboratory.

The laboratory has developed methods for the synthesis of new technetium compounds with long-chain cations of the tetraalkylammonium series, complexes with crown ethers and tripodands, to study their structure and properties, and on their basis to improve the methods of purification of technetium when it is separated from radioactive waste, and to increase efficiency and safety methods of obtaining targets for transmutation. Synthetic methods have been developed and new compounds of technetium and rhenium with tetraalkylammonium series cations have been obtained, their structure and properties have been studied. The kinetics and mechanism of Tc extraction from LMW by crown ethers and tripodands and the mechanism of precipitation of Tc compounds with TAA for improving methods for purifying preparations and materials containing technetium-99 isotope were studied using extraction methods. The kinetics and mechanism of conversion of technetium compounds to metal and carbide have been studied to improve the efficiency and safety of methods for obtaining targets for transmutation.

The salts of tetrapentyl-, tetrahexyl- and tetraheptyl-ammonium have been studied, the use of which, as precipitators, leads to the formation of easily combustible waste. (CnH2n+1)4NMeO4 (n = 5, 6, 7; Me = Tc, Re)  were obtained by the method of [4-6]. We determined the solubility, structural and thermal characteristics, and the thermal decomposition mechanism for (CnH2n+1)4NMeO4 (n = 5 – 7;  Me = Tc, Re) and some analogues.

Methods have been developed for the production of new metallocarbon materials based on the recently obtained new technetium and rhenium compounds with organic cations of various groups, promising from the viewpoint of obtaining technetium in the form of metal or carbide, and their thermal properties have been studied. New starting compounds and compositions have been proposed and methods have been developed for introducing higher concentrations of active carbon into the thermolysis phases, producing carbide phases of technetium and rhenium, and also new phases of metallic Tc with low carbon content, which are characterized by improved physical characteristics that simplify the preparation of transmutation targets.

Nanophases of rhenium metal and technetium can be formed by thermal decomposition of perrhenates and pertechnetates of organic cations in argon, while concurrent carbonization of cations provides conditions suitable for the formation of Re and Tc nano and micro-states. For hexamethyleneimine- and triphenylguanidinium pertechnetates, conversion occurs with the formation of Tc6C. Thermal decomposition of triphenylguanidinium perrhenate produces mixture of metallic rhenium, rhenium carbide and free carbon. The nanocrystalline phases are X-ray amorphous, and structural data can only be obtained using the EXAFS method. The microcrystalline phase of Tc6C has a cubic lattice with a = 3.98 Å. For the rhenium sample calcined at 1200 ° C, the parameter a = 5.095 Å and so on is set. Pm3m mean that the new Re carbide carbide phase is isostructural with a series of carbides of REE.

A nanodispersed powder of metallic technetium Tc-99, proposed by us earlier as a transmutation material, was studied by the non-destructive NMR method. providing a high separation factor Tc-Ru, and the parameters of this powder: K = 6872 ppm, Kan = –400 ppm, (T1 ´ T)–1 = 3,23 с–1 K–1 , CQ = 5,74 MHz, and h = 0. The absence of a quadrupole structure clearly indicates formation of a cubic lattice in the phase of nanodispersed metallic technetium, and a significant increase in the Knight shift in an nanodisperse sample may reflect a change in the density of states at the Fermi level in comparison with a microdispersed sample of metallic technetium with a hcp lattice. NMR also revealed that the corrosion of nanodispersed metallic technetium in air proceeds much faster than the corrosion of microdispersed samples and foils of metallic technetium under the same conditions.

Based on the study of the properties of compounds, methods for separating technetium from technological solutions of the nuclear industry have been developed. Together with Mayak, a technology has been developed for converting technetium into metallic and other materials of transmutational problems, and together with NIIAR, a full cycle of detoxification of technetium by its reactor transmutation into stable ruthenium in gram quantities has been realized.

