Skip to main content
SpringerLink
Log in

Temperature effects on the nitric acid oxidation of industrial grade multiwalled carbon nanotubes

  • Research Paper
  • Published:
Journal of Nanoparticle Research Aims and scope Submit manuscript

Abstract

In this study, we report an oxidative treatment of multiwalled carbon nanotubes (MWCNTs) by using nitric acid at different temperatures (25–175 °C). The analyzed materials have diameters varying from 10 to 40 nm and majority lengths between 3 and 6 μm. The characterization results obtained by different techniques (e.g., field emission scanning electron microscopy, thermogravimetric analysis, energy-filtered transmission electron microscopy, Braunauer, Emmet and Teller method, ζ-potential and confocal Raman spectroscopy) allowed us to access the effects of temperature treatment on the relevant physico-chemical properties of the MWCNTs samples studied in view of an integrated perspective to use these samples in a bio-toxicological context. Analytical microbalance measurements were used to access the purity of samples (metallic residue) after thermogravimetric analysis. Confocal Raman spectroscopy measurements were used to evaluate the density of structural defects created on the surface of the tubes due to the oxidation process by using 2D Raman image. Finally, we have demonstrated that temperature is an important parameter in the generation of oxidation debris (a byproduct which has not been properly taken into account in the literature) in the industrial grade MWCNTs studied after nitric acid purification and functionalization.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  • Alexander AJ (2007) Carbon nanotubes structures and compositions: implications for toxicological studies. In: Monteiro-Riviere NA, Tran CL (eds) Nanotoxicology: characterization, dosing and health effects, 1st edn. Eds. Informa Healthcare, New York, pp 7–18

    Chapter  Google Scholar 

  • Al-Jamal KT, Nunes A, Methven L, Ali-Boucetta H, Li SP, Toma FM, Herrero MA, Al-Jamal WT, ten Eikelder HMM, Foster J, Mather S, Prato M, Bianco A, Kostarelos K (2012) Degree of chemical functionalization of carbon nanotubes determines tissue distribution and excretion profile. Angew Chem Int Ed 51(26):6389–6393

    Article  CAS  Google Scholar 

  • Belin T, Epron F (2005) Characterization methods of carbon nanotubes: a review. Mater Sci Eng B Solid State Mater Adv Technol 119(2):105–118

    Article  Google Scholar 

  • Berhanu D, Dybowska A, Misra SK, Stanley CJ, Ruenraroengsak P, Boccaccini AR, Tetley TD, Luoma SN, Plant JA, Valsami-Jones E (2009) Characterisation of carbon nanotubes in the context of toxicity studies. Environ Health 8(Suppl 1):S3

    Article  Google Scholar 

  • Cancado LG, Jorio A, Ferreira EHM, Stavale F, Achete CA, Capaz RB, Moutinho MVO, Lombardo A, Kulmala TS, Ferrari AC (2011) Quantifying defects in graphene via Raman spectroscopy at different excitation energies. Nano Lett 11(8):3190–3196

    Article  CAS  Google Scholar 

  • Cheung W, Pontoriero F, Taratula O, Chen AM, He H (2010) DNA and carbon nanotubes as medicine. Adv Drug Deliv Rev 62(6):633–649

    Article  CAS  Google Scholar 

  • Cho J, Boccaccini AR, Shaffer MSP (2012) The influence of reagent stoichiometry on the yield and aspect ratio of acid-oxidised injection CVD-grown multi-walled carbon nanotubes. Carbon 50(11):3967–3976

    Article  CAS  Google Scholar 

  • Chun AL (2009) Carbon nanotubes: safe production? Nature Nanotechnology. doi: 10.1038/nnano.2009.339

  • Crinelli R, Carloni E, Menotta M, Giacomini E, Bianchi M, Ambrosi G, Giorgi L, Magnani M (2010) Oxidized ultrashort nanotubes as carbon scaffolds for the construction of cell-penetrating NF-kappaB decoy molecules. ACS Nano 4(5):2791–2803

    Article  CAS  Google Scholar 

  • Farbod M, Tadavani SK, Kiasat A (2011) Surface oxidation and effect of electric field on dispersion and colloids stability of multiwalled carbon nanotubes. Colloid Surf A 384(1–3):685–690

    Article  CAS  Google Scholar 

  • Faria AF, Martinez DST, Moraes ACM, Maia da Costa MEH, Barros EB, Souza Filho AG, Alves OL (2012) Unveiling the role of oxidation debris on the surface chemistry of graphene through the anchoring of Ag nanoparticles. Chem Mater 24(21):4080–4087

