Microchimica Acta

, 186:623 | Cite as

Preparation of reduced graphite oxide loaded with cobalt(II) and nitrogen co-doped carbon polyhedrons from a metal-organic framework (type ZIF-67), and its application to electrochemical determination of metronidazole

  • Han Chen
  • Xingxing Wu
  • Rui Zhao
  • Zhou Zheng
  • Qunhui YuanEmail author
  • Zhijun DongEmail author
  • Wei GanEmail author
Original Paper


The integration of derivatives of granular metal-organic frameworks (MOFs) and an electrically conductive carbon substrate is an effective way to circumvent the deficiency of powdered pristine MOFs or MOF-derived carbon in practical application. The authors describe the use of graphite oxide (GO) as a substrate for in-situ assembly with the zeolitic imidazole framework ZIF-67. The GO and ZIF-67 composites were converted, via pyrolysis, into reduced graphite oxide loaded with Co/N-co-doped carbon polyhedrons (ZIF-67C@rGO). By using various amounts of GO, a series of ZIF-67C@rGO-x with different fractions of GO were synthesized and utilized as electrode modifiers for the detection of the antibiotic metronidazole (MNZ). The results revealed that the ZIF-67C@rGO-0.06 display best sensing performance. This is likely to be due to its hierarchically open pores, abundant active sites and good electrical conductivity. The sensor, best operated near a working potential around −0.6 V (vs. SCE), has a linear response in the 0.5 to 1000 μM MNZ concentration range and a 0.05 μM detection limit. The sensor was applied to the analysis of pharmaceutical samples where it showed excellent selectivity, good repeatability and satisfying recoveries.

Graphical abstract

Schematic representation of preparation and application of ZIF-67C@rGO-x.


Chemically modified electrode ZIF-67C@rGO In-situ growth Electrochemical sensor Differential pulse voltammetry 



This work was financially supported by the National Natural Science Foundation of China (21473247), the fundamental research fund from Shenzhen (JCYJ20170811153306372, JCYJ20170307150520453) and Start up Foundations from Shenzhen and Harbin Institute of Technology (Shenzhen).

Compliance with ethical standards

The authors declare that they have no competing interests.

Supplementary material

604_2019_3737_MOESM1_ESM.doc (1.2 mb)
ESM 1 (DOC 1275 kb)


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Copyright information

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

Authors and Affiliations

  1. 1.State Key Laboratory of Advanced Welding and Joining, and School of Materials Science and EngineeringHarbin Institute of Technology (Shenzhen)ShenzhenChina
  2. 2.Institute of Technology for Marine Civil EngineeringShenzhen Institute of Information TechnologyShenzhenChina
  3. 3.State Key Laboratory of Advanced Welding and Joining, and School of ScienceHarbin Institute of Technology (Shenzhen)ShenzhenChina

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