alternativeАльтернативная энергетика и экология (ISJAEE)Alternative Energy and Ecology (ISJAEE)1608-8298Международный издательский дом научной периодики "Спейс10.15518/isjaee.2017.22-24.047-062alternative-1196Research ArticleВОДОРОДНАЯ ЭКОНОМИКАHYDROGEN ECONOMYЭКСПЕРИМЕНТАЛЬНАЯ ОЦЕНКА ПОЛНОЙ ВОДОРОДОЕМКОСТИ ФУЛЛЕРИТА C60EXPERIMENTAL EVALUATION OF TOTAL HYDROGEN CAPACITY FOR FULLERITE C60ЩурД. В.SchurD. V.

канд. хим. наук, зав. отделом № 67 «Водородного материаловедения и углеродных наноструктур»

Ph.D. (chemistry), Professor, Chief of Laboratory no. 67 “Investigation of Processes and Systems of Hydrogen and Solar-Hydrogen Energy Transformation” in Institute for Problems of Materials Science of NAS of Ukraine, Kiev

shurzag@ipms.kiev.uaЗагинайченкоС. Ю.ZaginaichenkoS. Yu.

д-р физ.-мат. наук, вед. научн. сотрудник отдела № 67

D.Sc. (physics and mathematics), Professor, Senior Researcher at Laboratory no. 67 “Investigation of Processes and Systems of Hydrogen and Solar-Hydrogen Energy Transformation” in Institute for Problems of Materials Science of NAS of Ukraine, Kiev

shurzag@ipms.kiev.uaСавенкоА. Ф.SavenkoA. F.shurzag@ipms.kiev.uaБоголеповВ. А.BogolepovV. A.shurzag@ipms.kiev.uaАникинаН. С.AnikinaN S.shurzag@ipms.kiev.uaЗолотаренкоА. Д.ZolotarenkoA. D.shurzag@ipms.kiev.uaМатысинаЗ. А.MatysinaZ. A.

д-р физ.-мат. наук, вед. научн. сотрудник отдела № 67 Института проблем материаловедения НАН Украины; профессор Днепропетровского национального университета имени Олеся Гончара; заслуженный профессор Днепропетровского национального университета

D.Sc. (physics and mathematics), Professor, Senior Researcher at Laboratory no. 67 “Investigation of Processes and Systems of Hydrogen and Solar-Hydrogen Energy Transformation” in Institute for Problems of Materials Science of NAS of Ukraine, Kiev; Professor at Oles Honchar Dnepropetrovsk National University; Honored Professor of Dnepropetrovsk National University

shurzag@ipms.kiev.uaВезироглуТ. Н.VezirogluT. N.

д-р наук (теплообмен), профессор, президент Международной ассоциации водородной энергетики

Ph.D. in Heat Transfer, Professor, President of International Association for Hydrogen Energy

shurzag@ipms.kiev.uaСкрябинаН. Е.SkryabinaN. E.shurzag@ipms.kiev.uaИнститут проблем материаловедения им И.Н. Францевича НАН УкраиныУкраинаInstitute for Problems of Materials Science of NAS of UkraineUkraineДнепропетровский национальный университетУкраинаDnepropetrovsk National UniversityUkraineМеждународная ассоциация водородной энергетикиСоединённые Штаты АмерикиInternational Association for Hydrogen EnergyUnited StatesПермский государственный университетРоссияPerm State UniversityRussian Federation201703012018022-244762Copyright © Международный издательский дом научной периодики "Спейс, 20182018Международный издательский дом научной периодики "СпейсМеждународный издательский дом научной периодики "Спейсhttps://www.isjaee.com/jour/about/submissions#copyrightNoticehttps://www.isjaee.com/jour/article/view/1196

