Magnetic Properties of Nitrogen-Doped Graphene Induced by Dopant Configurations

In this study, we experimentally demonstrate that the magnetic properties of nitrogen-doped graphene (NG) are influenced by the configuration of nitrogen dopants, namely graphitic, pyridinic, and pyrrolic, along with the overall nitrogen concentration. The NG materials were prepared via a two-step thermal treatment process. The first step involved heating in ammonia at 400 °C, followed by a second post-annealing step at 600 °C. Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy (SEM-EDS) analysis performed at 25 μm resolution confirmed uniform elemental distribution across the samples. X-ray photoelectron spectroscopy (XPS) revealed that while the total nitrogen content decreased from 11.9 at.% in NG to 5.5 at.% in the post-annealed sample, the ratio of graphitic to pyrrolic nitrogen increased from 0.4% to 3.8% and the ratio of graphitic to pyridinic nitrogen increased from 0.8% to 2.5%. Raman spectroscopy confirmed the presence of prominent D and G bands at ~1352 cm^-1 and ~1589 cm^-1, respectively, along with a 2D band at ~2692 cm^-1, indicating the presence of few-layered graphene and defect-related features. The IDIG ratio increased from 1.12 to 1.27 in the post-annealed sample, indicating increased disorder after annealing. Magnetic characterization showed a marked enhancement in the magnetic properties with increased graphitic nitrogen content. The saturation magnetization (<i>M_s</i>) reached 0.13 emu g^-1, ~42% higher than that of the material heated in ammonia, with the coercivity increasing from 40 Oe to 750 Oe. These results emphasize the pivotal role of nitrogen configuration in the graphene host, specifically the promotion of graphitic nitrogen species, in tailoring the ferromagnetic response of NG.