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Electrochemical detection of 2,4,6-trinitrotoluene on carbon nanotube modified electrode: Effect of acid functionalization

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Abstract

This work presents new insights on the electrocatalytic reduction of 2,4,6-trinitrotoluene (TNT) on carbon nanotubes (CNTs)-modified electrodes (multi-walled carbon nanotubes and double-walled carbon nanotubes). Cyclic voltammetry showed at least 5-fold current increase in the electrochemical reduction of TNT on GCE modified with pristine (“as received”) CNTs. The improved performance was also verified after 60 s of accumulation and scanning using adsorptive stripping voltammetry, with slope values 20-fold higher. Acid functionalization removed residual metals from CNTs and reduced their surface area. Hence, the improved electrochemical response of TNT on pristine CNTs seems to be not only due to surface roughness (electroactive area) but mainly originating from residual metallic catalysts on CNTs. The modified electrode with pristine CNTs was applied for the determination of TNT residues on different surfaces contaminated with the explosive, showing its applicability for forensic investigations.

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References

  1. De Volder MFL, Tawfick SH, Baughman RH, Hart AJ (2013) Carbon nanotubes: Present and future commercial applications. Science 339(6119):535–539

    PubMed  Google Scholar 

  2. Bozal-Palabiyik B, Dogan-Topal B, Uslu B et al (2013) Sensitive voltammetric assay of etoposide using modified glassy carbon electrode with a dispersion of multi-walled carbon nanotube. J Solid State Electrochem 17:2815–2822

    CAS  Google Scholar 

  3. Dogan-Topal B (2013) Electrooxidative behavior and determination of trifluoperazine at multiwalled carbon nanotube-modified glassy carbon electrode. J Solid State Electrochem 17:1059–1066

    CAS  Google Scholar 

  4. Fagan-Murphy A, Kataria S, Patel BA (2016) Electrochemical performance of multi-walled carbon nanotube composite electrodes is enhanced with larger diameters and reduced specific surface area. J Solid State Electrochem 20:785–792

    CAS  Google Scholar 

  5. Rezaei B, Damiri S (2010) Development of a voltammetric procedure for assay of thebaine at a multi-walled carbon nanotubes electrode: Quantification and electrochemical studies. J Solid State Electrochem 14:1079–1088

    CAS  Google Scholar 

  6. De Zhang W, Xu B, Hong YX et al (2010) Electrochemical oxidation of salicylic acid at well-aligned multiwalled carbon nanotube electrode and its detection. J Solid State Electrochem 14:1713–1718

    CAS  Google Scholar 

  7. Ziyatdinova G, Gainetdinova A, Morozov M et al (2012) Voltammetric detection of synthetic water-soluble phenolic antioxidants using carbon nanotube based electrodes. J Solid State Electrochem 16:127–134

    CAS  Google Scholar 

  8. Zukalová M, Tarábek J, Kalbáč M et al (2008) In situ optical spectroelectrochemistry of single-walled carbon nanotube thin films. J Solid State Electrochem 12:1279–1284

    Google Scholar 

  9. Ordeñana-Martínez AS, Rincón ME, Vargas M et al (2012) Carbon nanotubes/carbon xerogel-nafion electrodes: A comparative study of preparation methods. J Solid State Electrochem 16:3777–3782

    Google Scholar 

  10. Montes RHO, Dornellas RM, Silva LAJ et al (2016) Amperometric determination of the insecticide fipronil using batch injection analysis: comparison between unmodified and carbon-nanotube-modified electrodes. J Solid State Electrochem 20:2453–2459

    CAS  Google Scholar 

  11. Moutab Sahihazar M, Ahmadi MT, Nouri M, Rahmani M (2019) Quantum conductance investigation on carbon nanotube–based antibiotic sensor. J Solid State Electrochem 23:1641–1650

    CAS  Google Scholar 

  12. Banks CE, Crossley A, Salter C et al (2006) Carbon nanotubes contain metal impurities which are responsible for the “electrocatalysis” seen at some nanotube-modified electrodes. Angew Chemie - Int Ed 45:2533–2537

    CAS  Google Scholar 

  13. Stefano JS, Rocha DP, Dornellas RM et al (2017) Highly sensitive amperometric detection of drugs and antioxidants on non-functionalized multi-walled carbon nanotubes: Effect of metallic impurities? Electrochim Acta 240:80–89

    CAS  Google Scholar 

  14. Wang J (2005) Carbon-nanotube based electrochemical biosensors: A review. Electroanalysis 17:7–14

    CAS  Google Scholar 

  15. Cardoso RM, Montes RHO, Lima AP et al (2015) Multi-walled carbon nanotubes: Size-dependent electrochemistry of phenolic compounds. Electrochim Acta 176:36–43

