Comparative first principles‐based molecular dynamics study of catalytic mechanism and reaction energetics of water oxidation reaction on 2D‐surface

Abstract The study of the water‐splitting process, which can proceed in 2e − as well as 4e − pathway, reveals that the process is entirely an uphill process, and the third step, that is, the oxooxo bond formation is the rate‐determining step. The kinetic barrier of the oxygen evolution reaction (OER) on the 2D material catalysts in the presence of explicit solvents is scarcely studied. Here, we investigate the dynamics of the OER on the undoped graphene and the activation energy barrier of each step using first principles molecular dynamics simulations. Here we provide a detailed analysis of the kinetics of all the 4e − transfer steps of OER on the graphene surface. We also compare the accuracy of one of the density functional theory (DFT) functionals and density functional based tight binding (DFTB) method in explaining the OER steps. The comparative study reveals that DFTB can be used for performing metadynamics simulations quipped with much less computational cost than DFT functionals. By both Perdew–Burke–Ernzerhof and DFTB methods, the third step is revealed to be the rate‐determining step with an energy barrier of 21.19 ± 0.51 and 20.23 ± 0.20 kcal mol −1 , respectively. DFTB gives an impression of being successful in predicting the energy barriers of OER in 4e‐ transfer pathway and comparable to the DFT method, and we would like to extend the use of DFTB for further studies with a sizable and complex system.