Skip to main content
SpringerLink
Log in

Synthesis and characterization of a single-walled carbon nanotubes/l-cysteine/Nafion-ionic liquid nanocomposite and its application in the ultrasensitive determination of Cd(II) and Pb(II)

  • Research Article
  • Published:
Journal of Applied Electrochemistry Aims and scope Submit manuscript

Abstract

In this paper, an electrochemical sensor was fabricated for the sensitive and simultaneous analysis of Pb(II) and Cd(II) by the modification of glassy carbon electrodes (GCEs) with a dispersion of l-cysteine-functionalized single-walled carbon nanotubes (SWCNs) incorporating Nafion and ionic liquid (IL) (SWCNs/l-cysteine/Nafion-IL/GCE). The SWCNs were functionalized by the covalent interaction between the −NH3 groups of l-cysteine and −COOH groups of pyrene carboxylic acid (PCA), and this interaction was activated by N-ethyl-N′(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxysulfosuccinimide (NHS). The modification of PCA on the SWCNs was realized by noncovalent π–π stacking interactions between the PCA molecules and SWCNs. The prepared nanocomposite was characterized by square-wave anodic stripping voltammetry (SWASV), electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) and cyclic voltammetry (CV). By combining the outstanding adsorption capacity of l-cysteine and Nafion toward Pb(II) and Cd(II) with the advantages of SWCNs and ILs, the modified SWCNs/l-cysteine/Nafion-IL/GCE composite showed excellent detection performance, including good stability, high sensitivity and selectivity. Under the optimal conditions, the concentration of target heavy metals (HMs) was significantly linear with corresponding stripping currents for Pb(II) and Cd(II) in the concentration range of 0–50 μg L−1. The limits of detection for Cd(II) and Pb(II) were 0.05 μg L−1 and 0.08 μg L−1, respectively. Finally, SWCNs/l-cysteine/Nafion-IL/GCEs were successfully applied in the determination of Pb(II) and Cd(II) in real samples, and the results were compared with those of an atomic absorption spectrometry (AAS) analysis.

Graphical abstract

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
Fig. 8

Similar content being viewed by others

References

  1. Waters CN, Zalasiewicz J, Summerhayes C, Barnosky AD, Poirier C, Gałuszka A, Cearreta A, Edgeworth M, Ellis EC, Ellis M, Jeandel C, Leinfelder R, McNeill JR, Richter DD, Steffen W, Syvitski J, Vidas D, Wagreich M, Williams M, Zhisheng A, Grinevald J, Odada E, Oreskes N, Wolfe AP (2016) The anthropocene is functionally and stratigraphically distinct from the holocene. Science. https://doi.org/10.1126/science.aad2622

    Article  PubMed  PubMed Central  Google Scholar 

  2. Wright IA, Ryan MM (2016) Impact of mining and industrial pollution on stream macro invertebrates: importance of taxonomic resolution, water geochemistry and EPT indices for impact detection. Hydrobiologia 772:103

    Article  CAS  Google Scholar 

  3. Wan M-W, Kan C-C, Rogel BD, Dalida MLP (2010) Adsorption of copper (II) and lead (II) ions from aqueous solution on chitosan-coated sand. Carbohydr Polym 80:891

    Article  CAS  Google Scholar 

  4. Mohammed H, Sadeek S, Mahmoud AR, Zaky D (2016) Comparison of AAS, EDXRF, ICP-MS and INAA performance for determination of selected heavy metals in HFO ashes. Microchem J 128:1

    Article  CAS  Google Scholar 

  5. Armendariz CR, Garcia T, Soler A, Fernandez AJG, Glez-Weller D, Gonzalez GL, de la Torre AH, Girones CR (2015) Heavy metals in cigarettes for sale in Spain. Environ Res 143:162

    Article  CAS  Google Scholar 

  6. Dimpe KM, Ngila JC, Mabuba N, Nomngongo PN (2014) Evaluation of sample preparation methods for the detection of total metal content using inductively coupled plasma optical emission spectrometry (ICP-OES) in wastewater and sludge. Phys Chem Earth 76–78:42

    Article  Google Scholar 

  7. Caballero-Segura B, Avila-Pérez P, Barrera C, Ramírez J, Zarazúa G, Soria R, Ortiz-Oliveros HB (2014) Metal content in mosses from the metropolitan area of the Toluca Valley: a comparative study between inductively coupled plasma optical emission spectrometry (ICP-OES) and total reflection X-ray fluorescence spectrometry (TXRF). Int J Environ Anal Chem 94:1288

    Article  CAS  Google Scholar 

  8. Dede ÖT (2016) A case study for measurement uncertainty of heavy metal analysis in drinking water with inductively coupled plasma-mass spectrometry (ICP-MS). Anal Methods 8:5087

    Article  CAS  Google Scholar 

  9. Su S, He M, Zhang N, Cui C (2014) Calconcarboxylic acid dynamically modified nanometer-sized zirconia for on-line flow injection-inductively coupled plasma optical emission spectrometry determination of trace heavy metals in environmental water samples. Anal Methods 6:1182

