Mechanisms of direct hydrogen peroxide synthesis on silicon and phosphorus dual-doped graphene: a DFT-D study

Hydrogen peroxide (H₂O₂) is an important chemical commodity, with demand growing significantly in chemical synthesis due to its green characteristics. The mechanisms of the direct synthesis of hydrogen peroxide (DSHP) on metal-free silicon and phosphorus dual-doped graphene (Si-P-G) catalyst, based on a dispersion-corrected density functional theory (DFT-D) method, are systematically investigated. The most stable Si-P-G catalyst is presented, with the local region of dopants shown to play an important role in the adsorption and reduction of oxygen. A two-electron pathway is probable for DSHP on Si-P-G according to kinetic and thermodynamic analyses. The hydrogenation of O₂ to OOH is the rate-limiting step, with a small barrier energy of 0.66 eV, and the potential energy surface is downhill by Gibbs free energy calculations. All results indicate that Si-P-G is a novel catalyst with high activity and good selectivity for DSHP.