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Nonenzymatic electrochemical sensing of hydrogen peroxide based on a polyaniline-MnO2 nanofiber-modified glassy carbon electrode

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Abstract

We report the synthesis of polyaniline-manganese dioxide (PANI-MnO2) nanofibers and their applications as nonenzymatic electrochemical sensors for the determination of hydrogen peroxide (H2O2). The PANI-MnO2 nanofibers were synthesized via a one-step mixing process from the as-prepared PANI nanofiber aqueous dispersion and the aqueous solution of KMnO4. The morphology and chemical composition of the synthesized PANI-MnO2 nanofibers were characterized by field-emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy, and X-ray diffraction. A facile electrochemical hydrogen peroxide sensor based on a PANI-MnO2-modified glassy carbon electrode (PANI-MnO2/GCE) was fabricated by a drop-casting method, and its electrochemical behavior was investigated using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and amperometry. The results clearly exhibited good electrocatalytic activity of the PANI-MnO2/GCE toward H2O2 reduction in pH 7.4 phosphate buffer solution (PBS). The nonenzymatic H2O2 sensor displayed a wide linear range (5–50 μM and 0.05–10 mM), low detection limit (0.8 μM at S/N = 3), high sensitivity (403.3 μA mM−1 cm−2), and negligible interference from ascorbic acid, uric acid, l-cysteine, and glucose at an applied detection potential of −0.4 V (vs. Ag/AgCl).

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References

  1. Chen W, Cai S, Ren Q-Q, Wen W, Zhao Y-D (2012) Recent advances in electrochemical sensing for hydrogen peroxide: a review. Analyst 137:49–58

    Article  CAS  Google Scholar 

  2. Klassen NV, Marchington D, McGowan HCE (1994) H2O2 determination by the I3 − method and by KMnO4 titration. Anal Chem 66:2921–2925

    Article  CAS  Google Scholar 

  3. Hanaoka S, Lin J-M, Yamada M (2001) Chemiluminescent flow sensor for H2O2 based on the decomposition of H2O2 catalyzed by cobalt(II)-ethanolamine complex immobilized on resin. Anal Chim Acta 426:57–64

    Article  CAS  Google Scholar 

  4. Li Y, Townshend A (1998) Evaluation of the adsorptive immobilisation of horseradish peroxidase on PTFE tubing in flow systems for hydrogen peroxide determination using fluorescence. Anal Chim Acta 359:149–156

    Article  CAS  Google Scholar 

  5. Matsubara C, Kawamoto N, Takamura K (1992) Oxo[5, 10, 15, 20-tetra(4-pyridyl)porphyrinato]titanium(IV): an ultra-high sensitivity spectrophotometric reagent for hydrogen peroxide. Analyst 117:1781

    Article  CAS  Google Scholar 

  6. Chen A, Chatterjee S (2013) Nanomaterials based electrochemical sensors for biomedical applications. Chem Soc Rev 42:5425–5438

    Article  CAS  Google Scholar 

  7. Wang Y, Ma X, Wen Y, Xing Y, Zhang Z, Yang H (2010) Direct electrochemistry and bioelectrocatalysis of horseradish peroxidase based on gold nano-seeds dotted TiO2 nanocomposite. Biosens Bioelectron 25:2442–2446

    Article  CAS  Google Scholar 

  8. Huang K-J, Niu D-J, Liu X, Wu Z-W, Fan Y, Chang Y-F, Wu Y-Y (2011) Direct electrochemistry of catalase at amine-functionalized graphene/gold nanoparticles composite film for hydrogen peroxide sensor. Electrochim Acta 56:2947–2953

    Article  CAS  Google Scholar 

  9. Xiang C, Zou Y, Sun L-X, Xu F (2008) Direct electron transfer of cytochrome c and its biosensor based on gold nanoparticles/room temperature ionic liquid/carbon nanotubes composite film. Electrochem Commun 10:38–41

    Article  CAS  Google Scholar 

  10. Guo H-L, Liu D-Y, Yu X-D, Xia X-H (2009) Direct electrochemistry and electrocatalysis of hemoglobin on nanostructured gold colloid-silk fibroin modified glassy carbon electrode. Sensors Actuators B 139:598–603

    Article  CAS  Google Scholar 

  11. Mu Y, Jia D, He Y, Miao Y, Wu H-L (2011) Nano nickel oxide modified non-enzymatic glucose sensors with enhanced sensitivity through an electrochemical process strategy at high potential. Biosens Bioelectron 26:2948–2952

    Article  CAS  Google Scholar 

  12. Salimi A, Hallaj R, Soltanian S, Mamkhezri H (2007) Nanomolar detection of hydrogen peroxide on glassy carbon electrode modified with electrodeposited cobalt oxide nanoparticles. Anal Chim Acta 594:24–31

    Article  CAS  Google Scholar 

  13. Wang B, Luo L, Ding Y, Zhao D, Zhang Q (2012) Synthesis of hollow copper oxide by electrospinning and its application as a nonenzymatic hydrogen peroxide sensor. Colloids Surf B Biointerfaces 97:51–56

