Nitrogen-Doped Graphene Materials with High Electrical Conductivity Produced by Electrochemical Exfoliation of Graphite Foil

Nitrogen-doped graphene-based materials are of utmost importance in sensing and energy conversion devices due to their unique physicochemical properties. However, the presence of defects such as pyrrolic nitrogen and oxygenated functional groups reduces their electrical conductivity. Herein, a two-step approach based on the electrochemical exfoliation of graphite foils in aqueous mixed electrolytes followed by thermal reduction at 900 °C is used to prepare high-quality few layers of N-doped graphene-based materials. The exfoliations were conducted in 0.1 M (NH₄)₂SO₄ or H₂SO₄ and HNO₃ (5 mM or 0.1 M) electrolytes mixtures and the HNO₃ vol% varied. Chemical analysis demonstrated that the as-prepared graphene oxides contain nitro and amine groups. Thermal reduction is needed for substitutional N-doping. Nitrogen and oxygen surface concentrations vary between 0.23-0.96% and 3-8%, respectively. Exfoliation in (NH₄)₂SO₄ and/or 5 mM HNO₃ favors the formation of pyridinic-N (10-40% of the total N), whereas 1 M HNO₃ favors the formation of graphitic-N (≈60%). The electrical conductivity ranges between 166-2705 Scm⁻¹. Raman spectroscopy revealed a low density of defects (ID/IG ratio between 0.1 and 0.7) and that most samples are composed of mono-to-bilayer graphene-based materials (IG/I2D integrated intensities ratio). Structural and compositional stability of selected samples after storage in air for three months is demonstrated. These results confirm the high quality of the synthesized undoped and N-doped graphene-type materials.