RADIOECOLOGY. The laboratory demonstrated for the first time the possibilities of purification of lake water from radionuclides of cesium, technetium and actinides due to microbiological absorption by bottom sediments on the example of lakes in the Moscow and Tver regions. [German, Firsova, Peretrukhin, Khizhnyak, Simonoff. Bioaccumulation of Tc, Pu, and Np on Bottom Sediments in Two Types of Freshwater Lakes of the Moscow Oblast - Radiochemistry, Vol. 45, No. 3, 2003, pp. 250 256].

International scientific

International scientific and scientific-organizational activity of the laboratory

The laboratory has historically concentrated scientific personnel who have extensive experience in international scientific cooperation. Laboratory of KE German and prof. V.F. Peretrukhin previously participated in the international PhD program for graduate students from Libya, the Long-Term Cooperative Program with the CNRS and the Commissariat for Nuclear Energy / CEA, France in 1995-2008, for a long term projects in such nuclear research centers like the Institute of Nuclear Physics Orsay, the Nuclear Center Marcool, ESRF Grenoble, Center for Nuclear Research Bordeaux Gradignan, Center for Nuclear Research Cadarache, University of Bordeaux and others. A.V. Kopytin has a long-term experience of cooperation with the Hungarian Academy of Sciences and the Budapest Technical University. Leading res.advisor A.V. Afanasiev had worked for 1 year at the University of Mexico.

In 1995-2010, series of research projects were carried out in the laboratory on the appointment with the US Department of Energy / Hanford and Savannah River centers.

In 2008 – 2014  intensive collaboration with Nevada Las-Vegas University the basic center for the preparation of radiochemists in the USA, has resulted in 6 jointly published scientific articles on the peak topycs of technetium chemistry.

In 2013-2015 Prof. K.E. German delivered a course of lectures at the Warsaw University (Poland) in the framework of the European School for Nuclear Energy and Medicine.

The laboratory also has the following assets:

 organizing and conducting the “7th International Symposium of Technetium and Renium – Science and Applications” (ISTR2011) 04 – 08 July 2011

 organization and holding of the 8th International Technetium and Renius Symposium – Science and Applications (ISTR2014) in 2014. In France

 assistance for the organization of the 9th International Technetium and Renius Symposium – Science and Applications (ISTR2017) in 2017. In Australia, in conjunction with ANSTO http://www.ansto.gov.au/Events/ISTR9/

 organizing and conducting of the “10th International Symposium of Technetium and Renium – Science and Applications” (ISTR2018) is planned for 01 – 05 October 2018

