Advertisement

Journal of Nanoparticle Research

, Volume 12, Issue 6, pp 2125–2133 | Cite as

Single-walled carbon nanotube formation on iron oxide catalysts in diffusion flames

  • Chad J. Unrau
  • Richard L. Axelbaum
  • Phil Fraundorf
Research Paper

Abstract

Single-walled carbon nanotubes (SWCNTs) are shown to grow rapidly on iron oxide catalysts on the fuel side of an inverse ethylene diffusion flame. The pathway of carbon in the flame is controlled by the flame structure, leading to formation of SWCNTs free of polycyclic aromatic hydrocarbons (PAH) or soot. By using a combination of oxygen-enrichment and fuel dilution, fuel oxidation is favored over pyrolysis, PAH growth, and subsequent soot formation. The inverse configuration of the flame prevents burnout of the SWCNTs while providing a long carbon-rich region for nanotube formation. Furthermore, flame structure is used to control oxidation of the catalyst particles. Iron sub-oxide catalysts are highly active toward SWCNT formation while Fe and Fe2O3 catalysts are less active. This can be understood by considering the effects of particle oxidation on the dissociative adsorption of gas-phase hydrocarbons. The optimum catalyst particle composition and flame conditions were determined in near real-time using a scanning mobility particle sizer (SMPS) to measure the catalyst and SWCNT size distributions. In addition, SMPS results were combined with flame velocity measurement to measure SWCNT growth rates. SWCNTs were found to grow at rates of over 100 μm/s.

Keywords

Single-wall carbon nanotubes Diffusion flames Differential mobility analyzer Iron oxide catalyst Oxy-fuel combustion 

Notes

Acknowledgments

The authors thank Xiaofeng Zhang for his efforts in collecting TEM data and Dr. John Gleaves for his helpful discussions. This research was funded by the Center for Materials Innovation at Washington University and NASA.

