Atomistic characterisation of graphite oxidation and thermal decomposition mechanism under isothermal and Non-Isothermal heating scheme

The oxidation of graphene-based material (i.e. graphite, graphene) is a reaction of immense importance owing to its extensive industrial application (i.e. nanocomposites, flame retardants, energy storage). Although immense experimental works were carried out for identifying the thermal degradation and oxidation process of graphene, they generally lack atomistic-level observation of the surface reactions, thermal formation pathways from solid to product volatiles and structural evolutions during oxidation. To analyse the favourable properties of graphene from its carbon-chain molecular structure viewpoint, it is essential to investigate graphene-based materials at an atomic level. This study bridges the missing knowledge by performing quantitative reactive forcefield coupled molecular dynamics simulation (MD-ReaxFF) to determine the oxidation kinetics of graphite under computational characterisation schemes with temperatures ranging from 4000 K to 6000 K. The kinetics parameters (i.e. activation energy) were extracted through proposed numerical characterisation methods and demonstrated good agreement with the thermogravimetric analysis experiments and other literature. Activation energy at 193.84 kJ/mol and 224.26 kJ/mol were extracted under the isothermal scheme by two distinct characterisation methods, achieving an average relative error of 11.3 % and 2.5 % compared to the experiment data, which is 218.60 kJ/mol. In comparison, the non-isothermal simulations yielded 214.53 kJ/mol, with a significant improvement on the average relative error of 1.86 %. © 2022 Elsevier B.V.