Фуллерен является четвертой аллотропной формой углерода. Такие его свойства, как объемная, весовая и электрохимическая емкости превосходят многие аналогичные свойства металлогидридов и углеводородов. Решение вопроса реверсивного гидрирования каждого атома углерода в каркасе фуллереновой молекулы позволит создать хранилище водорода с емкостью до 7,7 мас.% H. В настоящей работе оценена полная водородоемкость фуллерита С60. Экспериментально получены гидрофуллерены с различным содержанием водорода. Определен оптимальный режим гидрирования С60, приводящий к полному гидрированию фуллереновой молекулы С60. Образование гидрированной фуллереновой молекулы С60Н60 имеет следующую последовательность: растворение молекулярного водорода в окта- порах ГЦК-решетки фуллерита, диссоциация молекул при переходе водорода в тетрапустоты, взаимодействие атома водорода с молекулой фуллерена. Продемонстрировано, что процесс хемосорбции водорода молекулой С60 после концентрации водорода, отвечающей С60Н36, лимитируется диффузионными процессами в фуллерите. Анализ показал, что процесс второй стадии хемосорбции подчиняется модели сжимающейся оболочки. Предложена модель взаимодействия H2 c фуллеритом C60, а также механизм определения степени гидрирования молекулы С60.

 

The fullerene is the fourth allotropic modification of carbon and its properties, as volume, gravimetric and electrochemical capacities, are in excess of many similar properties of metal hydrides and hydrocarbons. The solution of the problem of the reversible hydrogenation of each carbon atom in the frame of fullerene molecule will allow to create the hydrogen storage with the capacity up to 7.7 wt.% H. A series of experiments have been conducted to evaluate the full hydrogenation of fullerite C60; hydrofullerenes have been produced experimentally with the variable content of hydrogen. The optimum regime of C60 hydrogenation has been determined resulting in the full hydrogenation of fullerene molecule C60. As was apparent after the tests, the sequence of formation of hydrogenated fullerene molecule C60H60 in fullerite has been going in the following order: the molecular hydrogen dissolution in octahedral interstices of fcc lattice of fullerite, the dissociation of hydrogen molecules in going from octa- to tetrahedral interstices, the interaction of hydrogen atoms with fullerene molecule. It has been demonstrated that chemisorption process of hydrogen by molecule C60 is limited by diffusive processes in fullerite after hydrogen concentration conformed to C60H36. The spectral analysis has shown that the second stage process of chemisorption follows the compressive shell model. The suggestion of the model of processes going on at the interaction between H2 and fullerite C60 has been made. The mechanism for the definition of hydrogenation degree of molecule C60 has been proposed in the present paper.

 

