N-Doped Graphene Oxide Nanoparticles Studied by EPR

Graphene-derived materials attract a great deal of attention because of the peculiar properties that make them suitable for a wide range of applications. Among such materials, nano-sized systems show very interesting behaviour and high reactivity. Often such materials have unpaired electrons that make them suitable for electron paramagnetic resonance (EPR) spectroscopy. In this work we study by continuous wave and pulse EPR spectroscopy undoped and nitrogen-doped graphene quantum dots (GQD) with a size of about 2 nm. The analysis of the spectra allows identify- ing different types of paramagnetic centers related to electrons localized on large graphenic flakes and molecular-like radicals. By hyperfine spectroscopies on nitro- gen-doped samples, we determine the hyperfine coupling constant of paramagnetic centers (limited-size π-delocalized unpaired electrons) with dopant nitrogen atoms. The comparison of the experimental data with models obtained by density func- tional theory (DFT) calculations supports the interpretation of doping as due to the insertion of nitrogen atoms in the graphene lattice. The dimension of the delocalized regions in the flakes observed by pulse EPR is of about 20–25 carbon atoms; the nitrogen dopant can be classified as pyridinic or graphitic.