    Article  CAS  Google Scholar 

  10. Olorundare OFM, Msagati TA, Krause RWM, Okonkwo JO, Mamba B (2015) Polyurethane composite adsorbent using solid phase extraction method for preconcentration of metal ion from aqueous solution. Int J Environ Sci Technol 12:2389

    Article  CAS  Google Scholar 

  11. Liao Y, Li Q, Wang N, Shao S (2015) Development of a new electrochemical sensor for determination of Hg(II) based on Bis (indolyl) methane/mesoporous carbon nanofiber/Nafion/glassy carbon electrode. Sens Actuators B 215:592

    Article  CAS  Google Scholar 

  12. Morton J, Havens N, Mugweru A, Wanekaya AK (2009) Detection of trace heavy metal ions using carbon nanotube- modified electrodes. Electroanalysis 21:1597

    Article  CAS  Google Scholar 

  13. Deng W, Tan Y, Fang Z, Xie Q, Li Y, Liang X, Yao S (2009) ABTS-multiwalled carbon nanotubes nanocomposite/Bi film electrode for sensitive determination of Cd and Pb by differential pulse stripping voltammetry. Electroanalysis 21:2477

    CAS  Google Scholar 

  14. Chamjangali MA, Kouhestani H, Masdarolomoor F, Daneshinejad H (2015) A voltammetric sensor based on the glassy carbon electrode modified with multi-walled carbon nanotube/poly(pyrocatechol violet)/bismuth film for determination of cadmium and lead as environmental pollutants. Sens Actuators B 216:384

    Article  CAS  Google Scholar 

  15. Li NC, Manning RA (1955) Some metal complexes of sulfur-containing amino acids. J Am Chem Soc 77:5225

    Article  CAS  Google Scholar 

  16. Shah BG (1981) Chelating agents and biovailability of minerals. Nutr Res 1:617

    Article  CAS  Google Scholar 

  17. Aliberti A, Vaiano P, Caporale A, Consales M, Ruvo M, Cusano A (2017) Fluorescent chemosensors for Hg2+ detection in aqueous environment. Sens Actuators B 247:727

    Article  CAS  Google Scholar 

  18. Gilsanz C, Gusmão R, Chekmeneva E, Serrano N, Díaz-Cruz JM, Ariño C, Esteban M (2011) Electroanalysis of the binding and adsorption of Hg2+ with seleno aminoacids by differential pulse and elimination voltammetry at the Au-disk electrode. Electrochim Acta 56:5988

    Article  CAS  Google Scholar 

  19. Wang J, Musameh M, Lin Y (2003) Solubilization of carbon nanotubes by nafion toward the preparation of amperometric biosensors. J Am Chem Soc 125:2408

    Article  CAS  PubMed  Google Scholar 

  20. Rubianes MD, Rivas GA (2007) Dispersion of multi-wall carbon nanotubes in polyethylenimine: a new alternative for preparing electrochemical sensors. Electrochem Commun 9:480

    Article  CAS  Google Scholar 

  21. Jalit Y, Rodríguez MC, Rubianes MD, Bollo S, Rivas GA (2008) Glassy carbon electrodes modified with multiwall carbon nanotubes dispersed in polylysine. Electroanalysis 20:1623

    Article  CAS  Google Scholar 

  22. Tiwari I, Singh KP, Singh M, Banks CE (2012) Polyaniline/polyacrylic acid/multi-walled carbon nanotube modified electrodes for sensing ascorbic acid. Anal Methods 4:118

    Article  CAS  Google Scholar 

  23. Legeai S, Vittori O (2006) A Cu/Nafion/Bi electrode for on-site monitoring of trace heavy metals in natural waters using anodic stripping voltammetry: an alternative to mercury-based electrodes. Anal Chim Acta 560:184

    Article  CAS  Google Scholar 

  24. Krasnodêbska-Ostrêga B, Kowalska J (2003) Ultrasound-assisted acetic acid extraction of metals from soils. Chem Anal 48:967

    Google Scholar 

  25. Zhao G, Wang H, Liu G, Wang Z (2016) Optimization of stripping voltammetric sensor by a back propagation artificial neural network for the accurate determination of Pb(II) in the presence of Cd(II). Sensors 16:1540

    Article  CAS  Google Scholar 

  26. Zhao G, Wang H, Liu G (2017) Direct quantification of Cd2+ in the presence of Cu2+ by a combination of anodic stripping voltammetry using a Bi-film-modified glassy carbon electrode and an artificial neural network. Sensors 17:1558

    Article  CAS  Google Scholar 

  27. Xu H, Zeng L, Huang D, Xian Y, Jin L (2008) A nafion-coated bismuth film electrode for the determination of heavy metals in vegetable using differential pulse anodic stripping voltammetry: an alternative to mercury-based electrodes. Food Chem 109:834