фуллерен С60водородфуллеритпоглощениехемосорбцияводородfullerene C60hydrogenfulleriteabsorptionchemisorptionhydrogen capacityReferencesSchur, D.V. Hydrogen in fullerites [Text] / D.V. Schur [et al.] // Carbon. – 2003. – Vol. 41. – P. 331– 1342.[1] Schur D.V., Tarasov B.P., Shul’ga Y.M., Zaginaichenko S.Yu., Matysina Z.A., Pomytkin A.P. Hydrogen in fullerites. Carbon, 2003;41:1331–1342.Jin, C. Direct solid-phase hydrogenation of fuller-enes [Text] / C. Jin [et al.] // J. Phys. Chem. – 1994. – Vol. 98. – No 16. – P. 4215–4217.[2] Jin C., Hettich R., Compton R., Joyce D., Blencoe J., Burch T. Direct solid-phase hydrogenation of fuller-enes. J. Phys. Chem., 1994;98(16):4215–4217.Lobach, A.S. The D2 reaction with palladium fulleride C60Pd4,9 [Text] / A.S. Lobach [et al.] // Izv. RAN., Ser. khim. – 1996. – P. 483–484.[3] Lobach A.S., Tarasov B.P., Shul'ga Yu.M., Perov A.A., Stepanov A.N. The D2 reaction with palladium fulleride C60Pd4,9. Izv. RAN., Ser. khim. 1996:483–484.Shigematsu, K. Catalytic hydrogenation of fuller-ene C60 [Text] / K. Shigematsu [et al.] // Chem. Express. – 1992. – Vol. 7. – No 12. – P. 37–40.[4] Shigematsu K., Abe K., Mitani M., Tanaka K. Catalytic hydrogenation of fullerene C60. Chem. Express., 1992; 7(12):37–40.Attalla, M.I. Preparation of hydrofullerenes by hydrogen radical induced hydrogenation [Text] / M.I. Attalla [et al.] // J. Phys. Chem. – 1993. – Vol. 97. – P. 6329–6331.[5] Attalla M.I., Vassallo A.M., Tattam B.N., Hanna J.V. Preparation of hydrofullerenes by hydrogen radical induced hydrogenation. J. Phys. Chem., 1993;97:6329–6331.Haufler, L.E. Reduction with tithium in ammonia in the presence of t-BuOH [Text] / L.E. Haufler [et al.] // J. Phys. Chem. – 1990. – Vol. 94. No 24. – P. 8634– 8636.[6] Haufler L.E. Conceicao J., Chibante L.P.F., Chai Y., Byrne N.E. Flanagan S. et. al. Reduction with tithium in ammonia in the presence of t-BuOH. J. Phys. Chem., 1990;94(24):8634–8636.Henderson, C.C. Synthesis of the simplest С60 hydrocarbon derivative [Text] / C.C. Henderson, P.A. Cahill // Science. – 1993. – Vol. 259. – P. 1885–1887.[7] Henderson C.C., Cahill P.A. Synthesis of the simplest С60 hydrocarbon derivative. Science, 1993;259:1885–1887.Bashkin, I.O. Hydrogen in the vibrational spectra of high-pressure hydrofullerite [Text] / I.O. Bashkin [et al.] // Molecular Materials. – 2000. – Vol. 13. – No 1–4. – P. 251–256.[8] Bashkin I.O., Antonov V.E., Kolesnikov A.I., Ponyatovsky E.G., Mayers J., Parker S.F., Tomkinson J., Moravsky A.P., Shul'ga Yu.M. Hydrogen in the vibrational spectra of high-pressure hydrofullerite. Molecular Materials 2000;13(1–4):251–256.Gerst, M. Benzanthrone, a catalyst for the transfer hydrogenation of C60 and C70 by 9, 10-dihydroanthracene. [Text] / M. Gerst [et al.] // Tetrahedron Lett. – 1993. – Vol. 34. – P. 7729–7732.[9] Gerst M., Beckhaus H.-D., Ruchardt C., Campbell E.E.B., Tellgmann R. Benzanthrone, a catalyst for the transfer hydrogenation of C60 and C70 by 9, 10-dihydroanthracene. Tetrahedron Lett., 1993; 34:7729–7732.Darwish, A.D.M. [Text] / A.D.M. Darwish, R. Taylor, R. Loutfy // In: Proc. of 197th Meeting of Electrochemical Society, Toronto, 2000. – Abstract. – No 693.[10] Darwish A.D.M., Taylor R., Loutfy R. In: Proc. of 197th Meeting of Electrochemical Society, Toronto, 2000, Abstract, No 693.Nozu R., Matsumoto O. Electrochemical hydrogenation of fullerenes in a 30 % KOH solution / R. Nozu, O. Matsumoto // J. Electrochem. Soc. – 1996. – Vol. 143. – No 6. – P. 1919–1923.