V M Martynenko

Publications (11)9.74 Total impact

• Article: The structure of fullerite C60 intercalated with molecular oxygen

  Yu. M. Shul’ga, V. M. Martynenko, E. M. Anokhin, A. V. Maksimychev, A. N. Trukhanenok, A. V. Mishchenko
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  ABSTRACT: A (O2) x C60 sample with a high content of oxygen (x ≥ 0.4) and free of technological solvent impurities was obtained by precipitation from solution. For the first time, the results of the determination of the x coefficients using 13C NMR and elemental analysis were compared. It was shown by Raman spectroscopy, mass spectrometry, and NMR that the inclusion of oxygen into fullerite was accompanied by a decrease in the frequency of O=O stretching vibrations by no less than 12 cm−1 compared with gaseous O2. Nevertheless, oxygen exists in the molecular form in (O2)0.4C60 and is released in the form of O2 as the sample is heated to 373 K. The number of oxygen molecules occupying octahedral pores closets to the fullerene molecule takes on all the possible values, from 0 to 6. At room temperature, the (O2) x C60 sample lost oxygen much more slowly than similar products prepared by diffusion saturation of pure fullerite with oxygen.
  Russian Journal of Physical Chemistry B 04/2012; 4(4):543-547. · 0.26 Impact Factor
• Article: Dimerization of defect fullerenes and the orientational phase transition in oxidized C60 fullerite.

  G L Gutsev, K G Belay, C A Weatherford, V N Vasilets, E M Anokhin, A V Maksimychev, O V Val'ba, V M Martynenko, S A Baskakov, E S Leskova, Y M Shulga
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  ABSTRACT: Oxidized fullerite was obtained by heating a fullerite sample intercalated with oxygen, (O2)0.44C60, up to 300 degrees C. Orientational phase transitions in the oxidized fullerite are studied using differential scanning calorimetry (DSC) and have been found to possess a specific enthalpy whose value is lower by 25% than in the initial (O2)0.44C60 sample. In order to find possible reasons for hindrance to the buckyball rotations, we performed optimizations of defect buckyball fullerenes C60-n with different distributions of vacancies along with the dimers C60-n-C60-n and C60-C60-n for n = 1-4 using density functional theory with generalized gradient approximation. We found that the dimerization energy ranges from 1.07 eV (C58-C58) to 6.56 eV (C56-C56) and from 1.81 eV (C60-C58) to 4.29 eV (C60-C56), respectively. The formation of such dimers, which could in addition interact with defect buckyball cages and form larger aggregates, is to be related to the lowering of the orientational transition enthalpy.
  Journal of Nanoscience and Nanotechnology 03/2011; 11(3):1887-96. · 1.56 Impact Factor
• Article: Dimerization of Defect Fullerenes and the Orientational Phase Transition in Oxidized C60 Fullerite

  G.L. Gutsev, K.G. Belay, C.A. Weatherford, V.N. Vasilets, E.M. Anokhin, A.V. Maksimychev, O.V. Val'ba, V.M. Martynenko, S.A. Baskakov, E.S. Leskova, Y.M. Shulga
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  ABSTRACT: Oxidized fullerite was obtained by heating a fullerite sample intercalated with oxygen, (O2)0.44C60, up to 300 °C. Orientational phase transitions in the oxidized fullerite are studied using differential scanning calorimetry (DSC) and have been found to possess a specific enthalpy whose value is lower by 25% than in the initial (O2)0.44C60 sample. In order to find possible reasons for hindrance to the buckyball rotations, we performed optimizations of defect buckyball fullerenes C60−n with different distributions of vacancies along with the dimers C60−n-C60−n and C60-C60−n for n = 1-4 using density functional theory with generalized gradient approximation. We found that the dimerization energy ranges from 1.07 eV (C58-C58) to 6.56 eV (C56-C56) and from 1.81 eV (C60-C58) to 4.29 eV (C60-C56), respectively. The formation of such dimers, which could in addition interact with defect buckyball cages and form larger aggregates, is to be related to the lowering of the orientational transition enthalpy.
  Journal of Nanoscience and Nanotechnology 02/2011; 11(3):1887-1896. · 1.56 Impact Factor
• Article: Oxidation of C60 Fullerite by Interstitial Oxygen

