Electrochemical Determination of Copper in Aqueous Media at a Carbon Paste Electrode Modified with Natural-Based Nanocomposite and Carbon Nanotubes

 Somayeh Mohammadi Somayeh Mohammadi, Mohammad Ali TaherMohammad Ali Taher, Hadi BeitollahiHadi Beitollahi
Российский электрохимический журнал
Abstract / Full Text

We report a simple method of accumulation and electrochemical determination of copper(II) ions using a carbon paste electrode modified with a nanocomposite of Fe3O4/eggshell and carbon nanotubes in aqueous samples. Under stirring, Cu(II) was deposited on the modified electrode and the electrochemical response was amplified. The accumulated Cu(II) on the electrode showed a voltammetric peak at a potential about –0.1 V in 0.2 M HCl solution, which could be used for the measurement of Cu(II). Under optimal conditions, Cu(II) could be detected in the range from 0.5 to 310 ng mL–1 with a detection limit of 0.033 ng mL–1. In particular, with the use of the reduction peak of Cu(II), the modified electrode exhibits excellent performance for Cu(II) determination even in the presence of interference ions. The regeneration of the electrode is facile with good reproducibility. The electrochemical system was applied to analyze Cu(II) in drinking water, wastewater, hair samples, and certified reference materials. In addition to Fourier transform infrared spectroscopy (FT-IR) and vibrating sample magnetometer (VSM) for the characterization of the prepared magnetic nanocomposite, the morphology and structure of Fe3O4/eggshell were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD).

Author information
  • Department of Chemistry, Faculty of Sciences, Shahid Bahonar University of Kerman, Kerman, Iran

    Somayeh Mohammadi & Mohammad Ali Taher

  • Young Researchers Society, Shahid Bahonar University of Kerman, Kerman, Iran

    Somayeh Mohammadi

  • Environment Department, Institute of Science and High Technology and Environmental Sciences, Graduate University of Advanced Technology, Kerman, Iran

