Chemistry, Physics and Technology of Surface

ISSN 2518-1238 (Online), ISSN 2079-1704 (Print)

Complex compounds of various types and nature have been widely applied in many fields of science and technology. Complex aggregates based on nanostructures such as nanotubes and other coordination compounds, for example, metallocenes, have unique properties, since a combination of their individual characteristics provides for further growing interest to the research in chemistry, physics, electronics, medicine, etc. 
The initial structure was a (5.5)@(10.10) nanotube (CNT) having 270 carbon atoms. Intercalation of this double-walled carbon nanotubes (DWCNT) assumes placing the intercalate inside the (5.5) CNT, into intertubular space, and its differently oriented sorption on the outer surface of the (10.10) CNT. 
By employing the methods of MM+, РМ3 and Monte-Carlo, the positioning has been studied of molecules of tricarbonyl(cyclopentadienyl)manganese, monocyclopentadienylferrum(ІІ), bis(cyclopentadienyl)nickel and bis(η⁵-cyclopentadienyl)cobalt in a double-walled (5,5)@(10,10) carbon nanotube depending on intercalate concentration and intercalation temperature. The temperature increase (over ~455–460 K) causes gradual bond ruining followed by extrusion of interwall intercalate. Further temperature increase up to 620–650 K is characterised with intercalate external surface desorption, stabilising the whole systems and keeping the interwall intercalate only. 
It is necessary to note that the suggested model variant allows to demonstrate the thermodynamic selectivity of physical and chemical sorption-desorption. At lower temperatures there appears physical sorption, its natural feature is most likely to overlap the non-hybridized orbital 3d_xy of the metal ions with the π-system of the DWCNT side surface while chemisorption is observed at higher temperatures that is peculiar or π-π interactions of aromatic and quasiaromatic cyclic (heterocyclic) systems. 
Moreover, simultaneous presence of donor/acceptor feature of the DWCNT’s intertube space as a result of positive and negative Gaussian curvature, makes it possible to regulate orientation of intercalate donor and acceptor edges what allows us to view it as a potential molecular switch. There have been calculated the UV-spectra for (5,5)@(10,10) DWCNT depending on the intercalate concentration as well as an association constant of the systems which makes 26.45 l·mol^–1 (for system with ferrocene); 36.2 l·mol^–1 (for system with nickelocene); 76.8 l·mol^–1 (for system with cobaltocene) and 6.745 l·mol^–1 (for system with manganocene).

intercalation; double-walled carbon nanotube; “host-guest” complex tricarbonyl(cyclopentadienyl)mangan ese; monocyclopentadienylferrum(ІІ); bis(cyclopentadienyl)n ickel; bis(η5-cyclopentadienyl)cobalt

1. Novoselov K.S., Jiang D., Schedin F., Booth T.J., Khotkevich V.V., Morozov S.V., Geim A.K. Two-dimensional atomic crystals. Proc. Nat. Acad. Sci. USA. 2005. 102(30): 10451. https://doi.org/10.1073/pnas.0502848102 

2. Son Y.-W., Cohen M.L., Louie S.G. Half-metallic graphene nanoribbons. Nature. 2006. 444: 347. https://doi.org/10.1038/nature05180 

3. Geim A.K., Novoselov K.S. The structure of suspended graphene sheets. Nature. 2007. 446: 60. https://doi.org/10.1038/nature05545 

4. Matsui D.V., Prylutskyy Yu.I., Matzuy L.Yu., Le Normand F., Ritter U., Scharff P. Transverse and longitudinal magnetoresistance in graphite intercalated by Co. Physica E. 2008. 40(7): 2630. https://doi.org/10.1016/j.physe.2007.09.121 

5. Matsui D., Ovsiyenko I., Lazarenko O., Prylutskyy Yu., Matsui V. Abnormal electron transport in graphite intercalation compounds with iron. Mol. Cryst. Liq. Cryst. 2011. 535(1): 64. https://doi.org/10.1080/15421406.2011.537941 

6. Ritter U., Scharff P., Grechnev G.E., Desnenko V.A., Fedorchenko A.V., Panfilov A.S., Prylutskyy Yu.I., Kolesnichenko Yu.A. Structure and magnetic properties of multi-walled carbon nanotubes modified with cobalt. Carbon. 2011. 49(13): 4443. https://doi.org/10.1016/j.carbon.2011.06.039 