  Y. M. Shulga, V. M. Martynenko, V. V. Open’ko, A. V. Kulikov, A. Michtchenko, E. Johnson, M. D. Mochena, G. L. Gutsev
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  ABSTRACT: Processes induced by the heating of C60 fullerite intercalated by oxygen are analyzed using mass-spectrometry, thermogravimetry, differential scanning calorimetry, and electronic spin resonance (ESR) techniques. It was found that the primary gas produced at the heating temperatures below 100 °C is molecular oxygen while at higher temperatures up to 200 °C carbon mono- and dioxides were also observed. The heating was accompanied by an appreciable increase in the ESR signal intensity. In order to gain insight into the oxidation products that are capable to contribute to the ESR signal, we performed all-electron density functional theory computations for C58On (n = 0−4), C59On (n = 0−2), and endohedral complexes O2@C58, O2@C59, and O2@C60. It is found that the triplet states of C58, C58O3, O2@C58O2, O2@C58, and O2@C60 are lower in total energy than the corresponding triplet states. The singlet and triplet states of C59, O2@C59, and C602− are nearly degenerate in total energy. Thus, there are a number of species that can be responsible for the paramagnetic behavior observed in the oxidized fullerene.
  07/2008;
• Article: Fullerite with intercalated freon Ch2F2

  Yu. M. Shul’ga, V. M. Martynenko, S. A. Baskakov, G. V. Shilov, E. E. Khorkin, T. N. Fursova, A. V. Bazhenov, A. F. Shestakov, Yu. G. Morozov
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  ABSTRACT: Fullerite C60 with intercalated CH2F2 (Freon-32) was prepared for the first time. The sample was studied by elemental analysis, X-ray powder diffraction, mass spectrometry, and IR spectroscopy. The composition of the sample was found to be (CH2F2)C60. The sample had a face-centered cubic lattice with the lattice parameter (1.4284 nm) much larger than that of pure fullerite (1.416 nm). The gas released from the sample during heating in a vacuum to 450°C largely consisted of initial Freon (mass spectrometry data); no Freon destruction products were observed at this temperature. The C-F stretching vibration frequency (1058 cm−1) was shifted in (CH2F2)C60 by 30 cm−1 toward lower wave numbers compared with the gas phase. The absorption bands at 1182 and 1428 cm−1 (IR active modes (F 1u ) of high-symmetry (I h ) C60 molecules) did not change their positions in the intercalate.
  Russian Journal of Physical Chemistry 06/2008; 82(7):1159-1163. · 0.46 Impact Factor
• Chapter: GAS INTERSTITIAL FULLERENES PRECIPITATED FROM THE SOLUTION OF C60 IN 1,2-DICHLOROBENZENE

  Y.M. SHULGA, S.A. BASKAKOV, V.M. MARTYNENKO, Y.G. MOROZOV, V.N. VASILETS, V.F. RAZUMOV, D.V. SCHUR, A. MICHTCHENKO
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  ABSTRACT: Gas interstitial fullerenes was produced by precipitation of C60 from the solution in 1,2 dichlorobenzene saturated by O2, N2, or Ar. The structure and chemical composition of the fullerenes was characterized by X-ray powder diffraction analysis, FTIR spectroscopy, thermal desorption mass spectrometry, differential scanning calorimetric and chemical analysis.
  05/2007: pages 41-52;
• Article: Doping of fullerite with molecular oxygen at low temperature and pressure