    Article  CAS  Google Scholar 

  • Fogden S, Verdejo R, Cottam B, Shaffer M (2008) Purification of single walled carbon nanotubes: the problem with oxidation debris. Chem Phys Lett 460(1–3):162–167

    Article  CAS  Google Scholar 

  • Fraczek-Szczypta A, Menaszek E, Syeda TB, Misra A, Alavijeh M, Adu J, Blazewicz S (2012) Effect of MWCNT surface and chemical modification on in vitro cellular response. J Nanopart Res 14(10):1181

    Article  Google Scholar 

  • Freiman SW, Hooker SA, Migler KD, Arepalli S (2008) Measurement issues in single wall carbon nanotubes. In National Institute of Standards and Technology 960(19):4–15

    Google Scholar 

  • Grobert N (2006) Carbon nanotubes—becoming clean. Mater Today 10(1–2):28–35

    Google Scholar 

  • Guo L, Morris DG, Liu XY, Vaslet C, Hurt RH, Kane AB (2007) Iron bioavailability and redox activity in diverse carbon nanotube samples. Chem Mater 19(14):3472–3478

    Article  CAS  Google Scholar 

  • Gutierrez-Praena D, Pichardo S, Sanchez E, Grilo A, Camean AM, Jos A (2011) Influence of carboxylic acid functionalization on the cytotoxic effects induced by single wall carbon nanotubes on human endothelial cells (HUVEC). Toxicol In Vitro 25(8):1883–1888

    Article  CAS  Google Scholar 

  • Heister E, Lamprecht C, Neves V, Tilmaciu C, Datas L, Flahaut E, Soula B, Hinterdorfer P, Coley HM, Silva SRP, McFadden J (2010) Higher dispersion efficacy of functionalized carbon nanotubes in chemical and biological environments. ACS Nano 4(5):2615–2626

    Article  CAS  Google Scholar 

  • Hondow N, Brydson R, Wang P, Holton MD, Brown MR, Rees P, Summers HD, Brown A (2012) Quantitative characterization of nanoparticle agglomeration within biological media. J Nanopart Res 14(977):1–15

    Google Scholar 

  • Hull MS, Kennedy AJ, Steevens JA, Bednar AJ, Weiss CA, Vikesland PJ (2009) Release of metal impurities from carbon nanomaterials influences aquatic toxicity. Environ Sci Technol 43(11):4169–4174

    Article  CAS  Google Scholar 

  • Hussain SM, Braydich-Stolle LK, Schrand AM, Murdock RC, Yu KO, Mattie DM, Schlager JJ, Terrones M (2009) Toxicity evaluation for safe use of nanomaterials: recent achievements and technical challenges. Adv Mater 21(16):1549–1559

    Article  CAS  Google Scholar 

  • Kitamura H, Sekido M, Takeuchi H, Ohno M (2011) The method for surface functionalization of single-walled carbon nanotubes with fuming nitric acid. Carbon 49(12):3851–3856

    Article  CAS  Google Scholar 

  • Kuempel ED (2011) Carbon nanotube risk assessment: implications for exposure and medical monitoring. J Occup Environ Med 53(6 Suppl):S91–S97

    CAS  Google Scholar 

  • Lehman JH, Terrones M, Mansfield E, Hurst KE, Meunier V (2011) Evaluating the characteristics of multiwall carbon nanotubes. Carbon 49(8):2581–2602

    Article  CAS  Google Scholar 

  • Marques RRN, Machado BF, Faria JL, Silva AMT (2010) Controlled generation of oxygen functionalities on the surface of single-walled carbon nanotubes by HNO3 hydrothermal oxidation. Carbon 48(5):1515–1523

    Article  CAS  Google Scholar 

  • Murdock RC, Braydich-Stolle L, Schrand AM, Schlager JJ, Hussain SM (2008) Characterization of nanomaterial dispersion in solution prior to in vitro exposure using dynamic light scattering technique. Toxicol Sci 101(2):239–253

    Article  CAS  Google Scholar 

  • Osswald S, Havel M, Gogotsi Y (2007) Monitoring oxidation of multiwalled carbon nanotubes by Raman spectroscopy. J Raman Spectrosc 38(6):728–736

