, Volume 25, Issue 11, pp 5527–5536 | Cite as

Electrospun Au nanoparticle-containing ZnO nanofiber for non-enzyme H2O2 sensor

  • Xuan Li
  • Guodong Zhu
  • Jinlei Dou
  • Jianmao Yang
  • Yuanxin Ge
  • Jianyun LiuEmail author
Original Paper


In recent years, metal oxides, especially ZnO, have received extensive attention for non-enzyme biosensors. Au-ZnO composite nanofibers were prepared by one-pot electrospinning a dimethylformamide solution of chloroauric acid and zinc acetate containing polyacrylonitrile and polyvinylpyrrolidone followed by calcination. The morphology, composition, and crystal structure of the prepared Au-ZnO nanofibers were investigated by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction methods. The Au nanoparticles with a face-centered cubic structure were uniformly distributed on the fine ZnO nanofibers. The ZnO fiber with the diameter of 100 ± 20 nm consisted of hexagonal wurtzite structural ZnO particle. Compared to the individual ZnO sample, the presence of Au nanoparticles retains the fibrous structure and enhances the electrical conductivity of the fibers, proved by cyclic voltammetry and electrochemical impedance analysis. By fine-tuning the molar ratio of Au/Zn in the precursor solution, the morphology of Au-ZnO can be controlled. The Au-ZnO composite fiber was used as an enzyme-like catalyst for the sensitive detection of H2O2 based on synergetic catalytic effect of Au nanoparticles and ZnO. Au-ZnO electrode with the Au/Zn atomic ratio of 0.24 shows the highest activity for H2O2 reduction. There was a good linear relationship between catalytic current and H2O2 concentration in the range of 1 × 10−6–6 × 10−3 M (R2 = 0.9994). The detection limit is calculated to be 0.1 × 10−6 M (S/N>3). This Au-ZnO composite fiber can be used as a non-enzyme sensing material for the high sensitive and selective determination of H2O2.


Electrospinning Au-ZnO nanofibers H2O2 Non-enzyme sensor 


Funding information

This work was financially supported by the National Natural Science Foundation (No. 21776045, 21476047).

Supplementary material

11581_2019_3118_MOESM1_ESM.pdf (1.4 mb)
ESM 1 (PDF 1425 kb)