  Yu. M. Shul’ga, V. M. Martynenko, A. F. Shestakov, S. A. Baskakov, S. V. Kulikov, V. N. Vasilets, T. L. Makarova, Yu. G. Morozov
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  ABSTRACT: Two methods are described for doping of fullerite C60 with molecular oxygen at a pressure of ∼104 Pa and at temperature 20–30 °C. It was found by mass spectrometry using oxygen 18O as dopant that a portion of molecular oxygen absorbed by the pre-decontaminated fullerite (first method) is removed as CO and CO2 at the heating temperature ≤200 °C. Doping during fullerite precipitation from the liquid phase (second method) makes it possible to prepare samples with the oxygen content ≥1.2 at.%. The fullerite doped with oxygen to this level is diamagnetic. The paramagnetic properties of an O2 molecule disappear when O2 is incorporated into the fullerene lattice. This is interpreted on the basis of quantum chemical calculations as a sequence of equilibrium formation of the adduct C60O2. Calculations showed that the subsequent chemical transformation of C60O2 resulting in the O-O bond cleavage is energetically favorable, enabling prerequisites for the formation of products of incomplete (CO) and deep (CO2) oxidation of fullerene under mild conditions.
  Russian Chemical Bulletin 03/2006; 55(4):687-696. · 0.38 Impact Factor
• Article: Effect of ultrasound treatment of C60 solutions on the crystalline structure of precipitated fullerite

  Yu. M. Shul’ga, S. A. Baskakov, V. M. Martynenko, V. I. Petinov, V. F. Razumov, D. V. Shchur
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  ABSTRACT: The structure of fullerite precipitated from solutions of C60 in toluene, chlorobenzene, and 1,2-dichlorobenzene by adding isopropanol was studied. It was demonstrated that, irrespective of the nature of the solvent, the parameter of the fcc lattice of precipitated fullerite decreases markedly when the process occurs in the presence of a ultrasound field. No effect of ultrasound sonication on the size of the precipitated crystallites was observed.
  Russian Journal of Physical Chemistry 03/2006; 80(4):654-658. · 0.46 Impact Factor
• Article: Thermal decomposition of deuterofullerite

  Yu. M. Shul"ga, V. M. Martynenko, B. P. Tarasov, V. N. Fokin, N. V. Chapysheva
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  ABSTRACT: The volative products of thermal decomposition of deuterofullerite C60D19 were studied by mass spectrometry. It was found that D2, CD4, and C6D6 molecules are present in the gas phase above deuterofullerite heated to 773 K. Deuterocarbons appear in the gas phase already at 673 K.
  Russian Chemical Bulletin 12/2001; 51(1):96-98. · 0.38 Impact Factor
• Article: Gaseous products of thermo- and photo-reduction of graphite oxide

  Y.M. Shulga, V.M. Martynenko, V.E. Muradyan, S.A. Baskakov, V.A. Smirnov, G.L. Gutsev
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  ABSTRACT: The composition of gases over a graphite oxide is found to depend on the temperature with CO2 being the main component with a range of 23–460 °C. In the temperature range of 150–230 °C, where the most intense yield of gases was observed, CO forms in small amounts. CH4 and CH2O were produced at temperatures below 230 °C, O2 was observed at 150–300 °C, while the complex H2OH·COOH was produced at temperatures above 150 °C. When films composed of graphite oxide nano-sheets were exposed to UV radiation, CO2, CO, H2O, and O2 were produced.Graphical abstractView high quality image (231K)Research highlights► Gaseous products of graphite oxide reduction formed in the course of the heating or under UV irradiation contain CO2, CO, H2O, and O2. ► Besides CO2, H2O, and CO, small concentrations of methane and formaldehyde were present at temperatures up to 230 °С. ► The complex H2OH·COOH was produced at temperatures above 150 °С. ► The relative amount of molecular oxygen yielded during the UV irradiation exceeds substantially the relative amount of O2 formed during the heating of graphite oxide.
  Chemical Physics Letters 498:287-291. · 2.34 Impact Factor
• Article: Synthesis and properties of C60 fullerite intercalated by acetylene

  Y.M. Shulga, V.M. Martynenko, S.A. Baskakov, A.N. Trukhanenok, E.M. Anokhin, A.V. Maksimychev, S.S. Khasanov, K.G. Belay, C.A. Weatherford, G.L. Gutsev
  Chemical Physics Letters 483:115-119. · 2.34 Impact Factor