    Article  CAS  Google Scholar 

  14. Liu Z, Zhao B, Shi Y, Guo C, Yang H, Li Z (2010) Novel nonenzymatic hydrogen peroxide sensor based on iron oxide-silver hybrid submicrospheres. Talanta 81:1650–1654

    Article  CAS  Google Scholar 

  15. Butwong N, Zhou L, Ng-eontae W, Burakham R, Moore E, Srijaranai S, Luong JHT, Glennon JD (2014) A sensitive nonenzymatic hydrogen peroxide sensor using cadmium oxide nanoparticles/multiwall carbon nanotube modified glassy carbon electrode. J Electroanal Chem 717–718:41–46

    Article  Google Scholar 

  16. Wang Q, Zheng J (2010) Electrodeposition of silver nanoparticles on a zinc oxide film: improvement of amperometric sensing sensitivity and stability for hydrogen peroxide determination. Microchim Acta 169:361–365

    Article  CAS  Google Scholar 

  17. Xiao X, Song Y, Liu H, Xie M, Hou H, Li Wang, Li Z (2013) Electrospun carbon nanofibers with manganese dioxide nanoparticles for nonenzymatic hydrogen peroxide sensing. J Mater Sci 48:4843–4850

    Article  CAS  Google Scholar 

  18. Luo L, Li F, Zhu L, Zhang Z, Ding Y, Deng D (2012) Non-enzymatic hydrogen peroxide sensor based on MnO2-ordered mesoporous carbon composite modified electrode. Electrochim Acta 77:179–183

    Article  CAS  Google Scholar 

  19. Wang A-J, Zhang P-P, Li Y-F, Feng J-J, Dong W-J, Liu X-Y (2011) Hydrogen peroxide sensor based on glassy carbon electrode modified with β-manganese dioxide nanorods. Microchim Acta 175:31–37

    Article  CAS  Google Scholar 

  20. Xu B, Ye M-L, Yu Y-X, Zhang W-D (2010) A highly sensitive hydrogen peroxide amperometric sensor based on MnO2-modified vertically aligned multiwalled carbon nanotubes. Anal Chim Acta 674:20–26

    Article  CAS  Google Scholar 

  21. Li Y, Zhang J, Zhu H, Yang F, Yang X (2010) Gold nanoparticles mediate the assembly of manganese dioxide nanoparticles for H2O2 amperometric sensing. Electrochim Acta 55:5123–5128

    Article  CAS  Google Scholar 

  22. Yao S, Xu J, Wang Y, Chen X, Xu Y, Hu S (2006) A highly sensitive hydrogen peroxide amperometric sensor based on MnO2 nanoparticles and dihexadecyl hydrogen phosphate composite film. Anal Chim Acta 557:78–84

    Article  CAS  Google Scholar 

  23. Yao S, Yuan S, Xu J, Wang Y, Luo J, Hu S (2006) A hydrogen peroxide sensor based on colloidal MnO2/Na-montmorillonite. Appl Clay Sci 33:35–42

    Article  CAS  Google Scholar 

  24. Hocevar S, Ogorevc B, Schachl K, Kalcher K (2004) Glucose microbiosensor based on MnO2 and glucose oxidase modified carbon fiber microelectrode. Electroanalysis 16:1711–1716

    Article  CAS  Google Scholar 

  25. Han Y, Zheng J, Dong S (2013) A novel nonenzymatic hydrogen peroxide sensor based on Ag–MnO2–MWCNTs nanocomposites. Electrochim Acta 90:35–43

    Article  CAS  Google Scholar 

  26. Li L, Du Z, Liu S, Hao Q, Wang Y, Li Q, Wang T (2010) A novel nonenzymatic hydrogen peroxide sensor based on MnO2/graphene oxide nanocomposite. Talanta 82:1637–1641

    Article  CAS  Google Scholar 

  27. Wang L, Deng M, Ding G, Chen S, Xu F (2013) Manganese dioxide based ternary nanocomposite for catalytic reduction and nonenzymatic sensing of hydrogen peroxide. Electrochim Acta 114:416–423

    Article  CAS  Google Scholar 

  28. Do S-H, Batchelor B, Lee H-K, Kong S-H (2009) Hydrogen peroxide decomposition on manganese oxide (pyrolusite): kinetics, intermediates, and mechanism. Chemosphere 75:8–12

    Article  CAS  Google Scholar 

  29. Yu G, Hu L, Vosgueritchian M, Wang H (2011) Solution-processed graphene/MnO2 nanostructured textiles for high-performance electrochemical capacitors. Nano Lett 11:2905–2911

    Article  CAS  Google Scholar 

  30. Babu KJ, Zahoor A, Nahm KS, Ramachandran R, Rajan MAJ, Gnana kumar G (2014) The influences of shape and structure of MnO2 nanomaterials over the non-enzymatic sensing ability of hydrogen peroxide. J Nanopart Res 16:2250

