Molecular Mechanism for the Self-Supported Synthesis of Graphitic Carbon Nitride from Urea Pyrolysis.

Quantum chemical calculations combined with kinetic Monte Carlo simulations are performed to decipher the kinetics for the one-pot synthesis of two-dimensional graphitic carbon nitride (-CN) from urea pyrolysis. Two mechanisms are considered, one involving ammelide as the intermediate compound and the other considering cyanuric acid. Different grid growing patterns are investigated, and the size, shape, and density of the grids as well as the number and position of the defects are evaluated. We find that the mechanistic pathway involving ammelide is preferred. Larger -CN grids with lower density are achieved when the rate constant for melon growing is inversely proportional to the number of local reaction sites, while nearly filled smaller grids are obtained in the opposite scenario. Larger defects appear at the grid periphery while smaller holes appear throughout the grid. The synthesis of extended -CN structures is favored if the -CN growing propensity is directly proportional to the number of reaction sites.