Ozone generation mechanism over phosphorus and the impact of H2O with density functional modeling

Abstract

The O₃ generation reaction mechanisms over P₄ in a water solution were investigated in this theoretical work using density functional modeling. The results showed that the association interaction between P₄ and O₂ resulted from van der Waals forces. The generation of a free O atom was the control step in the O₃ generation process, and the generation of O₃ was based on the existence of the free O atom. The generation of a P–O bond was a continuous process but was not conducive to the generation of O₃ and the free O atom. The H₂O molecule was conducive for the generation of a free O atom and O₃. Meanwhile, the involvement of the H₂O molecule changed the adsorption effect among the reactant molecules by changing the interaction from van der Waals forces to the chemical bond effect. In addition, the H₂O molecule decreased all the reaction energy barriers by H atom migration and promoted the generation of free O atoms. Herein, detailed reaction mechanisms were investigated using the all-electron density functional theory (DFT) computational method. As such, this study provides a theoretical insight for future applications and development.