    Article  Google Scholar 

  31. Toupin M, Brousse T, Bélanger D (2002) Influence of microstucture on the charge storage properties of chemically synthesized manganese dioxide. Chem Mater 14:3946–3952

    Article  CAS  Google Scholar 

  32. Bakardjieva S, Bezdička P, Grygar T, Vorm P (2000) Reductive dissolution of microparticulate manganese oxides. J Solid State Electrochem 4:306–313

    Article  CAS  Google Scholar 

  33. Li D, Huang J, Kaner RB (2009) Polyaniline nanofibers: a unique polymer nanostructure for versatile applications. Acc Chem Res 42:135–145

    Article  CAS  Google Scholar 

  34. Huang W, Humphrey BD, MacDiarmid AG (1986) Polyaniline, a novel conducting polymer. Morphology and chemistry of its oxidation and reduction in aqueous electrolytes. J Chem Soc Faraday Trans 82:2385–2400

    Article  CAS  Google Scholar 

  35. Šljukić B, Stojković I, Cvijetićanin N, Ćirić-Marjanović G (2011) Hydrogen peroxide sensing at MnO2/carbonized nanostructured polyaniline electrode. Russ J Phys Chem A 85:2406–2409

    Article  Google Scholar 

  36. Huang J, Kaner RB (2004) A general chemical route to polyaniline nanofibers. J Am Chem Soc 126:851–855

    Article  CAS  Google Scholar 

  37. Jiang H, Ma J, Li C (2012) Polyaniline–MnO2 coaxial nanofiber with hierarchical structure for high-performance supercapacitors. J Mater Chem 22:16939–16942

    Article  CAS  Google Scholar 

  38. Anu PMU, Srivastava R, Satpati B (2013) Simultaneous detection of guanine, adenine, thymine, and cytosine at polyaniline/MnO2 modified electrode. Electrochim Acta 114:285–295

    Article  Google Scholar 

  39. Dong X, Shen W, Gu J, Xiong L, Zhu Y, Li H, Shi J (2006) MnO2-embedded-in-mesoporous-carbon-wall structure for use as electrochemical capacitors. J Phys Chem B 110:6015–6019

    Article  CAS  Google Scholar 

  40. Xiao F, Li Y, Zan X, Liao K, Xu R, Duan H (2012) Growth of metal-metal oxide nanostructures on freestanding graphene paper for flexible biosensors. Adv Funct Mater 22:2487–2494

    Article  CAS  Google Scholar 

  41. Li D, Huang J, Kaner RB (2009) Polyaniline nanofibers: a unique polymer nanostructure for versatile applications. Acc Chem Res 42:135–145

    Article  CAS  Google Scholar 

  42. Luo J, Chen Y, Ma Q, Liu R, Liu X (2013) Layer-by-layer self-assembled hybrid multilayer films based on poly(sodium 4-styrenesulfonate) stabilized graphene with polyaniline and their electrochemical sensing properties. RSC Adv 3:17866–17873

    Article  CAS  Google Scholar 

  43. Cheng F, Su Y, Liang J, Tao Z, Chen J (2010) MnO2-based nanostructures as catalysts for electrochemical oxygen reduction in alkaline media. Chem Mater 22:898–905

    Article  CAS  Google Scholar 

  44. Mao L, Zhang D, Sotomura T, Nakatsu K, Koshiba N, Ohsaka T (2003) Mechanistic study of the reduction of oxygen in air electrode with manganese oxides as electrocatalysts. Electrochim Acta 48:1015–1021

    Article  CAS  Google Scholar 

  45. Gong K, Yu P, Su L, Xiong S, Mao L (2007) Polymer-assisted synthesis of manganese dioxide/carbon nanotube nanocomposite with excellent electrocatalytic activity toward reduction of oxygen. J Phys Chem C 111:1882–1887

    Article  CAS  Google Scholar 

  46. Roche I, Scott K (2010) Effect of pH and temperature on carbon-supported manganese oxide oxygen reduction electrocatalysts. J Electroanal Chem 638:280–286

    Article  CAS  Google Scholar 

  47. Liu Z, Han Q, Ni P, Liu Z, Dong X, Wang Y, Li Z (2014) Enhanced hydrogen peroxide sensing by incorporating manganese dioxide nanowire with silver nanoparticles. Electrochem Commun 38:110–113

    Article  Google Scholar 

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  1. Department of Chemistry Education, Seoul National University, Seoul, 151-748, Korea

    Jong-Hyeok Lee & Hun-Gi Hong

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  1. Jong-Hyeok Lee
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Correspondence to Hun-Gi Hong.

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Lee, JH., Hong, HG. Nonenzymatic electrochemical sensing of hydrogen peroxide based on a polyaniline-MnO2 nanofiber-modified glassy carbon electrode. J Appl Electrochem 45, 1153–1162 (2015). https://doi.org/10.1007/s10800-015-0881-5

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