Elucidating the enhanced decomposition of alkyl hydroperoxides on oxygen vacancy rich TiO 2- x surfaces using DFT for polyethylene decomposition.

Effective photocatalytic polyethylene degradation by TiO 2 is hindered by the sluggish kinetics of alkyl hydroperoxide decomposition. Introduction of oxygen vacancies onto TiO 2 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 TiO 2 .