Publications

  • Wang, Qinggao, German, Konstantin E., Oganov, Artem R., Dong, Huafeng, Feya, Oleg D., Zubavichus, Ya. V., Murzin, V. Yu. Explaining stability of transition metal carbides – and why TcC does not exist \\ RSC ADVANCES,  Vol. 6 , 20, pp.: 16197-16202 :
  • Valerii P. Tarasov, Gayana А. Kirakosyan, Konstantin E. German.  99Tc NMR determination of the oxygen isotope content in 18O‐enriched water. Magn Reson Chem. 2017;1–7.  DOI: 10.1002/mrc.4680.
  • Konstantin E. German, Mikhail S. Grigoriev, Bogdan L. Garashchenko, Alexander V. Kopytina, Ekaterina A. Tyupina. Redetermination of the crystal structure of NaTcO4 at 100 and 296 K based on single-crystal X-ray data //Acta Cryst. (2017). E73, 1037–1040. doi:10.1107/S2056989017008362.  Q3.
  • Poineau, F.; Koury, D. J.; Bertoia, J.; Kolman, D. G. Mausolf, E. J.; Goff, G. S.; Kim, E.; Jarvinen, G.; German, K. E.; Сzerwinski, K. R., Electrochemical Studies of Technetium-Ruthenium Alloys in HNO3: Implications for the Behavior of Technetium Waste Forms. RADIOCHEMISTRY 2017, Vol. 59, No. 1, pp. 41-47.  DOI:10.1134/S1066362217010040, Q4.
  • K. V. Rotmanov, A. G. Maslennikov, L. V. Zakharova, Yu. D. Goncharenko, and V. F. Peretrukhin. Electrochemical Dissolution of Тс–Ru. Alloys in Nitric Acid Solutions . Radiochemistry, 2017, Vol. 59, No. 1, pp. 48-53.
  • А. Б. Мелентьев, А.Н. Машкин, К.Э. Герман.  Поведение технеция в процессах переработки ОЯТ на заводе РТ-1. \\ ВОПРОСЫ РАДИАЦИОННОЙ БЕЗОПАСНОСТИ.  № 1, 2017, стр.42-53. (РИНЦ). Q4.
  • Inga Zinicovscaia, Alexey Safonov, Tatiana Khijniak BIOSORPTION OF HEXAVALENT CHROMIUM AND URANIUM BY BACTERIA, MICROALGA, AND FUNGI chapter in book Heavy Metals and others Pollutants in Contaminated Environment Hard ISBN: 9781771884372 E-Book ISBN: 9781771884389. https://doi.org/10.1201/9781315366029-21
  • Isakova, A.A., Safonov, A.V., Alexandrovskaya, A.Y. et al. The effect of nanodiamond surface modification on interaction with Pseudomonas putida K12 //Prot Met Phys Chem Surf (2017) 53: p. 220. doi:10.1134/S2070205117020137 IF 0.707
  • German,K.E. ; Obruchnikova, Ya. A., Safonov, A. V.; Tregubova, V.E.; Afanas’ev, A.V., Kopytin, A. V.; Kryzhovets, O. S. ; Poineau, F. ; Abkhalimov, E. V.; Shiryaev, A. A. Kinetics of the formation of precipitates and the physicochemical properties of technetium-99 and rhenium sulfides according to small-angle X-ray scattering and ultramicrocentrifugation data \\ RUSSIAN JOURNAL OF INORGANIC CHEMISTRY,  Том: 61,  Выпуск: 11, стр.: 1445-1450 DOI: 10.1134/S0036023616110061,  Опубликовано: NOV 2016.   WOS:000388704300017
  • Melent’ev, A. B.; Mashkin, A. N., German, K. E. The influence of deviations in process parameters on the purification of uranium from different radionuclides, THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING, Том: 50 Выпуск: 4  Стр.: 554-561.  2016  WOS:000382998000028 ISSN: 0040-5795
  • Zaitsev, N. K. , Melnikov, P. V., Alferov, V. A. Kopytin, A. V., German, K. E. Stable optical oxygen sensing material based on perfluorinated polymer and fluorinated platinum(II) and palladium(II) porphyrins  eds.:Barsony, I; Zolnai, Z; Battistig, G // PROCEEDINGS OF THE 30TH ANNIVERSARY EUROSENSORS CONFERENCE – EUROSENSORS 2016, Серия книг: Procedia Engineering Том: 168  Стр.: 309-312  DOI: 10.1016/j.proeng.2016.11.203   Опубликовано: 2016 Конференция: 30th Eurosensors Conference Местоположение: Budapest, HUNGARY публ.: SEP 04-07, 2016  WOS:000391641300074.
