Elucidating the enhanced decomposition of alkyl hydroperoxides on oxygen vacancy rich TiO2−x surfaces using DFT for polyethylene decomposition

Abstract

Effective photocatalytic polyethylene degradation by TiO₂ is hindered by the sluggish kinetics of alkyl hydroperoxide decomposition. Introduction of oxygen vacancies onto TiO₂ destabilizes the hydroperoxide O–O bond due to mid-gap states and the elevated Fermi level. Downshift of the d-band center by oxygen vacancies also enhanced adsorbate–surface interactions and lowered the activation energy barrier from Gibbs calculations. Experimental evidence additionally substantiated enhanced polyethylene degradation on TiO_2−x compared to TiO₂.