Citation: . Detection of dopamine at graphene-ZIF-8 nanocomposite modified electrode[J]. Chinese Chemical Letters, ;2017, 28(7): 1473-1478. doi: 10.1016/j.cclet.2017.03.014 shu

Detection of dopamine at graphene-ZIF-8 nanocomposite modified electrode

Received Date: 5 December 2016
Revised Date: 8 March 2017
Accepted Date: 9 March 2017
Available Online: 11 July 2017

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A hybrid graphene-ZIF-8 (G-ZIF-8) nanocomposite modified electrode was prepared in our work. SEM characterization shows that nanocrystals of zeolitic imidazolate frameworks (ZIF-8) were homogeneously well-intergrown on the surface of graphene and thus the graphene sheets were refrained from restacking, which implies the high accessible surface area. The BET results further testifies that G-ZIF-8 composites had a larger surface area than 3D graphene. G-ZIF-8 modified electrode exhibited excellent electroanalytical performance for dopamine. The linear concentration range was from 3.0 μmol/L to 1.0 μmol/L with the detection sensitivity of 0.34 μA/μmol/L and the detection limit of 1.0 μmol/L was obtained. The interference study, electrode stability and reproducibility were carried out. In addition, the prepared sensor was applied to the detection of DA in serum sample with recoveries from 96.8% to 100.7%. It is believable that the structure characteristic of G-ZIF-8 nanocomposite is favorable for using MOFs to fabricate highly sensitive electrochemical sensor.
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Figure 1. SEM images of ZIF-8 (A), G (B) and G-ZIF-8 composite (C and D) on the surface of GCE at different magnifications.

Figure 2. N₂ adsorption-desorption isotherms and pore size distributions for ZIF-8 (A, B) G-ZIF-8 (C, D) and G (E, F). (STP = standard temperature and pressure).

Figure 3. (A) Cyclic voltammograms of bare GCE, ZIF8/GCE, G/GCE and G-ZIF8/GCE at a scan rate of 50 mV/s. (B) Cyclic voltammograms of G-ZIF8/GCE with different scan rates: 20, 50, 100, 150, 200, 250, 300 and 400 mV/s (from inner to outer). Electrolyte: 5.0 × 10^-3 mol/L Ru(NH₃)₆Cl₃/0.1 mol/L KCl solution. Inset: plots of the anodic and cathodic peak currents (I_Pa and I_Pc) vs. the square root of scan rate.

Figure 4. Cyclic voltammograms of 50 μmol/L DA at bare GCE, ZIF8/GCE, G/GCE and GZIF8/GCE in 0.1 mol/L PBS (pH 7.0). Scan rate: 50 mV/s. Insert: magnification of CV curves of ZIF8/GCE and bare GCE.

Figure 5. Cyclic voltammograms of G-ZIF8/GCE in pH 7.0 PBS containing of 50 mmol/L DA at different scan rates (as the arrow direction): 50, 100, 150, 200, 250, 300, 400 and 500 mV/s. Inset: calibration plot for corresponding anodic and cathodic peak currents versus the scan rate.

Figure 6. Cyclic voltammograms obtained at G-ZIF8/GCE in 0.1 mol/L PBS containing 50 μmol/L DA with various pH value: 5.0 (black line), 6.0 (red line), 7.0 (blue line), 8.0 (purple line), 9.0 (green line). Scan rate: 50 mV/s. Inset: plot of E^0' against pH value.

Figure 7. (A) Current-time response curves of ZIF8/GCE, G/GCE and G-ZIF8/GCE upon successive additions of (a) 3.0' 10^-6 mol/L, (b) 2.0 ×10^-6 mol/L, (c) 5 × 10^-6 mol/L, (d) 1.0 × 10^-5 mol/L and (e) 1.0 × 10^-4 mol/L DA in pH 7.0 PBS with a constant stirring rate at an applied potential of 0.30 V. (B) Calibration plots for response current versus the concentration of DA.

Figure 8. Amperometric response curve of G-ZIF8/GCE upon successive additions of (a) 0.20 mmol/L DA, (b) 0.40 mmol/L uric acid, (c) 20mmol/L glucose, (d) 0.88 mmol/L hydrogen peroxide, (e) 30 μmol/L ascorbic acid and (f) 0.20 mmol/L DA to a stirred 0.1 mol/L pH 7.0 PBS at a potential of 0.30 V.