  • Kopytin, A. V, German, K. E. Zhizhin, K. Yu., Zhukov, A. F ; Ilyin, E. G., Zhukova, T. V. Ion selective potentiometric sensor based on single crystalline KTiOPO4 for determination of K+-ions Eds:Barsony, I; Zolnai, Z; Battistig, G. PROCEEDINGS OF THE 30TH ANNIVERSARY EUROSENSORS CONFERENCE – EUROSENSORS 2016. Серия книг: Procedia Engineering. Том: 168 Стр.: 440-443 DOI: 10.1016/j.proeng.2016.11.539 Опубликовано: 2016 Конференция: 30th Eurosensors Conference. Местоположение: Budapest, HUNGARY. публ.: SEP 04-07, 2016: WOS:000391641300105
  • Tarasov, V. P.  Kirakosyan, G. A.  O16/O18 Oxygen Isotope Exchange Kinetics in MnO4- as Probed by Mn-55 NMR \ RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B, Том: 10 Выпуск: 4  Стр.: 582-586  DOI: 10.1134/S1990793116040278  Опубликовано: JUL 2016 WOS:000388140400006
  • Safonova, Evgeniya A, Martynov, Alexander G., Nefedov, Sergey E. Kirakosyan, Gayane A. , Gorbunova, Yulia G., Tsivadze, Asian Yu.A Molecular Chameleon: Reversible pH- and Cation-Induced Control of the Optical Properties of Phthalocyanine-Based Complexes in the Visible and Near-Infrared Spectral Ranges. INORGANIC CHEMISTRY Том: 55 Выпуск: 5 Стр.: 2450-2459 DOI: 10.1021/acs.inorgchem.5b02831  опубликовано: MAR 7 2016  Идентификационный номер: WOS:000371753500056
  • Nefedova, Irina V. ;  Martynov, Alexander G. Averin, Alexey A. Kirakosyan, Gayane A. , Tsivadze, Aslan Yu., Gorbunova, Yulia G. New Octopus-like Phthalocyanines as Fullerene Receptors: Synthesis and Photophysical Investigation  ISRAEL JOURNAL OF CHEMISTRY Том: 56  Выпуск: 2-3 Стр.: 181-187  Специальный выпуск: SI DOI: 10.1002/ijch.201500024 MAR 2016  WOS:000371987400009
  • Tregubova, V. E.; Ostalkevich, S. S. ; Safonov, A. V.; Gorbunova, O. A. ; Ershov, B. G Treatment of liquid radioactive waste using microorganisms. THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING \\ Том: 50 Выпуск: 4  Стр.: 562-567  DOI: 10.1134/S0040579516040308  Опубликовано: JUL 2016 / Идентификационный номер: WOS:000382998000029
  • Inga ZINICOVSCAIA, Alexey SAFONOV, Varvara TREGUBOVA, Victor ILIN, Liliana CEPOI, Tatiana CHIRIAC, Ludmila RUDI and Marina V. FRONTASYEVA UPTAKE OF METALS FROM SINGLE AND MULTI-COMPONENT SYSTEMS BY Spirulina platensis BIOMASS //ECOL CHEM ENG S. 2016;23(3) p.401-412 .  WOS:000386997400003        DOI: 10.1515/eces-2016-0028
  • Inga Zinicovscaia, Liudmila Rudi, Ana Valuta, Liliana Cepoi, Konstantin Vergel, Marina V. Frontasyeva, Alexey Safonov, Markus Wells, Dmitrii Grozdov. Biochemical Changes in Nostoc linckia Associated with Selenium Nanoparticles Biosynthesis //Ecological Chemistry and Engineering S. Volume 23, Issue 4, Pages 559–569, ISSN (Online) 1898-6196, , December 2016    WOS:00039281480000       DOI: 10.1515/eces-2016-0039
  • Tsebrikova, G. S.; Baulin, V. E.; Kalashnikova, I. P . Ragulin, V. V. Zavel’skii, V. O. ; Kodina, G. E., Tsivadze, A. Yu. NMR Study of 1,7-Diamino-4-oxyheptane-1,1,7,7-tetraphosphonic Acid Interaction with Samarium(III) Cation RUSSIAN JOURNAL OF GENERAL CHEMISTRY Том: 86 Выпуск: 3  Стр.: 639-644 DOI: 10.1134/S107036321603021X Опубликовано: MAR 2016  : WOS:000376040500021