    CAS  Google Scholar 

  16. Pumera M, Miyahara Y (2009) What amount of metallic impurities in carbon nanotubes is small enough not to dominate their redox properties? Nanoscale 1:260–265

    CAS  PubMed  Google Scholar 

  17. Smith JP, Foster CW, Metters JP et al (2014) Metallic Impurities in Graphene Screen-Printed Electrodes Can Influence Their Electrochemical Properties. Electroanalysis 26:2429–2433

    CAS  Google Scholar 

  18. Kruusma J, Mould N, Jurkschat K et al (2007) Single walled carbon nanotubes contain residual iron oxide impurities which can dominate their electrochemical activity. Electrochem commun 9:2330–2333

    CAS  Google Scholar 

  19. Pumera M (2007) Carbon nanotubes contain residual metal catalyst nanoparticles even after washing with nitric acid at elevated temperature because these metal nanoparticles are sheathed by several graphene sheets. Langmuir 23:6453–6458

    CAS  PubMed  Google Scholar 

  20. Mendoza E, Henley SJ, Poa CHP et al (2005) Large area growth of carbon nanotube arrays for sensing platforms. Sensors Actuators, B Chem 109:75–80

    CAS  Google Scholar 

  21. Pumera M, Iwai H (2009) Metallic impurities within residual catalyst metallic nanoparticles are in some cases responsible for “electrocatalytic” effect of carbon nanotubes. Chem - An Asian J 4:554–560

    CAS  Google Scholar 

  22. Jones CP, Jurkschat K, Crossley A et al (2007) Use of high-purity metal-catalyst-free multiwalled carbon nanotubes to avoid potential experimental misinterpretations. Langmuir 23:9501–9504

    CAS  PubMed  Google Scholar 

  23. Alwarappan S, Erdem A, Liu C, Li C-Z (2009) Probing the Electrochemical Properties of Graphene Nanosheets for Biosensing Applications. J Phys Chem C 113:8853–8857

    CAS  Google Scholar 

  24. Wang L, Chua C, Khezri B, Webster R (2016) Remarkable electrochemical properties of electrochemically reduced graphene oxide towards oxygen reduction reaction are caused by residual metal-based. Electrochemistry 62:17–20

    CAS  Google Scholar 

  25. Sljukić B, Banks CE, Compton RG (2006) Iron oxide particles are the active sites for hydrogen peroxide sensing at multiwalled carbon nanotube modified electrodes. Nano Lett 6:1556–1558

    PubMed  Google Scholar 

  26. Dai X, Wildgoose GG, Compton RG (2006) Apparent “electrocatalytic” activity of multiwalled carbon nanotubes in the detection of the anaesthetic halothane: occluded copper nanoparticles. Analyst 131:901–906

    CAS  PubMed  Google Scholar 

  27. Yu HA, DeTata DA, Lewis SW, Silvester DS (2017) Recent developments in the electrochemical detection of explosives: Towards field-deployable devices for forensic science. TrAC - Trends Anal Chem 97:374–384

    CAS  Google Scholar 

  28. Pereira De Oliveira L, Rocha DP, Reis De Araujo W et al (2018) Forensics in hand: New trends in forensic devices (2013-2017). Anal Methods 10:5135–5163

    Google Scholar 

  29. de Araujo WR, Cardoso TMG, da Rocha RG et al (2018) Portable analytical platforms for forensic chemistry: A review. Anal Chim Acta 1034:1–21

    PubMed  Google Scholar 

  30. Wang J, Hocevar SB, Ogorevc B (2004) Carbon nanotube-modified glassy carbon electrode for adsorptive stripping voltammetric detection of ultratrace levels of 2,4,6-trinitrotoluene. Electrochem commun 6:176–179

    CAS  Google Scholar 

  31. Pedrotti JJ, Angnes L, Gutz IGR (1996) Miniaturized reference electrodes with microporous polymer junctions. Electroanalysis 8:673–675

    Google Scholar 

  32. Vuković G, Marinković A, Obradović M et al (2009) Synthesis, characterization and cytotoxicity of surface amino-functionalized water-dispersible multi-walled carbon nanotubes. Appl Surf Sci 255:8067–8075

    Google Scholar 

  33. Krzyzaniak SR, Iop GD, Holkem AP et al (2019) Determination of inorganic contaminants in carbon nanotubes by plasma- based techniques : Overcoming the limitations of sample preparation. Talanta 192:255–262

    CAS  PubMed  Google Scholar 

  34. Brauner S, Emmet PH, Teller E (1936) Adsorption of Gases in Multimolecular Layers. J Am Chem Soc 60:309–319

    Google Scholar 

  35. Barrett EP, Joyner LG, Halenda PP (1951) The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms. J Am Chem Soc 73:373–380