[11] Nozu R., Matsumoto O. Electrochemical hydrogenation of fullerenes in a 30 % KOH solution. J. Electrochem. Soc., 1996;143(6):1919–1923.Тарасов, Б.П. Гидрирование фуллерита в присутствии гидридов металлов [Текст] / Б.П. Тарасов [и др.] // Изв. РАН. Сер. хим. – 1997. – № 4. – С. 679–683.[12] Tarasov B.P., Fokin V.N., Moravsky A.P., Shul'ga Yu.M. Hydrogenation of fullerite in the presence of intermetallic compounds (Gidrirovanie fullerita v prisutstvii gidridov metallov). Izv. RAN., Ser. khim., 1997;4:679–683 (in Russ.).Tarasov, B.P. Hydrogenation of fullerenes C-60 and C-70 in the presence of hydride-forming metals and intermetallic compounds [Text] / B.P. Tarasov [et al.] // J. Alloys and Comp. – 1997. – Vol. 25. – P. 253–254.[13] Tarasov B.P., Fokin V.N., Moravsky A.P., Shul’ga Yu.M., Yartys’ V.A. Hydrogenation of fuller-enes C-60 and C-70 in the presence of hydride-forming metals and intermetallic compounds. J. Alloys and Comp., 1997;25:253–254.Тарасов, Б.П. Механизм гидрирования фуллерит металлических композиций [Текст] / Б.П. Тарасов // Журнал общей химии. – 1998. – Т. 68. – № 8. – С. 1245–1248.[14] Tarasov B.P. Mechanism of hydrogenation of fullerite-metallic compositions (Mekhanizm gidrirovaniya fullerit metallicheskikh kompozitsii). Zhurn obshchei khimii, 1998;68:1245–1248 (in Russ.).Tarasov B.P., Promotion of fullerene hydride synthesis by intermetallic compounds [Text] / B.P. Tarasov [et al.] // Proc. of 12th World Hydrogen Energy Conference, Buenos Aires, Argentina. – 1998. – Vol. 2. – P. 1221–1230.[15] Tarasov B.P., Fokin V.N., Moravsky A.P., Shul’ga Yu.M., Yartys’ V.A., Schur D.V. Promotion of fullerene hydride synthesis by intermetallic compounds. Proc. of 12th World Hydrogen Energy Conference, Bue-nos Aires, Argentina, 1998;2:1221–1230.Гольдшлегер, Н.Ф. Взаимодействие фуллерида платины C60Pt с дейтерием [Текст] / Н.Ф. Гольдшлегер [и др.] // Изв. А.Н. Сер. хим. – 1999. – № 5. – С. 999–1002.[16] Goldshleger N.F., Tarasov B.P., Shul’ga Yu.M., Perov A.A., Roschupkina O.S., Moravsky A.P. Vzaimodeistvie fullerida platiny C60Pt s deiteriem (Vzaimodeistvie fullerida platiny CeoPt s deiteriem). Izv. RAN, Ser. khim., 1999;5:999–1002 (in Russ.).Goldshleger, N.F. [Text] / N.F. Goldshleger [et al.]. – In Fullerenes, Recent Advances in the Chemistry and Physics of Fullerenes and Related Materials. – Eds. Kadish K.M., Kamat P.V., Guldi D. – Vol. 7. – Penning-ton, NJ: The Electrochemical Society, 1999. – P. 647.[17] Goldshleger N.F., Tarasov B.P., Shul'ga Yu.M., Roschupkina O.S., Perov A.A., Moravsky A.P. In Full-erenes, Recent Advances in the Chemistry and Physics of Fullerenes and Related Materials. Eds. Kadish K.M., Kamat P.V., Guldi D., vol. 7, Pennington, NJ: The Electrochemical Society, 1999:647.Матысина З.А. Водород и твердофазные превращения в металлах, сплавах и фуллеритах: Монография / З.А. Матысина, Д.В. Щур. – Днепропетровск: Наука и образование, 2002. – 420 с.[18] Matysina ZA, Schur DV Hydrogen and solid-phase transformations in metals, alloys and fullerites (Vodorod i tverdofaznye prevrashcheniya v metallakh, splavakh i fulleritakh): Monograph. Dnepropetrovsk: “Science and Education” Publ., 2002, 420 p. (in Russ.).Schur, D.V. The peculiarities of hydrogenation of pentatomic carbon molecules in the frame of fullerene molecule C60 [Text] / D.V. Schur, S.Yu. Zaginaichenko, T.N. Veziroglu // International Journal of Hydrogen Energy. – 2008. – Vol. 33. – No 13. – P. 3330–3345.