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Nonenzymatic amperometric sensor for hydrogen peroxide released from living cancer cells based on hierarchical NiCo2O4-CoNiO2 hybrids embedded in partially reduced graphene oxide

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Abstract

The synthesis of hierarchical NiCo2O4-CoNiO2 hybrids embedded in partially reduced graphene oxide (represented by NiCo2O4/CoNiO2@pPRGO) is described. They were derived from ultrathin CoNi-based zeolitic imidazolate framework (CoNi-ZIF) nanosheets vertically grew on three-dimensional (3D) pRGO networks by pyrolysis at different temperatures (300, 600, and 900 °C) in N2 atmosphere. Transmission electron microscopy, X-ray diffraction, and X-ray photoemission spectroscopy measurements showed that the metal coordination centers (Co or Ni) were transferred into NiCo2O4 spinel and CoNiO2 nanostructures, along with a small number of metallic states of Co and Ni. In view of good electrochemical conductivity and large specific surface area of pRGO, good catalytic activity of Co- and Ni-contained NPs, and homogeneous distribution of NPs within the pRGO network, the NiCo2O4/CoNiO2@pRGO600 nanohybrid calcined at 600 °C displayed superior electrocatalytic activity toward hydrogen peroxide (H2O2) reduction. A glassy carbon electrode modified with NiCo2O4/CoNiO2@pRGO600 was used for determination of H2O2 by amperometry at an applied potential of − 0.4 V vs. Ag/AgCl. The nonenzymatic amperometric sensor exhibited high sensitivity and low detection limit (0.41 μM) within a wide working range (5 μM–3 mM and 3–12 mM) toward H2O2, as well as good selectivity, reproducibility, and long-term stability. Benefiting from the good biocompatibility and remarkable analytical performances of NiCo2O4/CoNiO2@pRGO600, the assay was used to determine real-time H2O2 released from living cancer cells.

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Funding

This work was financially supported by the National Natural Science Foundation of China (No. U1604127), the Scientific and Technological Project of Henan Province (Nos. 192102310261 and 192102310460), the Key Research Project of University of Henan Province (No. 19zx004), the Scientific Research Fund of Doctor in Zhengzhou University of Light Industry (No. 2018BSJJ028), and the Young Backbone Teacher Training Program in Universities of Henan Province (No. 2018GGJS089).

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Authors and Affiliations

  1. Henan Provincial Key Laboratory of Surface and Interface Science, Zhengzhou University of Light Industry, Zhengzhou, 450001, People’s Republic of China

    Minghua Wang, Changbao Wang, Yongkang Liu, Bin Hu, Linghao He, Yashen Ma, Zhihong Zhang, Bingbing Cui & Miao Du

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  1. Minghua Wang
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  2. Changbao Wang
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Wang, M., Wang, C., Liu, Y. et al. Nonenzymatic amperometric sensor for hydrogen peroxide released from living cancer cells based on hierarchical NiCo2O4-CoNiO2 hybrids embedded in partially reduced graphene oxide. Microchim Acta 187, 436 (2020). https://doi.org/10.1007/s00604-020-04419-z

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