Journals →  Materialy Elektronnoi Tekhniki →  2013 →  #3 →  Back

MODELING OF PROCESSES AND MATERIALS
ArticleName Theoretical Investigation of the Hydrogenation Process in Singleand Double-Layered Pyrolized Acryl-Nitril Nanopolymer
ArticleAuthor I. V. Zaporotskova, N. A. Anikeev, L. V. Kozhitov, A. V. Popkova
ArticleAuthorData

Volgograd State University:

I. V. Zaporotskova

N. A. Anikeev


National University of Science and Technology «MISIS» Theoretical Investigation of the Hydrogenation Process in Singleand Double-Layered Pyrolized Acryl-Nitril Nanopolymer:

L. V. Kozhitov
A. V. Popkova

Abstract

The article reports a theoretical quantum chemical study of the adsorption mechanisms in atomic and molecular hydrogen on the surface of an advanced polymeric material – pyrolized polyacrylonitrile (PPAN). Three variants of atomic hydrogen orientation and five variants of molecular hydrogen orientation over one− and two−layer PPAN surface have been considered. The variants differed in the positions of nitrogen atoms in the close vicinity of a selected adsorption center in the polymer. Potential adsorption energy profiles of atomic hydrogen and hydrogen moleculeshave been constructed and analyzed, and the main power and geometrical characteristics of the processes have been defined. Charge redistributions in the systems have been studied. We show that neither a hydrogen atom, nor a hydrogen molecule can be adsorbed over the hexagon center of single−layer PPAN surfaces, and in other cases chemical adsorption occurs. For adsorption over the surface of two−layer PPAN, any orientation variants of a hydrogen molecule are possible. A negative influence of nitrogen atom of the polymer surface on the efficiency of atomic hydrogen adsorption has been established, whereas its influence on the adsorption of molecular hydrogen is positive.

keywords Pyrolized polyacrylonitrile, atomic hydrogen, molecular hydrogen, hydrogenation, adsorption, potential energy profile
References

1. Zemcov, L. M. Himicheskie prevrasheniya poliakrilonitrila pod deistviem nekogerentnogo infrakrasnogo izlucheniya / L. M. Zemcov, G. P. Karpacheva // Vysokomolek. soed. Ser. A. − 1994. − T. 36, N 6. − P. 919.
2. Kozlov, V. V. O himicheskih prevrasheniyah poliakrilonitrila pri termicheskoi obrabotke v vakuume i atmosfere ammiaka / V. V. Kozlov, G. P. Karpacheva, V. S. Petrov, E. V. Lazovskaya, S. A. Pavlov // Izv. vuzov. Materialy elektron. tehniki. − 2004. − N 4. − P. 45—49.
3. Kozlov, V. V. Osobennosti obrazovaniya sistemy polisopryazhennyh svyazei poliakrilonitrila v usloviyah vakuuma pri termicheskoi obrabotke / V. V. Kozlov // Vysokomolek. soedineniya. − Seriya A. − 2001. − T. 43, N 1. − P. 3—26.
4. Kozhitov, L. V. Struktura i fiziko−himicheskie svoistva organicheskogo poluprovodnika na osnove poliakrilonitrila i ego kompozita s nanochasticami medi / L. V. Kozhitov, V. V. Krapuhin, G. P. Karpacheva, V. V. Kozlov // Izv. vuzov. Materialy elektron. tehniki. − 2004. − N 4. − P. 7—10
5. Kozhitov, L. V. Sozdanie dlya nanoelektroniki novyh materialov na osnove uglerodnogo nanokristallicheskogo materiala i metallopolimernyh nanokompozitov / L. V. Kozhitov, V. V. Kozlov, V. V. Krapuhin // Izv. vuzov. Materialy elektron. tehniki. − 2006. − N 4. − P. 4—10.
6. Shul’ga, Yu. M. Izuchenie pirolizovannyh plenok poliakrilonitrila metodami rentgenovskoi fotoelektronnoi spektroskopii, elektronnoi Ozhe−spektroskopii i spektroskopii poter’ energii elektronov / Yu. M. Shul’ga, V. I. Rubcov, O. N. Efimov, G.P. Karpacheva, L. M. Zemcov, V. V. Kozlov // Vysokomolekulyarnye soedineniya. Ser. A. − 1996. − T. 38, N 6. − P. 989—992.
7. Sazanov, Yu. N. Thermochemical reactions of polyacrylonitrile with fullerene C60 / Yu. N. Sazanov, M. V. Mokeev, A. V. Novoselova, V. L. Ugolkov, G. N. Fedorova, A. V. Gribanov, V. N. Zgonnik // Russ. J. Appl. Chem. − 2003. − V. 76, N 3. − P. 452—456.
8. Setnescu, R. IR and X−ray characterization of the ferromagnetic phase of pyrolysed polyacrylonitrile / R. Setnescu, S. Jipa, T. Setnescu, W. Kappel, S. Kobayashi, Z. Osawa // Carbon. − 1999. − V. 37, N. 1. − P. 1—6.
9. Kozlov, V. V. Strukturnye prevrasheniya kompozita na osnove poliakrilonitrila i fullerena S60 pod vozdeistviem IK−izlucheniya / V. V. Kozlov, Yu. M. Korolev, G. P. Karpacheva // Vysokomol. soed. Ser. A. − 1999. − T. 41, N 5. − P. 836.
10. Zaporockova, I. V. Protonnaya provodimost’ uglerodnyh nanostruktur na osnove pirolizovannogo poliakrilonitrila i ee prakticheskoe primenenie / I. V. Zaporockova, V. V. Kozlov, L. V. Kozhitov, V. V. Krapuhin, O. A. Davletova, D. G. Muratov // Izv. vuzov. Materialy elektron. tehniki. − 2008. − N 1. − P. 59—65.
11. Zaporockova, I. V. Uglerodnye i neuglerodnye nanomaterialy i kompozitnye struktury na ih osnove: stroenie i elektronnye svoistva / I. V. Zaporockova. − Volgograd : Izd−vo VolGU, 2009. − 490 s.
12. Davletova, O. A. Struktura i elektronnye harakteristiki pirolizovannogo poliakrilonitrila: diss. … kand. fiz.−mat. nauk / O. A. Davletova. − Volgograd : Volgogradskii gosudarstvennyi universitet, 2010.
13. Dewar, M. J. S. Ground states of molecules. The MNDO method. Approximations and Parameters / M. J. S. Dewar, W. Thiel // J. Amer. Chem. Soc. − 1977. − V. 99. − P. 4899—4906.
14. Dewar, M. J. S. A semiempirical model for the two−center repulsion integrals in the NDDO approximation / M. J. S. Dewar, W. Thiel // Theoret. Chem. Acta. − 1977. − V. 46. − P. 89—104.
15. Voityuk, A. A. Primenenie metoda MNDO dlya issledovaniya svoistv i reakcionnoi sposobnosti molekul / A. A. Voityuk // Zhurn. strukturnoi himii. − 1988. − T. 29, N 1. − P. 138—162.
16. Koch, W. A Chemist’s guide to density functional theory / W. Koch, M. Holthausen. − Weinheim : Wiley−VCH, 2002. − P. 19.

Language of full-text russian
Full content Buy
Back