    Article  CAS  Google Scholar 

  • Paradise M, Goswami T (2007) Carbon nanotubes—production and industrial applications. Mater Design 28(5):1477–1489

    Article  CAS  Google Scholar 

  • Patlolla AK, Hussain SM, Schlager JJ, Patlolla S, Tchounwou PB (2010) Comparative study of the clastogenicity of functionalized and nonfunctionalized multiwalled carbon nanotubes in bone marrow cells of Swiss-Webster mice. Environ Toxicol 25(6):608–621

    Article  CAS  Google Scholar 

  • Paula AJ, Stefani D, Souza Filho AG, Kim YA, Endo M, Alves OL (2011) Surface chemistry in the process of coating mesoporous SiO(2) onto carbon nanotubes driven by the formation of SiOC bonds. Chemistry 17(11):3228–3237

    Article  CAS  Google Scholar 

  • Petersen EJ, Henry TB (2012) Methodological considerations for testing the ecotoxicity of carbon nanotubes and fullerenes: review. Environ Toxicol Chem 31(1):60–72

    Article  CAS  Google Scholar 

  • Premkumar T, Mezzenga R, Geckeler KE (2012) Carbon nanotubes in the liquid phase: addressing the issue of dispersion. Small 8(9):1299–1313

    Article  CAS  Google Scholar 

  • Raffa V, Ciofania G, Nitodasb S, Karachaliosb T, D’Alessandrod D, Masinie M, Cuschieria A (2008) Can the properties of carbon nanotubes influence their internalization by living cells? Carbon 46(12):1600–1610

    Article  CAS  Google Scholar 

  • Raffa V, Ciofani G, Vittorio O, Riggio C, Cuschieri A (2010) Physicochemical properties affecting cellular uptake of carbon nanotubes. Nanomedicine 5(1):89–97

    Article  CAS  Google Scholar 

  • Romanos GE, Likodimos V, Marques RRN, Steriotis TA, Papageorgiou SK, Faria JL, Figueiredo JL, Silva AMT, Falaras P (2011) Controlling and quantifying oxygen functionalities on hydrothermally and thermally treated single-wall carbon nanotubes. J Phys Chem C 115(17):8534–8546

    Article  CAS  Google Scholar 

  • Rosca ID, Watari F, Uo M, Akaska T (2005) Oxidation of multiwalled carbon nanotubes by nitric acid. Carbon 43(15):3124–3131

    Article  CAS  Google Scholar 

  • Rourke JP, Pandey PA, Moore JJ, Bates M, Kinloch IA, Young RJ, Wilson NR (2011) The real graphene oxide revealed: stripping the oxidative debris from the graphene-like sheets. Angew Chem Int Ed 50(14):3173–3177

    Article  CAS  Google Scholar 

  • Sharifi S, Behzadi S, Laurent S, Forrest ML, Stroeve P, Mahmoudi M (2012) Toxicity of nanomaterials. Chem Soc Rev 41(6):2323–2343

    Article  CAS  Google Scholar 

  • Singh RP, Das M, Thakare V, Jain S (2012) Functionalization density dependent toxicity of oxidized multiwalled carbon nanotubes in a murine macrophage cell line. Chem Res Toxicol 25(10):2127–2137

    Article  CAS  Google Scholar 

  • Smith B, Wepasnick K, Schrote KE, Bertele AH, Ball WP, O’Melia C, Fairbrother DH (2009) Colloidal properties of aqueous suspensions of acid-treated, multi-walled carbon nanotubes. Environ Sci Technol 43(3):819–825

    Article  CAS  Google Scholar 

  • Stefani D, Paula AJ, Vaz BG, Silva RA, Andrade NF, Justo GZ, Ferreira CV, Filho AG, Eberlin MN, Alves OL (2011) Structural and proactive safety aspects of oxidation debris from multiwalled carbon nanotubes. J Hazard Mater 189(1–2):391–396

    Article  CAS  Google Scholar 

  • Tan CW, Tan KH, Ong YT, Mohamed AR, Zein SHS, Tan SH (2012) Energy and environmental applications of carbon nanotubes. Environ Chem Lett 10(3):265–273

    Article  CAS  Google Scholar 

  • Tobias G, Shao LD, Ballesteros B, Green MLH (2009) Enhanced sidewall functionalization of single-wall carbon nanotubes using nitric acid. J Nanosci Nanotechnol 9(10):6072–6077

