Electrochemical determination of lead(II) and copper(II) by using phytic acid and polypyrrole functionalized metal-organic frameworks.

A glassy carbon electrode (GCE) was modified with a composite prepared from phytic acid, polypyrrole and a ZIF type metal-organic framework (PA/PPy)/ZIF-8@ZIF-67). The nanocomposite was prepared by in-situ chemical polymerization in the presence of ferric chloride and subsequently functionalized with PA to form PA/PPy/ZIF-8@ZIF-67. The materials were characterized by XRD, FT-IR, BET, XPS, SEM and TEM. The modified GCE was applied to individual and simultaneous detection of Pb(II) and Cu(II), with peak voltages of -0.6 and - 0.1 V, respectively (vs. SCE). The amount of PPy, the ZIF-8@ZIF-67 concentration, polymerization potential, polymerization time and pH value were optimized. Under optimized conditions, the calibration plots have two linear ranges. These are from 0.02 to 200 μM and from 200 to 600 μM for Pb(II), and from 0.2 to 200 μM and 200 to 600 μM for Cu(II). The detection limits are 2.9 nM and 14.8 nM, respectively. Simultaneous detection of Pb(II) and Cu(II) is also demonstrated. The good performance of the electrode is attributed to the large surface area of ZIF-8@ZIF-67, the good electrical conductivity of PPy, and the metal complexation power of PA. The modified GCE was successfully applied to the determination of Pb(II) and Cu(II) in real samples and gave satisfactory recoveries. Graphical abstractSchematic presentation of the construction process of PA/PPy/ZIF-8@ZIF-67/GCE sensor, and the mechanism of Pb(II) and Cu(II) at the prepared sensor.