Nitrogen–phosphorus doped graphitic nano onion-like structures: experimental and theoretical studies

Onion-like graphitic structures are of great importance in different fields. Pentagons, heptagons, and octagons are essential features of onion-like graphitic structures that could generate important properties for diverse applications such as anodes in Li metal batteries or the oxygen reduction reaction. These carbon nanomaterials are fullerenes organized in a nested fashion. In this work, we produced graphitic nano onion-like structures containing phosphorus and nitrogen (NP-GNOs), using the aerosol assisted chemical vapor deposition method. The NP-GNOs were grown at high temperature (1020 °C) using ferrocene, trioctylphosphine oxide, benzylamine, and tetrahydrofuran precursors. The morphology, structure, composition, and surface chemistry of NP-GNOs were characterized using different techniques. The NP-GNOs showed diameters of 110–780 nm with Fe-based nanoparticles inside. Thermogravimetric analysis showed that NP-GNOs are thermally stable with an oxidation temperature of 724 °C. The surface chemistry analysis by FTIR and XPS revealed phosphorus–nitrogen codoping, and several functionalities containing C–H, N–H, P–H, P–O, PO, CO, and C–O bonds. We show density functional theory calculations of phosphorus–nitrogen doping and functionalized C240 fullerenes. We present the optimized structures, electronic density of states, HOMO, and LUMO wave functions for P-doped and OH-functionalized fullerenes. The PO and P–O bonds attributed to phosphates or hydroxyl groups attached to phosphorus atoms doping the NP-GNOs could be useful in improving supercapacitor function.