7. Ritter U., Tsierkezos N.G., Prylutskyy Yu.I., Matzui L.Yu., Gubanov V.O., Bilyi M.M., Davydenko M.O. Structure-electrical resistivity relationship of N-doped multi-walled carbon nanotubes. J. Mater. Sci. 2012. 47(5): 2390. https://doi.org/10.1007/s10853-011-6059-6 

8. Durkop T., Kim B.M., Fuhrer M.S. Properties and applications of high-mobility semiconducting nanotubes. J. Phys.: Condens. Matter. 2004. 16(18): 553. https://doi.org/10.1088/0953-8984/16/18/R01 

9. Kane C.L., Mele E.J. Quantum Spin Hall Effect in Graphene. Phys. Rev. Lett. 2005. 95(22): 226801. https://doi.org/10.1103/PhysRevLett.95.226801 

10. Mykhailenko O., Matsui D., Prylutskyy Yu., Normand F., Eklund P., Scharff P. Monte Carlo simulation of intercalated carbon nanotubes. J. Mol. Model. 2007. 13(1): 283. https://doi.org/10.1007/s00894-006-0129-8 

11. Mykhailenko O.V., Prylutskyy Yu.I., Matsuy D.V., Strzhemechny Y.M., Le Normand F., Ritter U., Scharff P. Structure and thermal stability of Co- and Fe-intercalated double graphene layers. J. Comput. Theor. Nanosci. 2010. 7(6): 996. https://doi.org/10.1166/jctn.2010.1444 

12. Grechnev G.E., Lyogenkaya A.A., Kolesnichenko Y.A., Prylutskyy Y.I., Hayn R. Electronic structure and magnetic properties of graphite intercalated with 3d-metals. Low Temp. Phys. 2014. 40(5): 580. https://doi.org/10.1063/1.4876224 

13. Mykhailenko O.V., Prylutskyy Yu.I., Komarov I.V., Strungar A.V. Host-Guest Intercalate of Carbon Nanotube with Bis(η5-cyclopentadienyl)cobalt. In: II Ukrainian-Polish scientific conference Membrane and Sorption processes and technologies (December 2–4, 2015, Kyiv, Ukraine). P. 148.

14. Rapaport D.C. The Art of Molecular Dynamics Simulation. (Cambridge, UK: Cambridge University Press, 1995).

15. Tersoff J. Modelling Solid–State Chemistry: Interatomic Potentials for Multicomponent Systems. Phys. Rev. B. 1989. 39: 5566. https://doi.org/10.1103/PhysRevB.39.5566 

16. Dorfman S., Mundim K.C., Fuks D., Berner A., Ellis D.E. Snapshot of an Electron orbital. Mat. Sci. and Eng. 2001. 15: 191. https://doi.org/10.1016/S0928-4931(01)00308-3 

17. Mykhailenko O.V., Prylutskyy Yu.I., Komarov I.V., Strungar A.V., Ritter U. Guest-Host Intercalate of Carbon Nanotube with Tricarbonyl(cyclopentadienyl)mangan. In: 3rd International research and practice conference NANOTECHNOLOGY and NANOMATERIALS (NANO-2015), (August 26–29, 2015, Lviv, Ukraine). P. 540.

18. Ionescu M.I., Zhang Y., Li R., Sun X., Abou-Rachid H., Lussier L-S. Hydrogen-free spray pyrolysis chemical vapor deposition method for the carbon nanotube growth: Parametric studies. Appl. Surf. Sci. 2011. 257(15): 6843. https://doi.org/10.1016/j.apsusc.2011.03.011 

19. Mykhailenko O.V., Prylutskyy Y.I., Komarov I.V., Strungar A.V., Tsierkezos N.G. Guest-host intercalate of double-walled carbon nanotube with tricarbonyl(cyclopentadienyl)manganese. Materialwissenschaft und Werkstofftechnik 2016. 47(2–3): 203. https://doi.org/10.1002/mawe.201600477 

20. Mykhailenko O.V., Prylutskyy Y.I., Komarov I.V., Strungar A.V. Thermodynamic Complexing of Monocyclopentadienylferrum(II) Intercalates with Double-Walled Carbon Nanotubes. Nanoscale Res. Lett. 2016. 11(1): 128. https://doi.org/10.1186/s11671-016-1351-7 

21. Mykhailenko O.V. Formation of Double-Walled Nanotube-Bis (cyclopentadienyl)nickel Complexes By Host-Guest Type. In: Ukrainian Conference with International Participation Chemistry, Physics and Technology of Surface. (May 17–18, 2016, Kyiv, Ukraine). P. 127.