  1. 1.
    Bartlett PN, Birkin PR, Wang JH, Palmisano F, De Benedetto G (1998) An enzyme switch employing direct electrochemical communication between horseradish peroxidase and a poly(aniline) film. Anal Chem 70(17):3685–3694PubMedGoogle Scholar
  2. 2.
    Wang J, Lin Y, Chen L (1993) Organic-phase biosensors for monitoring phenol and hydrogen peroxide in pharmaceutical antibacterial products. Analyst 118(3):277–280PubMedGoogle Scholar
  3. 3.
    Nossol E, Zarbin AJG (2010) A simple and innovative route to prepare a novel carbon nanotube/prussian blue electrode and its utilization as a highly sensitive H2O2 amperometric sensor. Adv Funct Mater 19(24):3980–3986Google Scholar
  4. 4.
    Deyulia GJ, Cárcamo JM, Oriana BO, Shelton CC, Golde DW (2005) Hydrogen peroxide generated extracellularly by receptor-ligand interaction facilitates cell signaling. Proc Natl Acad Sci 102(14):5044–5049PubMedGoogle Scholar
  5. 5.
    Wei J, Liu H, Dick AR, Yamamoto H, He Y, Waldeck DH (2002) Direct wiring of cytochrome c’s heme unit to an electrode: electrochemical studies. J Am Chem Soc 124(32):9591–9599PubMedGoogle Scholar
  6. 6.
    Xiao Y, Patolsky F, Katz E, Hainfeld JF, Willner I (2003) “Plugging into enzymes”: nanowiring of redox enzymes by a gold nanoparticle. Science 299(5614):1877–1881PubMedGoogle Scholar
  7. 7.
    Cao Z, Jiang X, Xie Q, Yao S (2008) A third-generation hydrogen peroxide biosensor based on horseradish peroxidase immobilized in a tetrathiafulvalene-tetracyanoquinodimethane/multiwalled carbon nanotubes film. Biosens Bioelectron 24(2):222–227PubMedGoogle Scholar
  8. 8.
    Wu J, Wang X, Wang Q, Lou Z, Li S, Zhu Y, Qin L, Wei H (2019) Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes (II). Chem Soc Rev 48(4):1004–1076PubMedGoogle Scholar
  9. 9.
    Wen Z, Ci S, Li J (2009) Pt nanoparticles inserting in carbon nanotube arrays: nanocomposites for glucose biosensors. Jphyschemc 113(31):13482–13487Google Scholar
  10. 10.
    Yáñez-Sedeño P, Pingarrón JM (2008) Gold nanoparticle-based electrochemical biosensors. Anal Bioanal Chem 53(19):5848–5866Google Scholar
  11. 11.
    Luo Y, Liu H, Rui Q, Tian Y (2009) Detection of extracellular H2O2 released from human liver cancer cells based on TiO2 nanoneedles with enhanced electron transfer of cytochrome c. Anal Chem 81(8):3035–3041PubMedGoogle Scholar
  12. 12.
    Lee Y, Garcia MA, Frey Huls NA, Sun S (2010) Synthetic tuning of the catalytic properties of Au-Fe3O4 nanoparticles. Angew Chem Int Ed Engl 41(17):1271–1274Google Scholar
  13. 13.
    Park JB, Jesus G, Jaime E, Dario S, Shuguo M, Ping L, Akira N, Javier Fernández S, Jan H, Rodriguez JA (2009) High catalytic activity of Au/CeOx/TiO2(110) controlled by the nature of the mixed-metal oxide at the nanometer level. Proc Natl Acad Sci 106(13):4975–4980PubMedGoogle Scholar
  14. 14.
    Zhou M, Zhai Y, Dong S (2009) Electrochemical sensing and biosensing platform based on chemically reduced graphene oxide. Anal Chem 81(14):5603–5613PubMedGoogle Scholar
  15. 15.
    Xu X, Jiang S, Hu Z, Liu S (2010) Nitrogen-doped carbon nanotubes: high electrocatalytic activity toward the oxidation of hydrogen peroxide and its application for biosensing. ACS Nano 4(7):4292–4298PubMedGoogle Scholar
  16. 16.
    Zhang Y, Kang Z, Yan X, Liao Q (2015) ZnO nanostructures in enzyme biosensors. Sci China Mater 58(1):60–76Google Scholar
  17. 17.
    Li ZH, Gu BX, Manohari AG, Xu CX (2018) Hybrid structures of carbon fiber/ZnO nanorods and their application on enzyme-free sensors for H2O2. J Nanoelectron Optoelectron 13(4):449–453Google Scholar
  18. 18.
    Lin CY, Lai YH, Balamurugan A, Vittal R, Lin CW, Ho KC (2010) Electrode modified with a composite film of ZnO nanorods and Ag nanoparticles as a sensor for hydrogen peroxide. Talanta 82(1):340–347PubMedGoogle Scholar
  19. 19.
    Ke X, Zhu G, Dai Y, Shen Y, Yang J, Liu J (2018) Fabrication of Pt-ZnO composite nanotube modified electrodes for the detection of H2O2. J Electroanal Chem 817:176–183Google Scholar
  20. 20.
    Chen LL, Xu XL, Cui F, Qiu QY, Chen XJ, Xu JZ (2018) Au nanoparticles-ZnO composite nanotubes using natural silk fibroin fiber as template for electrochemical non-enzymatic sensing of hydrogen peroxide. Anal Biochem 554:1–8PubMedGoogle Scholar
  21. 21.
    Chen X, Zhang G, Shi L, Pan S, Liu W, Pan H (2016) Au/ZnO hybrid nanocatalysts impregnated in N-doped graphene for simultaneous determination of ascorbic acid, acetaminophen and dopamine. Mater Sci Eng C Mater Biol Appl 65:80–89PubMedGoogle Scholar
  22. 22.
    Gu H, Yang Y, Tian J, Shi G (2013) Photochemical synthesis of noble metal (Ag, Pd, Au, Pt) on graphene/ZnO multihybrid nanoarchitectures as electrocatalysis for H2O2 reduction. ACS Appl Mater Interfaces 5(14):6762–6768PubMedGoogle Scholar
