The Modification of Carbon Nanospheres with Oxygen-Containing Groups by the Oxidation in Nitric Acid

Костянтин Олексійович Кирпач, Євген Васильович Полункін

Abstract


Background. Purification and functionalization of carbon nanomaterials is an important task to get nanoparticles with a narrow size distribution which will be soluble in organic substrates that allow effectively find practical using of these nano-objects.

Objective. Specifying of the influence of nitric acid oxidation of carbon nanospheres on their structure and chemical composition.

Methods. The oxidation of the initial samples at 120 °C in solutions of nitric acid of different concentrations was carried out to estimate structural changes. Structural changes and chemical composition were evaluated according to Raman spectroscopy and infrared spectroscopy.

Results. For the first time it is presented the changes in the structure and chemical composition of the oxidized in nitric acid, which was selected as a relatively mild oxidizer, the samples of carbon nanospheres obtained by the high-frequency arc-discharge synthesis using both cyclohexane or propane-butane. The carbon nanospheres’ sizes are about 5 to 50 nm, the spheres have multilayer structure. It is found that with increasing the acid concentration from 15 to 60 wt.% oxidized product yield decreases and the percentage of oxygen in samples increases.

Conclusions. Functionalization of carbon nanospheres by oxidation results in nanoparticles with a significant amount of oxygen-containing groups including COOH, C=O, C–O–C, C–OH. It was found that the oxidation of carbon nanospheres with nitric acid leads to a change of their microstructure with increasing interaction between the graphene layers and the formation of “ideally” inserted layers, as revealed from the shift of the bands in the Raman spectra. 


Keywords


Carbon nanospheres; Oxidation; Nitric acid; Raman spectroscopy; Infrared spectroscopy

References


T.N. Hoheisel et al., “Nanostructured carbonaceous materials from molecular precursors”, Angew. Chem. Int. Ed., vol. 49, no. 37, pp. 6496–6515, 2010. doi: 10.1002/anie.200907180

H.W. Kroto et al., “C60: Buckminsterfullerene”, Nature, vol. 318, pp. 162–163, 1985. doi: 10.1038/318162a0

S. Iijima, “Helical microtubules of graphitic carbon”, Nature, vol. 354, pp. 56–58, 1991. doi: 10.1038/354056a0

Y. Ma et al., “A practical route to the production of carbon nanocages”, Carbon, vol. 43, no. 8, pp. 1667–1672, 2005. doi: 10.1016/j.carbon.2005.02.004

A.K. Geim and K.S. Novoselov, “The rise of graphene”, Nature Mater., vol. 6, pp. 183–191, 2007. doi: 10.1038/nmat1849

D. Ugarte, “Curling and closure of graphitic networks under electron-beam irradiation”, Nature, vol. 359, pp. 707–709, 1992. doi: 10.1038/359707a0

A.S. Rettenbacher et al., “Preparation and functionalization of multilayer fullerenes (Carbon Nano-Onions)”, Chem. Eur. J., vol. 12, no. 2, pp. 376–387, 2006. doi: 10.1002/chem.200690003

V. Datsyuk et al., “Chemical oxidation of multiwalled carbon nanotubes”, Carbon, vol. 46, no. 6, pp. 833–840, 2008. doi: 10.1016/j.carbon.2008.02.012

L.Z. Boguslavskiy et al., “The synthesis of nanocarbon by high pulse discharge method”, Nanosystemy, Nanomaterialy, Nanotekhnolohiyi, vol. 10, no. 1, pp. 159–167, 2012 (in Russian).

N. Dementev et al., “Purification of carbon nanotubes by dynamic oxidation in air”, J. Mater. Chem., vol. 19, pp. 7904–7908, 2009. doi: 10.1039/B910217E

A.V. Bazhenov et al., “Sorption of metal ions on multi-walled carbon nanotubes”, Fullerenes, Nanotubes and Carbon Nano­structures, vol. 18, no. 4–6, pp. 564–568, 2010. doi: 10.1080/1536383X.2010.488080

U. Kuhlmann et al., “Infrared active phonons in single-walled carbon nanotubes”, Chem. Phys. Lett., vol. 294, no. 1-3, pp. 237–240, 1998. doi: 10.1016/S0009-2614(98)00845-8

H. Yao et al., “Rheological properties and chemical analysis of nanoclay and carbon microfiber modified asphalt with Fourier transform infrared spectroscopy”, Construction and Building Materials, vol. 38, pp. 327–337, 2013. doi: 10.1016/j.con­build­mat.2012.08.004

