Nitrogen-Doped Graphene: The Influence of Doping Level on the Charge-Transfer Resistance and Apparent Heterogeneous Electron Transfer Rate

Three nitrogen-doped graphene samples were synthesized by the hydrothermal method using urea as doping/reducing agent for graphene oxide (GO), previously dispersed in water. The mixture was poured into an autoclave and placed in the oven at 160 degrees C for 3, 8 and 12 h. The samples were correspondingly denoted NGr-1, NGr-2 and NGr-3. The effect of the reaction time on the morphology, structure and electrochemical properties of the resulting materials was thoroughly investigated using scanning electron microscopy (SEM) Raman spectroscopy, X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), elemental analysis, Cyclic Voltammetry (CV) and electrochemical impedance spectroscopy (EIS). For NGr-1 and NGr-2, the nitrogen concentration obtained from elemental analysis was around 6.36 wt%. In the case of NGr-3, a slightly higher concentration of 6.85 wt% was obtained. The electrochemical studies performed with NGr modified electrodes proved that the charge-transfer resistance (R-ct) and the apparent heterogeneous electron transfer rate constant (K-app) depend not only on the nitrogen doping level but also on the type of nitrogen atoms found at the surface (pyrrolic-N, pyridinic-N or graphitic-N). In our case, the NGr-1 sample which has the lowest doping level and the highest concentration of pyrrolic-N among all nitrogen-doped samples exhibits the best electrochemical parameters: a very small R-ct (38.3 Omega), a large K-app (13.9 x 10(-2) cm/s) and the best electrochemical response towards 8-hydroxy-20-deoxyguanosine detection (8-OHdG).