  23. 23.
    Huang ZM, Zhang YZ, Kotaki M, Ramakrishna S (2003) A review on polymer nanofibers by electrospinning and their applications in nanocomposites. Compos Sci Technol 63(15):2223–2253Google Scholar
  24. 24.
    Pastoriza-Santos I, Liz-Marzán LM (2008) Formation of PVP-protected metal nanoparticles in DMF. Langmuir 18(7):2888–2894Google Scholar
  25. 25.
    Kim SM, Kim GS, Sang YL (2008) Effects of PVP and KCl concentrations on the synthesis of gold nanoparticles using a solution plasma processing. Mater Lett 62(28):4354–4356Google Scholar
  26. 26.
    Kan CX, Wang CS, Zhu JJ, Li HC (2010) Formation of gold and silver nanostructures within polyvinylpyrollidone (PVP) gel. J Solid State Chem 183(4):858–865Google Scholar
  27. 27.
    Fan X, Xu C, Hao X, Tian Z, Lin Y (2014) Synthesis and optical properties of Janus structural ZnO/Au nanocomposites. Europhys Lett 106(6):67001Google Scholar
  28. 28.
    Ju J, Chen W (2015) In situ growth of surfactant-free gold nanoparticles on nitrogen-doped graphene quantum dots for electrochemical detection of hydrogen peroxide in biological environments. Anal Chem 87(3):1903–1910PubMedGoogle Scholar
  29. 29.
    Kang Z, Yan X, Zhao L, Liao Q, Zhao K, Du H, Zhang X, Zhang X, Zhang Y (2015) Gold nanoparticle/ZnO nanorod hybrids for enhanced reactive oxygen species generation and photodynamic therapy. Nano Res 8(6):2004–2014Google Scholar
  30. 30.
    Kaneti YV, Moriceau J, Liu M, Yuan Y, Zakaria Q, Jiang X, Yu A (2015) Hydrothermal synthesis of ternary α-Fe2O3–ZnO–Au nanocomposites with high gas-sensing performance. Sensor Actuators B Chem 209:889–897Google Scholar
  31. 31.
    Lee SW, Han SM, Nix WD (2009) Uniaxial compression of fcc Au nanopillars on an MgO substrate: the effects of prestraining and annealing. Acta Mater 57(15):4404–4415Google Scholar
  32. 32.
    Fageria P, Gangopadhyay S, Pande S (2014) Synthesis of ZnO/Au and ZnO/Ag nano-particles and their photocatalytic application using UV and visible light. RSC Adv 4(48):24962–24972Google Scholar
  33. 33.
    Zhang Z, Jin C, Peterson G, Zhang C, Zhu K, Wei Y, Jian Z (2018) Influence of Au content on photocatalytic performance of C@ZnO@Au hollow nanospheres. Mate Sci Eng: B 230:24–30Google Scholar
  34. 34.
    Fragua DM, Abargues R, Rodriguez-Canto PJ, Sanchez-Royo JF, Agouram S, Martinez-Pastor JP (2015) Au–ZnO nanocomposite films for plasmonic photocatalysis. Adv Mater Interfaces 2(11):1500156–1500165Google Scholar
  35. 35.
    Al-Gaashani R, Radiman S, Daud AR, Tabet N, Al-Douri Y (2013) XPS and optical studies of different morphologies of ZnO nanostructures prepared by microwave methods. Ceram Int 39(3):2283–2292Google Scholar
  36. 36.
    Zhou H, Zhuang L (2005) Synthesis of nanowires, nanorods and nanoparticles of ZnO through modulating the ratio of water to methanol by using a mild and simple solution method. Mater Chem Phys 89(2):326–331Google Scholar
  37. 37.
    Wu M, Chen WJ, Shen YH, Huang FZ, Li CH, Li SK (2014) In situ growth of matchlike ZnO/Au plasmonic heterostructure for enhanced photoelectrochemical water splitting. ACS Appl Mater Interfaces 6(17):15052–15060PubMedGoogle Scholar
  38. 38.
    Zhao G, Xu JJ, Chen HY (2006) Interfacing myoglobin to graphite electrode with an electrodeposited nanoporous ZnO film. Anal Biochem 350(1):145–150PubMedGoogle Scholar
  39. 39.
    Tian H, Fan H, Ma J, Ma L, Dong G (2017) Noble metal-free modified electrode of exfoliated graphitic carbon nitride/ZnO nanosheets for highly efficient hydrogen peroxide sensing. Electrochim Acta 247:787–794Google Scholar
  40. 40.
    Sekar NK, Gumpu MB, Ramachandra BL, Nesakumar N, Sankar P, Babu KJ, Krishnan UM, Jbb R (2018) Fabrication of electrochemical biosensor with ZnO-PVA nanocomposite interface for the detection of hydrogen peroxide. J Nanosci Nanotechnol 18(6):4371–4379PubMedGoogle Scholar
  41. 41.
    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(3–4):361–365Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Xuan Li
    • 1
    • 2
  • Guodong Zhu
    • 1
    • 2
  • Jinlei Dou
    • 1
    • 2
  • Jianmao Yang
    • 3
  • Yuanxin Ge
    • 4
  • Jianyun Liu
    • 1
    • 2
    Email author
  1. 1.College of Environmental Science and Engineering, State Environmental Protection Engineering Center for Pollution Treatment and Control in Textile IndustryDonghua UniversityShanghaiChina
  2. 2.Shanghai Institute of Pollution Control and Ecological SecurityShanghaiPeople’s Republic of China
  3. 3.Research Center for Analysis & MeasurementDonghua UniversityShanghaiPeople’s Republic of China
  4. 4.Shanghai Institute of Supervision on Radiation EnvironmentShanghaiPeople’s Republic of China

Personalised recommendations