K. Krishnamoorthy et al., “Graphene oxide nanostructures modified multifunctional cotton fabrics”, Appl. Nanosci., vol. 2, no. 2, pp. 119–126, 2012. doi: 10.1007/s13204-011-0045-9

J. Zawadzki, “IR spectroscopic investigations of the mechanism of oxidation of carbonaceous films with HNO3 solution”, Carbon, vol. 18, no. 4, pp. 281–285, 1980. doi: 10.1016/0008-6223(80)90052-4

A.C. Ferrari, “Raman spectroscopy of graphene and graphite: Disorder, electron–phonon coupling, doping and nonadiabatic effects”, Solid State Comm., vol. 143, no. 1-2, pp. 47–57, 2007. doi: 10.1016/j.ssc.2007.03.052


GOST Style Citations


  1. Nanostructured carbonaceous materials from molecular precursors / T.N. Hoheisel, S. Schrettl, R. Szilluweit et al. // Angew. Chem. Int. Ed. – 2010. – 49, № 37. – P. 6496–6515.
     
  2. C60: Buckminsterfullerene / H.W. Kroto, J.R. Heath, S.C. O’Brien et al. // Nature. –1985. – 318. – P. 162–163.
     
  3. Iijima S. Helical microtubules of graphitic carbon // Nature. – 1991. – 354. – P. 56–58.
     
  4. A practical route to the production of carbon nanocages / Y. Ma, Z. Hu, K. Huo et al. // Carbon. – 2005. – 43, № 8. – P. 1667–1672.
     
  5. Geim A.K., Novoselov K.S. The rise of graphene // Nature Mater. – 2007. – 6. – P. 183–191.
     
  6. Ugarte D. Curling and closure of graphitic networks under electron-beam irradiation // Nature. – 1992. – 359. – P. 707–709.
     
  7. Preparation and functionalization of multilayer fullerenes (Carbon nano-onions) / A.S. Rettenbacher, B. Elliott, J.S. Hudson et al. // Chem. Eur. J. – 2006. – 12, № 2. – P. 376–387.
     
  8. Chemical oxidation of multiwalled carbon nanotubes / V. Datsyuk, M. Kalyva, K. Papagelis et al. // Carbon. – 2008. – 46, № 6. – P. 833–840.
     
  9. Синтез наноуглерода высокочастотным разрядно-импульсным методом / Л.З. Богуславский, Н.С. Назарова,  Д.В. Винниченко и др. // Наносистеми, наноматеріали, нанотехнології. – 2012. – 10, № 1. – С. 159–167.
     
  10. Purification of carbon nanotubes by dynamic oxidation in air / N. Dementev, S. Osswald, Y. Gogotsi et al. // J. Mater. Chem. – 2009. – 19. – P. 7904–7908.
     
  11. Sorption of metal ions on multi-walled Carbon nanotubes / A.V. Bazhenov, T.N. Fursova, S.S. Grazhulene et al. // Fullerenes, Nanotubes and Carbon Nanostructures. – 2010. – 18, № 4-6. – P. 564–568.
     
  12. Infrared active phonons in single-walled carbon nanotubes / U. Kuhlmann, H. Jantoljak, N. Pfander et al. // Chem. Phys. Lett. – 1998. – 294, № 1-3. – P. 237–240.
     
  13. Rheological properties and chemical analysis of nanoclay and carbon microfiber modified asphalt with Fourier transform infrared spectroscopy / H. Yao, Z. You, L. Li et al. // Construction and Building Materials. – 2013. – 38. – P. 327–337.
     
  14. Krishnamoorthy K., Navaneethaiyer U., Mohan R. Graphene oxide nanostructures modified multifunctional cotton fabrics // Appl. Nanosci. – 2012. – 2, № 2. – P. 119–126.
     
  15. Zawadzki J. IR spectroscopic investigations of the mechanism of oxidation of carbonaceous films with HNO3 solution // Carbon. – 1980. – 18, № 4. – P. 281–285.
     
  16. Ferrari A.C. Raman spectroscopy of graphene and graphite: Disorder, electron–phonon coupling, doping and nonadiabatic effects // Solid State Comm. – 2007. – 143, № 1-2. – P. 47–57.




DOI: https://doi.org/10.20535/1810-0546.2015.6.50447

Refbacks

  • There are currently no refbacks.


Copyright (c) 2017 NTUU KPI