    CAS  Google Scholar 

  36. Chua CK, Pumera M, Rulíšek L (2012) Reduction pathways of 2,4,6-trinitrotoluene: An electrochemical and theoretical study. J Phys Chem C 116:4243–4251

    CAS  Google Scholar 

  37. Castro SVF, Cardoso RM, Santana MHP et al (2019) Graphite sheet as a novel material for the collection and electrochemical sensing of explosive residues. Talanta 203:106–111

    CAS  PubMed  Google Scholar 

  38. Yang R, Wei Y, Yu Y et al (2012) Make it different: The plasma treated multi-walled carbon nanotubes improve electrochemical performances toward nitroaromatic compounds. Electrochim Acta 76:354–362

    CAS  Google Scholar 

  39. Lima AP, Catto AC, Longo E et al (2019) Investigation on acid functionalization of double-walled carbon nanotubes of different lengths on the development of amperometric sensors. Electrochim Acta 299:762–771

    CAS  Google Scholar 

  40. Ehrenberg H, Svoboda I, Wiesmann M et al (1999) A mixed transition metal molybdate, β-(Co0. 7Fe0. 3) MoO4. Acta Cryst C 55:1383–1384

    Google Scholar 

  41. Stuart EJE, Pumera M (2010) Electrochemistry of a whole group of compounds affected by metallic impurities within carbon nanotubes. J Phys Chem C 114:21296–21298

    CAS  Google Scholar 

  42. Cañete-Rosales P, Ortega V, Álvarez-Lueje A et al (2012) Influence of size and oxidative treatments of multi-walled carbon nanotubes on their electrocatalytic properties. Electrochim Acta 62:163–171

    Google Scholar 

  43. Mkhondo NB, Magadzu T (2014) Effects of different acid-treatment on the nanostructure and performance of carbon nanotubes in electrochemical hydrogen storage. Dig J Nanomater Biostructures 9:1331–1338

    Google Scholar 

  44. Hrapovic S, Majid E, Liu Y et al (2006) Metallic nanoparticle-carbon nanotube composites for electrochemical determination of explosive nitroaromatic compounds. Anal Chem 78:5504–5512

    CAS  PubMed  Google Scholar 

Download references

Acknowledgements

The authors are grateful to CAPES (PRO FORENSES–Process number 23038.007073/2014-12 and 001), CNPq (465389/2014-7 INCTBio and 307271/2017-0), FAPESP (2018/16896-7), FAPEMIG (RED-00042-16) for financial support. The authors would also like to thank the department of chemistry at Federal University of Minas Gerais for supplying the TNT samples and for assistance in the analysis. This work was partially supported by the Brazilian Institute of Science and Technology (INCT) in Bioanalytics (INCTBio) and in Carbon nanomaterials (INCTCarbon). We also thank the facilities for the AFM measurements at the Institute of Physics (INFIS) at Federal University of Uberlândia (UFU), supported by the grant “Pró-Equipamentos” from the Brazilian Agency CAPES. We also thank Prof. Koiti Araki (Laboratório de Química Supramolecular e Nanotecnologia, IQ-USP) for the use of XRD facility.

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Authors and Affiliations

  1. Institute of Chemistry, Federal University of Uberlândia, Av. João Naves de Ávila, Uberlândia, MG, 2121, Brazil

    Jéssica S. Stefano, Ana P. Lima, Eduardo M. Richter, Edson Nossol & Rodrigo A. A. Munoz

  2. Department of Chemistry, Federal University of Minas Gerais, Avenida Presidente Antônio Carlos, 6627, Pampulha, Belo Horizonte, MG, 31270-901, Brazil

    Clésia C. Nascentes

  3. Department of Chemistry, Federal University of Santa Maria, Av. Roraima, 1000, Santa Maria, RS, 97105-900, Brazil

    Sindy R. Krzyzaniak & Paola A. Mello

  4. Department of Fundamental Chemistry, Institute of Chemistry, University of São Paulo, Av. Prof. Lineu Prestes, 748, São Paulo, SP, 05508-000, Brazil

    Josué M. Gonçalves

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  1. Jéssica S. Stefano
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  2. Ana P. Lima
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Correspondence to Rodrigo A. A. Munoz.

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Stefano, J.S., Lima, A.P., Nascentes, C.C. et al. Electrochemical detection of 2,4,6-trinitrotoluene on carbon nanotube modified electrode: Effect of acid functionalization. J Solid State Electrochem 24, 121–129 (2020). https://doi.org/10.1007/s10008-019-04465-5

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