Journal of Solid State Electrochemistry

, Volume 23, Issue 2, pp 573–582 | Cite as

Thin layers formed by the oriented 2D nanocrystals of birnessite-type manganese oxide as a new electrochemical platform for ultrasensitive nonenzymatic hydrogen peroxide detection

  • Valeri P. Tolstoy
  • Larisa B. GulinaEmail author
  • Anastasia A. Golubeva
  • Sergei S. Ermakov
  • Vladislav E. Gurenko
  • Daria V. Navolotskaya
  • Nadezhda I. Vladimirova
  • Alexandra V. Koroleva
Original Paper


Thin layers formed by the arrays of the vertically oriented 2-dimensional nanocrystals of Birnessite-type manganese oxide CuxMnO2∙nH2O were synthesized for the first time by the reaction of gaseous ozone with the surface of aqueous solutions of manganese (II) acetate and copper (II) acetate salts mixture. The obtained layers were placed onto the surface of indium tin oxide (ITO)–coated glass electrodes and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), X-Ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). The electrochemical performance of the layers was examined by cyclic voltammetry (CV). It was found that the synthesized structures are formed by the 2D nanocrystals with the thickness of 3–6 nm. The atomic concentration of copper x depends on the ratio of Cu(CH3COO)2 and Mn(CH3COO)2 solution concentrations and can be as much as 0.35. The obtained layers were tested as the electrochemical platform for nonenzymatic hydrogen peroxide sensing. It was shown that the electrode can provide an ultrasensitive H2O2 determination with the limit of detection of 0.4 nМ and linear concentration range that lies in the region of nanomolar concentrations. We assume that the observed effects are due to the morphology of the synthesized layers, which ensures maximum contact of the analyte with the active sites of 2D nanocrystals of CuxMnO2 ∙ nH2O. Comparison of the obtained analytical characteristics with the literature data indicates the good prospects of the synthesized nanomaterial for its use as a working electrode for nonenzymatic H2O2 sensor.


2D crystals δ-MnO2 Gas-solution interface H2O2 Sensor 


Funding information

The study was financially supported by Russian Science Foundation, research project no 16-13-10223. The XRD measurements were carried out at the X-ray Diffraction Centre of Saint-Petersburg State University (SPbSU). The XPS spectra were obtained in the Centre for Physical Methods of Surface Investigation (SPbSU). The SEM and TEM studies were carried out by the Nanotechnology Centre of SPbSU. Electrochemical researches were performed at the Educational Resource Center of Chemistry of SPbSU Research park.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Valeri P. Tolstoy
    • 1
  • Larisa B. Gulina
    • 1
    Email author
  • Anastasia A. Golubeva
    • 1
  • Sergei S. Ermakov
    • 1
  • Vladislav E. Gurenko
    • 1
  • Daria V. Navolotskaya
    • 1
  • Nadezhda I. Vladimirova
    • 1
  • Alexandra V. Koroleva
    • 1
  1. 1.Saint Petersburg State UniversitySt. PetersburgRussia

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