References

  1. Anderson AB (1977) Interaction of hydrogen, carbon, acetylene, ethylene, and alkyl fragments with iron surfaces. Catalytic hydrogenation, dehydrogenation, carbon bond breakage and hydrogen mobility. J Am Chem Soc 99:696–707CrossRefGoogle Scholar
  2. Andrews R, Jacques D, Rao AM, Derbyshire F, Qian D, Fan X et al (1999) Continuous production of aligned carbon nanotubes: a step closer to commercial realization. Chem Phys Lett 303:467–474CrossRefADSGoogle Scholar
  3. Baker RTK, Alonzo JR, Dumesic JA, Yates DJC (1982) Effect of the surface state of iron on filamentous carbon formation. J Catal 77:74–84CrossRefGoogle Scholar
  4. Cheng HM, Li F, Sun X, Brown SDM, Pimenta MA, Marucci A et al (1998) Bulk morphology and diameter distribution of single-walled carbon nanotubes synthesized by catalytic decomposition of hydrocarbons. Chem Phys Lett 289:602–610CrossRefADSGoogle Scholar
  5. Dai H, Rinzler AG, Nikolaev P, Thess A, Colbert DT, Smalley RE (1996) Single-wall nanotubes produced by metal-catalyzed disproportionation of carbon monoxide. Chem Phys Lett 260:471–475CrossRefADSGoogle Scholar
  6. de Heer WA (2004) Nanotubes and the pursuit of applications. MRS Bulletin, Pittsburgh, pp 281–285Google Scholar
  7. Diener MD, Nichelson N, Alford JM (2000) Synthesis of single-walled carbon nanotubes in flames. J Phys Chem B 104:9615–9620CrossRefGoogle Scholar
  8. Dillon AC, Parialla PA, Alleman JL, Perkins JD, Heben MJ (2000) Controlling single-wall nanotube diameters with variation in laser pulse power. Chem Phys Lett 316:13–18CrossRefADSGoogle Scholar
  9. Donnet J-B, Bansal RC, Wang M-J (eds) (1993) Carbon black science and technology. Marcel Dekker, Inc., New YorkGoogle Scholar
  10. Du J, Axelbaum RL (1996) The effects of flame structure on extinction of CH4–O2–N2 diffusion flames. Proc Combust Inst 26:1137–1142Google Scholar
  11. Endo M, Takeuchi K, Kobori K, Takahashi K, Kroto HW, Sarkar A (1995) Pyrolytic carbon nanotubes from vapor-grown carbon-fibers. Carbon 33:873–881CrossRefGoogle Scholar
  12. Hafner JH, Bronikowski MJ, Azamian BR, Nikolaev P, Rinzler AG, Colbert DT et al (1998) Catalytic growth of single-wall carbon nanotubes from metal particles. Chem Phys Lett 296:195–202CrossRefADSGoogle Scholar
  13. Height MJ, Howard JB, Tester JW, Sande JBV (2004) Flame synthesis of single-walled carbon nanotubes. Carbon 42:2295–2307CrossRefGoogle Scholar
  14. Kamalakaran R, Terrones M, Seeger T, Kohler-Redlich P, Ruhle M, Kim YA et al (2000) Synthesis of thick and crystalline nanotube arrays by spray pyrolysis. Appl Phys Lett 77:3385–3387CrossRefADSGoogle Scholar
  15. Kong J, Soh HT, Cassell AM, Quate CF, Dai HJ (1998) Synthesis of individual single-walled carbon nanotubes on patterned silicon wafers. Nature 395:878–881CrossRefADSGoogle Scholar
  16. Kumfer BM, Skeen SA and Axelbaum RL (2008) Soot inception limits in laminar diffusion flames with application to oxy-fuel combustion. Combust Flame 154:546–556Google Scholar
  17. Megaridis CM, Dobbins RA (1990) Morphological description of flame-generated materials. Combust Sci Tech 71:95–109CrossRefGoogle Scholar
  18. Merchan-Merchan W, Saveliev AV, Kennedy LA (2003) Carbon nanostructures in opposed-flow methane oxy-flames. Combust Sci Tech 175:2217–2236CrossRefGoogle Scholar
  19. Moisala A, Nasibulin AG, Brown DP, Jiang H, Khriachtchev L, Kauppinen EI (2006) Single-walled carbon nanotube synthesis using ferrocene and iron pentacarbonyl in a laminar flow reactor. Chem Eng Sci 61:4393–4402CrossRefGoogle Scholar
  20. Nikolaev P (2004) Gas-phase production of single-walled carbon nanotubes from carbon monoxide: a review of the HiPco process. J Nanosci Nanotechnol 4:307–316CrossRefPubMedGoogle Scholar
  21. Nikolaev P, Bronikowski MJ, Bradley RK, Rohmund F, Colbert DT, Smith KA et al (1999) Gas-phase catalytic growth of single-walled carbon nanotubes from carbon monoxide. Chem Phys Lett 313:91–97CrossRefADSGoogle Scholar
  22. Padin J, Yang RT (1997) Tailoring new adsorbents based on π-complexation: cation and substrate effects on selective acetylene adsorption. Ind Eng Chem Resour 36:4224–4230CrossRefGoogle Scholar
  23. Puretzky AA, Geohegan DB, Fan X, Pennycook SJ (2000) Dynamics of single-wall carbon nanotube synthesis by laser vaporization. Appl Phys A 70:153–160CrossRefADSGoogle Scholar
  24. Raty JY, Gygi F, Galli G (2005) Growth of carbon nanotubes on metal nanoparticles: a microscopic mechanism from ab initio molecular dynamics simulations. Phys Rev Lett 95:096103CrossRefPubMedADSGoogle Scholar
  25. Saito Y, Kawabata K, Okuda M (1995) Single-layered carbon nanotubes synthesized by catalytic assistance of rare-earths in a carbon-arc. J Phys Chem 99:16076–16079CrossRefGoogle Scholar
  26. Sato H, Hori Y, Hata K, Seko K, Nakahara H, Saito Y (2006) Effect of catalyst oxidation on the growth of carbon nanotubes by thermal chemical vapor deposition. J Appl Phys 100:104321CrossRefADSGoogle Scholar
  27. Unrau CJ, Axelbaum RL, Biswas P, Fraundorf P (2007a) Online size characterization of nanofibers and nanotubes. Mansoori GA, George TF, Assoufid L, Zhang G (eds) Molecular building blocks for nanotechnology: from diamondoids to nanoscale materials and applications, vol 109. Springer, New York, pp 212–245Google Scholar
  28. Unrau CJ, Axelbaum RL, Biswas P, Fraundorf P (2007b) Synthesis of single-walled carbon nanotubes in oxy-fuel inverse diffusion flames with online diagnostics. Proc Combust Inst 31:1865–1872CrossRefGoogle Scholar
  29. Vander Wal RL, Hall LJ (2001) Flame synthesis of Fe catalyzed single-walled carbon nanotubes and Ni catalyzed nanofibers: growth mechanisms and consequences. Chem Phys Lett 349:178–184CrossRefADSGoogle Scholar
  30. Vander Wal RL, Ticich TM, Curtis VE (2000) Diffusion flame synthesis of single-walled carbon nanotubes. Chem Phys Lett 323:217–223CrossRefADSGoogle Scholar
  31. Xu F, Liu X, Tse S (2006) Synthesis of carbon nanotubes on metal alloy substrates with voltage bias in methane inverse diffusion flames. Carbon 44:570–577zbMATHCrossRefGoogle Scholar
  32. Yuan LM, Saito K, Hu WC, Chen Z (2001) Ethylene flame synthesis of well-aligned multi-walled carbon nanotubes. Chem Phys Lett 346:23–28CrossRefADSGoogle Scholar
  33. Yuan LM, Li TX, Saito K (2003) Synthesis of multiwalled carbon nanotubes using methane/air diffusion flames. Proc Combust Inst 29:1087–1092CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2009

Authors and Affiliations

  • Chad J. Unrau
    • 1
    • 2
  • Richard L. Axelbaum
    • 1
  • Phil Fraundorf
    • 3
  1. 1.Department of Energy, Environmental and Chemical Engineering/Center for Materials InnovationWashington University in St. LouisSt. LouisUSA
  2. 2.Cabot CorporationPampaUSA
  3. 3.Department of Physics & Astronomy/Center for Molecular ElectronicsUniversity of Missouri-St. LouisSt. LouisUSA

Personalised recommendations