    Article  CAS  Google Scholar 

  • Tripathi S, Sonkar SK, Sarkar S (2011) Growth stimulation of gram (Cicer arietinum) plant by water soluble carbon nanotubes. Nanoscale 3(3):1176–1181

    Article  CAS  Google Scholar 

  • Vardharajula S, Ali SZ, Tiwari PM, Eroglu E, Vig K, Dennis VA, Singh SR (2012) Functionalized carbon nanotubes: biomedical applications. Int J Nanomed 7:5361–5374

    CAS  Google Scholar 

  • Verdejo R, Lamoriniere S, Cottam B, Bismarck A, Shaffer M (2007) Removal of oxidation debris from multi-walled carbon nanotubes. Chem Commun 5:513–515

    Article  Google Scholar 

  • Villagarcia H, Dervishi E, de Silva K, Biris AS, Khodakovskaya MV (2012) Surface chemistry of carbon nanotubes impacts the growth and expression of water channel protein in tomato plants. Small 8(15):2328–2334

    Article  CAS  Google Scholar 

  • Wang Z, Korobeinyk A, Whitby RLD, Meikle ST, Mikhalovsky SV, Acquah SFA, Kroto HW (2010) Direct confirmation that carbon nanotubes still react covalently after removal of acid-oxidative lattice fragments. Carbon 48(3):916–918

    Article  CAS  Google Scholar 

  • Warheit DB (2008) How meaningful are the results of nanotoxicity studies in the absence of adequate material characterization? Toxicol Sci 101(2):183–185

    Article  CAS  Google Scholar 

  • Wick P, Manser P, Limbach LK, Dettlaff-Weglikowska U, Krumeich F, Roth S, Stark WJ, Bruinink A (2007) The degree and kind of agglomeration affect carbon nanotube cytotoxicity. Toxicol Lett 168(2):121–131

    Article  CAS  Google Scholar 

  • Worsley KA, Kalinina I, Bekyarova E, Haddon RC (2009) Functionalization and dissolution of nitric acid treated single-walled carbon nanotubes. J Am Chem Soc 131(50):18153–18158

    Article  CAS  Google Scholar 

  • Wu WH, Chen W, Lin DH, Yang K (2012) Influence of surface oxidation of multiwalled carbon nanotubes on the adsorption affinity and capacity of polar and nonpolar organic compounds in aqueous phase. Environ Sci Technol 46(10):5446–5454

    Article  CAS  Google Scholar 

  • Yu H, Jin YG, Peng F, Wang HJ, Yang J (2008) Kinetically controlled side-wall functionalization of carbon nanotubes by nitric acid oxidation. J Phys Chem C 112(17):6758–6763

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors acknowledge partial funding from CAPES through PROCAD and NANOBIOTEC programs and from CNPq-MCTI through INCTs Inomat and NanoBioSimes. A.G.S.F. acknowledges funding from Fundação Cearense de Apoio ao Desenvolvimento Científico e Tecnológico (FUNCAP) through PRONEX (Grant PR2-0054-00022.01.00/11) and CNPq (Grants 482767/2010-3 and 307317/2010-2). Finally, we also demonstrated that only an integrated characterization approach will make possible the association of the MWCNTs features with the biological effects manifested from the insertion of these nanomaterials in the nanobiotechnological context

Author information

Authors and Affiliations

  1. Departamento de Física, Universidade Federal do Ceará, P.O. Box 6030, Fortaleza, CE, CEP 60455-900, Brazil

    Nádia F. Andrade, José V. Silveira & Antonio G. Souza Filho

  2. Laboratório de Química do Estado Sólido (LQES), Instituto de Química, Universidade Estadual de Campinas (UNICAMP), Campinas, SP, CEP 13084-970, Brazil

    Diego Stéfani T. Martinez, Amauri J. Paula & Oswaldo L. Alves

Authors
  1. Nádia F. Andrade
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Diego Stéfani T. Martinez
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Amauri J. Paula
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. José V. Silveira
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Oswaldo L. Alves
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Antonio G. Souza Filho
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Nádia F. Andrade, Diego Stéfani T. Martinez, Amauri J. Paula, Oswaldo L. Alves or Antonio G. Souza Filho.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Andrade, N.F., Martinez, D.S.T., Paula, A.J. et al. Temperature effects on the nitric acid oxidation of industrial grade multiwalled carbon nanotubes. J Nanopart Res 15, 1761 (2013). https://doi.org/10.1007/s11051-013-1761-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11051-013-1761-8

Keywords

Search

Navigation