Two graphene samples co-doped with nitrogen and sulfur were synthesized by the hydrothermal method using thiourea as doping and reducing agent for graphene oxide (GO). An appropriate amount of thiourea was added to the aqueous dispersion of GO, previously sonicated for 30 min. The mixture was poured into an autoclave and placed in the oven for 3 h, at 120 and 200 °C. The samples were denoted NSGr-120 and NSGr-200, respectively, in agreement with the reaction temperatures. They were next morphologically and structurally characterized by advanced techniques, such as SEM/TEM, XPS, XRD, and FTIR. According to XPS analysis, the NSGr-120 sample has higher amounts of heteroatoms in comparison with NSGr-200, indicating that the reaction temperature is a crucial factor that affects the doping degree. In order to reveal the influence of the doping degree on the electrochemical performances of graphene-modified electrodes, they were tested in solutions containing L-cysteine molecules. The electrode with the best electrocatalytic performances, GC/NSGr-120, was tested to detect L-cysteine in a pharmaceutical drug, proving its applicability in real sample analysis.

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 °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 Ω), a large K_app (13.9 × 10⁻² cm/s) and the best electrochemical response towards 8-hydroxy-2′-deoxyguanosine detection (8-OHdG).

In this study, a graphene sample (EGr) was synthesized by electrochemical exfoliation of graphite rods in electrolyte solution containing 0.1 M ammonia and 0.1 M ammonium thiocyanate. The morphology of the powder deposited onto a solid substrate was investigated by the scanning electron microscopy (SEM) technique. The SEM micrographs evidenced large and smooth areas corresponding to the basal plane of graphene as well as white lines (edges) where graphene layers fold-up. The high porosity of the material brings a major advantage, such as the increase of the active area of the modified electrode (EGr/GC) in comparison with that of bare glassy carbon (GC). The graphene modified electrode was successfully tested for L-tyrosine detection and the results were compared with those of bare GC. For EGr/GC, the oxidation peak of L-tyrosine had high intensity (1.69 × 10⁻⁵ A) and appeared at lower potential (+0.64 V) comparing with that of bare GC (+0.84 V). In addition, the graphene-modified electrode had a considerably larger sensitivity (0.0124 A/M) and lower detection limit (1.81 × 10⁻⁶ M), proving the advantages of employing graphene in electrochemical sensing.

An electrochemical cell containing two graphite rods was filled with the appropriate electrolyte (0.2 M ammonia + 0.2 M ammonium sulphate) and connected to the exfoliation system to synthesize graphene (EGr). A bias of 7 V was applied between the anode and cathode for 3 h. After synthesis, the morphology and structure of the sample was characterized by SEM, XRD, and FTIR techniques. The material was deposited onto the surface of a glassy carbon (GC) electrode (EGr/GC) and employed for the electrochemical detection of azithromycin (AZT). The DPV signals recorded in pH 5 acetate containing 6 × 10⁻⁵ M AZT revealed significant differences between the GC and EGr/GC electrodes. For EGr/GC, the oxidation peak was higher and appeared at lower potential (+1.12 V) compared with that of bare GC (+1.35 V). The linear range for AZT obtained with the EGr/GC electrode was very wide, 10⁻⁸–10⁻⁵ M, the sensitivity was 0.68 A/M, and the detection limit was 3.03 × 10⁻⁹ M. It is important to mention that the sensitivity of EGr/GC was three times higher than that of bare GC (0.23 A/M), proving the advantages of using graphene-modified electrodes in the electrochemical detection of AZT.

The importance of nitrite ions has long been recognized due to their extensive use in environmental chemistry and public health. The growing use of nitrogen fertilizers and additives containing nitrite in processed food items has increased exposure and, as a result, generated concerns about potential harmful health consequences. This work presents the development of an electrochemical sensor based on graphene/glassy carbon electrode (EGr/GC) with applicability in trace level detection of nitrite in water samples. According to the structural characterization of the exfoliated material, it appears as a mixture of graphene oxide (GO; 21.53%), few-layers graphene (FLG; 73.25%) and multi-layers graphene (MLG; 5.22%) and exhibits remarkable enhanced sensing response towards nitrite compared to the bare electrode (three orders of magnitude higher). The EGr/GC sensor demonstrated a linear range between 3 × 10⁻⁷ and 10⁻³ M for square wave voltammetry (SWV) and between 3 × 10⁻⁷ and 4 × 10⁻⁴ M for amperometry (AMP), with a low limit of detection LOD (9.9 × 10⁻⁸ M). Excellent operational stability, repeatability and interference-capability were displayed by the modified electrode. Furthermore, the practical applicability of the sensor was tested in commercially available waters with excellent results.

Nitrogen-doped graphene (NGr) was synthesized by the hydrothermal method using urea as a reducing and doping agent for graphene oxide (GO). The crystalline structure of GO was revealed by the XRD intense peak recorded at 2θ = 11.4°, indicating that the interlayer distance within the structure was large (d = 0.77 nm), and the number of layers (n) was 9. Further, the transformation of GO in NGr also led to the decrease in the interlayer distance and number of layers (d = 0.387 nm; n = 3). As indicated by elemental analysis, the concentration of nitrogen in the NGr sample was 6 wt%. Next, the comparison between the performance of bare GC and the graphene-modified electrode (NGr/GC) towards piroxicam (PIR) detection was studied. Significant differences were observed between the two electrodes. Hence, in the case of bare GC, the oxidation signal of PIR was very broad and appeared at a high potential (+0.7 V). In contrast, the signal recorded with the NGr/GC electrode was significantly higher (four times) and shifted towards lower potentials (+0.54 V), proving the electro-catalytic effect of nitrogen-doped graphene. The NGr/GC electrode was also tested for its ability to detect piroxicam in pharmaceutical drugs (Flamexin), giving excellent recoveries.