    Hadi Beitollahi

  1. Wang, Z., Wang, H., Zhang, Z., and Liu, G., Electrochemical determination of lead and cadmium in rice by a disposable bismuth/electrochemically reduced graphene/ionic liquid composite modified screen-printed electrode, Sens. Actuator B-Chem., 2014, vol. 199, p. 7.
  2. Kang, W., Pei, X., Rusinek, C.A., Bange, A., Haynes, E.N., Heineman, W.R., and Papautsky, I., Determination of lead with a copper-based electrochemical sensor, Anal. Chem., 2017, vol. 89, p. 3345.
  3. Pokpas, K., Jahed, N., Baker, P.G., and Iwuoha, E.I., Complexation-based detection of nickel(II) at a graphene-chelate probe in the presence of cobalt and zinc by adsorptive stripping voltammetry, Sensors, 2017, vol. 17, p. 1711.
  4. De Jesus, R.M., Silva, L.O., Castro, J.T., de Azevedo Neto, A.D., de Jesus, R.M., and Ferreira, S.L., Determination of mercury in phosphate fertilizers by cold vapor atomic absorption spectrometry, Talanta, 2013, vol. 106, p. 293.
  5. Germiniano, T.O., Corazza, M.Z., Segatelli, M.G., and Tarley, C.R.T., Double-imprinted cross-linked poly(Acrylamide-co-Ethylene Glycol Dimethacrylate) as a novel sorbent for the on-line preconcentration and determination of copper(II) by flame atomic absorption spectrometry, Anal. Lett., 2014, vol. 48, p. 61.
  6. Richter, E.M., Augelli, M.A., Magarotto, S., and Angnes, L., Compact disks, a new source for gold electrodes. Application to the quantification of copper by PSA, Electroanalysis, 2001, vol. 13, p. 760.
  7. Sadeghi, S., Eslahi, M., Naseri, M.A., Sharghi, H., and Shameli, A., Copper ion selective membrane electrodes based on some schiff base derivatives, Electroanalysis, 2003, vol. 15, p.1327.
  8. Catalani, S., Paganelli, M., Gilberti, M.E., Rozzini, L., Lanfranchi, F., Padovani, A., and Apostoli, P., Free copper in serum: analytical challenge and its possible applications, J. Trace Elem. Med. Biol., 2018, vol. 45, p. 176.
  9. Bohrer, D., do Nascimento, P.C., Ramirez, A.G., Mendonca, J.K.A., De Carvalho, L.M., and Pomblum, S.C.G., Comparison of ultrafiltration and solid phase extraction for the separation of free and protein-bound serum copper for the Wilson’s disease diagnosis, Clin. Chim. Acta, 2004, vol. 345, p. 113.
  10. Synhaivska, O., Mermoud, Y., Baghernejad, M., Alshanski, I., Hurevich, M., Yitzchaik, S., Wipf, M., and Calame, M., Detection of Cu2+ ions with GGH peptide realized with Si-nanoribbon ISFET, Sensors, 2019, vol. 19, p. 4022.
  11. Nasiri-Majd, M., Taher, M.A., and Fazelirad, H., Preparation and application of a simple electrochemical sensor for the determination of copper in some real and standard samples, Ionics, 2016, vol. 22, p. 289.
  12. Niu, L.M., Luo, H.Q., Li, N.B., and Song, L., Electrochemical detection of copper (II) at a gold electrode modified with a self-assembled monolayer of penicillamine, J. Anal. Chem., 2007, vol. 62, p. 470.
  13. Ender Mulazioğlu, I., Electrochemical determination of copper(II) ions at naringenin-modified glassy carbon electrode: application in lake water sample, Desalin. Water Treat., 2012, vol. 44, p. 161.
  14. Wang, Z.H., Choi, C.J., Kim, B.K., Kim, J.C., and Zhang, Z.D., Characterization and magnetic properties of carbon-coated cobalt nanocapsules synthesized by the chemical vapor-condensation process, Carbon, 2003, vol. p. 1751.
  15. Huang, S.H., Liao, M.H., and Chen, D.H., Direct binding and characterization of lipase onto magnetic nanoparticles, Biotechnol. Prog., 2003, vol. 19, p. 1095.
  16. Rossi, L.M., Quach, A.D., and Rosenzweig, Z., Glucose oxidase-magnetite nanoparticle bioconjugate for glucose sensing, Anal. Bioanal. Chem., 2004, vol. 380, p. 606.
  17. Zhao, G., Feng, J.J., Zhang, Q.L., Li, S.P., and Chen, H.Y., Synthesis and characterization of Prussian blue modified magnetite nanoparticles and its application to the electrocatalytic reduction of H2O2, Chem. Mater., 2005, vol. 17, p. 3154.
  18. Katz, E. and Willner, I., Magnetic control of chemical transformations: application for programmed electrocatalysis and surface patterning, Electrochem. Commun., 2002, vol. 4, p. 201.
  19. Katz, E., Baron, R., and Willner, I., Magnetoswitchable electrochemistry gate by alkyl-chain-functionalized magnetic nanoparticles: control of diffusional and surface-sonfined electrochemical processes, J. Am. Chem. Soc., 2005, vol. 127, p. 4060.
  20. Willner, I. and Katz, E., Controlling chemical reactivity at solid-solution interfaces by means of hydrophobic magnetic nanoparticles, Langmuir, 2006, vol. 22, p. 1409.
