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.

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.