    Article  CAS  PubMed  Google Scholar 

  28. Ramírez ML, Tettamanti CS, Gutierrez FA, Gonzalez-Domínguez JM, Ansón-Casaos A, Hernández-Ferrer J, Martínez MT, Rivas GA, Rodríguez MC (2018) Cysteine functionalized bio-nanomaterial for the affinity sensing of Pb(II) as an indicator of environmental damage. Microchem J 141:271

    Article  CAS  Google Scholar 

  29. Gutierrez FA, Gonzalez-Dominguez JM, Ansón-Casaos A, Hernández-Ferrer J, Rubianes MD, Martínez MT, Rivas G (2017) Single-walled carbon nanotubes covalently functionalized with cysteine: a new alternative for the highly sensitive and selective Cd(II) quantification. Sens Actuators B 249:506

    Article  CAS  Google Scholar 

  30. Qin D, Hu X, Dong Y, Mamat X, Li Y, Wågberg T, Hu G (2018) An electrochemical sensor based on green γ-AlOOH-carbonated bacterial cellulose hybrids for simultaneous determination trace levels of Cd(II) and Pb(II) in drinking water. J Electrochem Soc 165:B328

    Article  CAS  Google Scholar 

  31. Xiao L, Xu H, Zhou S, Song T, Wang H, Li S, Gan W, Yuan Q (2014) Simultaneous detection of Cd(II) and Pb(II) by differential pulse anodic stripping voltammetry at a nitrogen-doped microporous carbon/Nafion/bismuth-film electrode. Electrochim Acta 143:143

    Article  CAS  Google Scholar 

  32. Dai H, Wang N, Wang D, Ma H, Lin M (2016) An electrochemical sensor based on phytic acid functionalized polypyrrole/graphene oxide nanocomposites for simultaneous determination of Cd(II) and Pb(II). Chem Eng J 299:150

    Article  CAS  Google Scholar 

  33. Zhu L, Xu L, Huang B, Jia N, Tan L, Yao S (2014) Simultaneous determination of Cd(II) and Pb(II) using square wave anodic stripping voltammetry at a gold nanoparticle-graphene-cysteine composite modified bismuth film electrode. Electrochim Acta 115:471

    Article  CAS  Google Scholar 

  34. Zhang Y, Zhang J, Liu Y, Huang H, Kang Z (2012) Highly ordered three-dimensional macroporous carbon spheres for determination of heavy metal ions. Mater Res Bull 47:1034

    Article  CAS  Google Scholar 

  35. Zhao G, Wang H, Yin Y, Liu G (2017) PSO-SVM applied to SWASV studies for accurate detection of Cd (II) based on disposable electrode. Int J Agr Biol Eng 10:251

    Google Scholar 

  36. Crowley K, Cassidy J (2002) Trace analysis of lead at a nafion-modified electrode using square-wave anodic stripping voltammetry. Electroanalysis 14:1077

    Article  CAS  Google Scholar 

  37. Kokkinos C, Economou A, Raptis I, Efstathiou CE (2008) Lithographically fabricated disposable bismuth-film electrodes for the trace determination of Pb(II) and Cd(II) by anodic stripping voltammetry. Electrochim Acta 53:5294

    Article  CAS  Google Scholar 

  38. Li BL, Wu ZL, Xiong CH, Luo HQ, Li NB (2012) Anodic stripping voltammetric measurement of trace cadmium at tin-coated carbon paste electrode. Talanta 88:707

    Article  CAS  PubMed  Google Scholar 

  39. Lezi N, Economou A, Dimovasilis PA, Trikalitis PN, Prodromidis MI (2012) Disposable screen-printed sensors modified with bismuth precursor compounds for the rapid voltammetric screening of trace Pb(II) and Cd(II). Anal Chim Acta 728:1

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

This work was supported by the General Program of the National Natural Science Foundation of China (No. 31671578) and the National High Technology Research and Development Program of China (No. 2013AA102302).

Author information

Authors and Affiliations

  1. Key Laboratory of Modern Precision Agriculture System Integration Research, Ministry of Education of China, China Agricultural University, Beijing, 100083, People’s Republic of China

    Guo Zhao & Gang Liu

  2. Key Laboratory of Agricultural Information Acquisition Technology, Ministry of Agricultural of China, China Agricultural University, Beijing, 100083, People’s Republic of China

    Guo Zhao & Gang Liu

Authors
  1. Guo Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Gang Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Gang Liu.

Ethics declarations

Conflict of interests

The author(s) declare that they have no competing interests.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhao, G., Liu, G. Synthesis and characterization of a single-walled carbon nanotubes/l-cysteine/Nafion-ionic liquid nanocomposite and its application in the ultrasensitive determination of Cd(II) and Pb(II). J Appl Electrochem 49, 609–619 (2019). https://doi.org/10.1007/s10800-019-01309-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10800-019-01309-y

Keywords

Search

Navigation