  • Rakhimov, M. G.; Maruk, A. Ya. ; Bruskin, A. B Compounds for radionuclide imaging and therapy of malignant foci characterized by the increased angiogenesis. RUSSIAN CHEMICAL BULLETIN. V: 65  N: 2 pp: 363-383: FEB 2016: WOS:000387600700004
  • K.E. German, A.B. Melent’ev, Ya.V. Zubavichyus et all. Synthesis, Structure, and Properties of New Difficultly Soluble Complex Compounds of Technetium with Diethylenetriaminepentaacetic Acid – Radiochemistry, 2011, Vol. 53, No. 2, pp. 178–185.
  • F. Poineau, Ph F. Weck, K. E. German et all.   Reactivity of HTcO4 with methanol in sulfuric acid: Tc-sulfate complexes revealed by XAFS spectroscopy and first principles calculations. // Dalton Trans., 2013, 42, pp. 4348 – 4352.
  • F. Poineau, Alesya Maruk, G. Kirakosyan, K. E. German, et all. On the Nature of Heptavalent Technetium in Concentrated Nitric and Perchloric Acid. Inorganica Chimica ActaVolume 398, 24 March 2013, Pages 147–150.
  • A.Ya. Maruk, M.S. Grigor’ev, K.E. German. Lithium Pertechnetate Trihydrate LiTcO4 · 3H2O: Synthesis and Crystal Structure. Russian Journal of Coordination Chemistry, 2011, Vol. 37, No. 6, pp. 444–446.
  • 7-th International Symposium on Technetium and Rhenium – Science and Utilization – Proceedings – July 4 -8, 2011, Moscow, Russia. Eds.:  K.E. German, B.F. Myasoedov, G.E. Kodina, I. D. Troshkina, T. Sekine. Publishing House GRANITZA, Moscow 2011, 204 p.
  • A.Maruk, M. Grigoriev, K. German. Synthesis, crystal structure, and properties of triphenylguanidinium perrhenate hemihydrate. doi:10.1134/S1070328413040076
  • G. V. Kolesnikov, K. E. German, G. Kirakosyan et all. Macrocyclic receptor for pertechnetate and perrhenate anions. RSC – Organic and Biomolecular Chemistry, 2011, No. 9, pp.7358-7364, DOI: 10.1039/C1OB05873H.
  • С.15.12С  РАЗРАБОТКА КОНЦЕПЦИИ БИОЛОГИЧЕСКОГО БАРЬЕРА ДЛЯ МИГРАЦИИ ТЕХНЕЦИЯ ИЗ ХРАНИЛИЩ ЖИДКИХ РАО Сафонов А.В., Трегубова В.Е., Абдуллин Р.Р. , Герман К.Э.,  Ильин В.А.  VII Московский международный конгресс  «Биотехнология: состояние и перспективы развития» и XI международная специализированная выставка «МИР БИОТЕХНОЛОГИИ’ 2013»  19-22 марта 2013 г. Москва, Новый Арбат, 36/9 (Здание Правительства Москвы)
  • T. N. Nazina, A. V. Safonov, I. M. Kosareva, B. G. Ershov. et all. Microbiological Processes in the Severnyi Deep Disposal Site for Liquid Radioactive Wastes Microbiology, 2010, Vol. 79, No. 4, pp. 528–537. DOI: 10.1134/S0026261710040156

Collaboration


In 2013-2016, 4 dissertations on the degree of Ph.D. in Chemistry were defended in the laboratory by N.G. Kravchenko, Ya.A. Obrucnikova A.Ya. Maruk and V. Tregubova.

In 2013-2017, 27 Master research works were completed and defended by students of the Russian Chemical Technical University. D. I. Mendeleyev, Moscow State University M.V. Lomonosov and others.

Head of the Laboratory Konstantin GERMAN is a member of the State Attestation Commission at the M.V. Lomonosov Moscow State University at the Department of Radiochemistry and the Department of Physical Chemistry of the Faculty of Chemistry and also the Professor at the Scientific and Educational Center – Russian Academy of Sciences giving the courses to 17 Ph.D. IPCE students.

 
 
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