[19] Schur D.V., Zaginaichenko S.Yu., Veziroglu T.N. The peculiarities of hydrogenation of pentatomic carbon molecules in the frame of fullerene molecule C60. International Journal of Hydrogen Energy, 2008;33(13):3330–3345.Башкин, И.О. Термостабильные соединения водорода на базе углеродных нанотрубок и нановолокон, полученные под высоким давлением / И.О. Башкин [и др.] // Письма в ЖЭТФ. – 2004. – Т. 79. – №. 5. – С. 280–285.[20] Bashkin I.O., Antonov V.E., Bazhenov A.V., Bdikin I.C., Borisenko D.N., Krinichnaya E.P., Moravsky A.P., Kharkunov A.I., Shulga Y.M., Osipyan Y.A., Ponyatovsky E.G. Thermo-stable hydrogen compounds based on carbon nanotubes and nanofibres obtained under high pressure (Termostabil'nye soedineniya vodoroda na baze uglerodnykh nanotrubok i nanovolokon, poluchennye pod vysokim davleniem). Pis'ma v ZhETF, 2004;79(5):280–285 (in Russ.).Bashkin, I.O. Carbon materials hydrogenated under high pressure [Text] / I.O. Bashkin [et al.] // Proc. of 8th International Conference “Hydrogen Materials Science and Chemistry of Carbon Nanomaterials”. – Sudak, Crimea, Ukraine. – September, 2003. – P. 796–799.[21] Bashkin I.O., Antonov V.E., Bazhenov A.V., Bdikin I.K., Borisenko D.N., Krinichnaya E.P., Moravsky A.P., Ossipyan Yu.A., Ponyatovsky E.G., Fursova T.N., Harkunov A.I., Shulga Yu.M. Carbon materials hydrogenated under high pressure. Proc. of 8th International Conference “Hydrogen Materials Science and Chemistry of Carbon Nanomaterials”, Sudak, Crimea, Ukraine, September 14–20, 2003, p. 796–799.Bashkin, I.O. High-pressure hydrogenation of graphite [Text] / I.O. Bashkin [et al.] // Proc. of 10th International Conference “Hydrogen Materials Science and Chemistry of Carbon Nanomaterials”. – Sudak, Crimea, Ukraine. – September, 2007. – P. 686–689.[22] Bashkin I.O., Antonov V.E., Bazhenov A.V., Fursova T.N., Lukashev R.V., Sakharov M.K., Shulga Yu.M., Zavaritskaya V.A. High-pressure hydrogenation of graphite. Proc. of 10th International Conference “Hydrogen Materials Science and Chemistry of Carbon Nanomaterials”, Sudak, Crimea, Ukraine, September 22–28, 2007, p. 686–689.Savenko, A.F. Structural and methodical features of the installation for investigations of hydrogen-sorption characteristics of carbon nanomaterials and their composites. Hydrogen Materials Science and Chemistry of Carbon Nanomaterials [Text] / A.F. Savenko [et al.] // Proc. of NATO ARW on HMSCCN, Sevastopol. – 2005. – P. 365–382 (Published by Springer, The Netherlands, 2007).[23] Savenko A.F., Bogolepov V.A., Meleshevich K.A., Zaginaichenko S.Yu., Schur D.V., Lototsky M.V., Pishuk V.K., Teslenko L.O., Skorokhod V.V. Structural and methodical features of the installation for investigations of hydrogen-sorption characteristics of carbon nanomaterials and their composites. Hydrogen Materials Science and Chemistry of Carbon Nanomaterials. Proc. of NATO ARW on HMSCCN, Sevastopol; 2005, pp. 365– 382 (Published by Springer, The Netherlands, 2007)Щур, Д.В. Углеродные наноматериалы и фазовые превращения в них [Текст] / Д.В. Щур, З.А. Матысина, С.Ю. Загинайченко. – Днепропетровск: Наука и образование, 2007. – 680 с.[24] Schur D.V., Matysina Z.A. , Zaginaichenko S.Yu. Carbon nanomaterials and phase transformations in them (Uglerodnye nanomaterialy i fazovye prevrashcheniya v nikh). Dnepropetrovsk: “Science and Education” Publ., 2007, 680 p.

The authors declare that there are no conflicts of interest present.