  21. Engineering of Polymers and Chemical Complexity: Current State of the Art and Perspectives, Liu, L. and Ballada, A., Eds., CRC Press, 2014, vol. 1.
  22. Souza, T.R., de Sa, A.C., dos Santos Franco, F., Fernanda, P., Barbosa, P., Andrade, R.D.A., da Costa, F.M., Alves, K., Carvalho, D.R.D.O., Cumba, L.R., and Paim, L.L., Voltammetric behavior of a chemically modified carbon paste electrode with cadmium nitroprusside prepared in different water to formamide ratios, Int. J. Electrochem. Sci., 2020, vol. 15, p. 774.
  23. Iijima, S., Helical microtubules of graphitic carbon, Nature, 1991, vol. 354, p. 56.
  24. Mohammadi, S., Beitollahi, H., and Mohadesi, A., Electrochemical behaviour of a modified carbon nanotube paste electrode and its application for simultaneous determination of epinephrine, uric acid and folic acid, Sens. Lett., 2013, vol. 11, p. 388.
  25. Beitollahi, H. and Mohammadi, S., Selective voltammetric determination of norepinephrine in the presence of acetaminophen and tryptophan on the surface of a modified carbon nanotube paste electrode, Mater. Sci. Eng. C, 2013, vol. 33, p. 3214.
  26. Beitollahi, H., Tajik, S., and Jahani, S., Electrocatalytic determination of hydrazine and phenol using a carbon paste electrode modified with ionic liquids and magnetic core-shell Fe3O4@SiO2/MWCNT nanocomposite, Electroanalysis, 2016, vol. 28, p. 1093.
  27. Wang, K., Huang, Y., Qin, X., Wang, M., Sun, X., and Yu, M., Effect of pyrolysis temperature of 3D graphene/carbon nanotubes anode materials on yield of carbon nanotubes and their electrochemical properties for Na-ion batteries, Chem. Eng. J., 2017, vol. 317, p. 793.
  28. Beitollahi, H., Raoof, J.B., and Hosseinzadeh, R., Application of a carbon-paste electrode modified with 2,7-bis(ferrocenyl ethyl)fluoren-9-one and carbon nanotubes for voltammetric determination of levodopa in the presence of uric acid and folic acid, Electroanalysis, 2011, vol. 23, p. 1934.
  29. Wang, Y., Cao, X., Li, J., and Chen, N., A new cataluminescence gas sensor based on SiO2 nanotubes fabricated using carbon nanotube templates, Talanta, 2011, vol. 84, p. 977.
  30. Beitollahi, H., Mohadesi, A., Mohammadi, S., and Akbari, A., Electrochemical behavior of a carbon paste electrode modified with 5-amino-3′,4′-dimethyl-biphenyl-2-ol/carbon nanotube and its application for simultaneous determination of isoproterenol, acetaminophen and N-acetylcysteine, Electrochim. Acta, 2012, vol. 68, p. 220.
  31. Wang, Y., Yeh, F.C., Lai, S.M., Chan, H.C., and Shen, H.F.F., Effectiveness of functionalized polyolefins as compatibilizers for polyethylene/wood flour composites, Polym. Eng. Sci., 2003, vol. 43, p. 933.
  32. Guru, P.S. and Dash, S., Sorption on eggshell waste – a review on ultrastructure, biomineralization and other applications, J. Colloid Interface Sci., 2014, vol. 209, p. 49.
  33. Mosaddegh, E., Hosseininasab, F.A., and Hassankhani, A., Eggshell/Fe3O4 nanocomposite: novel magnetic nanoparticles coated on porous ceramic eggshell waste as an efficient catalyst in the synthesis of 1,8‑dioxo-octahydroxanthene, RSC Adv., 2015, vol. 5, p. 106561.
  34. Mohammadnezhad, J., Khodabakhshi-Soreshjani, F., and Bakhshi, H., Preparation and evaluation of chitosan-coated eggshell particles as copper(II) biosorbent, Desalin. Water Treat., 2016, vol. 57, p. 1693.
  35. Rais, A., Kumar, R., and Haseeb, S., Adsorption of Cu2+ from aqueous solution onto iron oxide coated eggshell powder: evaluation of equilibrium, isotherms, kinetics, and regeneration capacity, Arab. J. Chem., 2012, vol. 5, p. 353.
  36. Engin, B., Demirtaş, H., and Eken, M., Temperature effects on egg shells investigated by XRD, IR and ESR techniques. Radiat. Phys. Chem., 2006, vol. 75, p. 268.
  37. Ashkenani, H. and Taher, M.A., Selective voltammetric determination of Cu(II) based on multiwalled carbon nanotube and nanoporous Cu-ion imprinted polymer, J. Electroanal. Chem., 2012, vol. 683, p. 80.
  38. Zhihua, W., Xiaole, L., Jianming, Y., Yaxin, Q., and Xiaoquan, L., Copper(II) determination by using carbon paste electrode modified with molecularly imprinted polymer, Electrochim. Acta, 2011, vol. 58, p. 750.
  39. Ashrafi, A.M. and Vytras, K., New procedures for voltammetric determination of copper(II) using antimony film-coated carbon paste electrodes, Electrochim. Acta, 2012, vol. 73, p. 112.
  40. Janegitz, B.C., Marcolino-Junior, L.H., Campana-Filho, S.P., Faria, R.C., and Fatibello-Filho, O., Anodic stripping voltammetric determination of copper(II) using a functionalized carbon nanotubes paste electrode modified with crosslinked chitosan, Sens. Actuators B, 2009, vol. 142, p. 260.