The activation of the C(sp3)-F bond is extremely difficult due to its unreactive nature. The importance of this bond activation is recently highlighted because extensive distribution of perfluorocarboxylic acids (PFCAs) (CnF2n+1COOH) has emerged as a challenging environmental issue. Photocatalytic degradation of PFCAs over a few semiconducting light absorbers is known to remove these water and soil resilient contaminants but with limited efficiency. This work reports density functional theory calculations, through which we present a detailed mechanistic study of photocatalytic degradation of CF3COOH (the shortest member of the PFCA family) over hexagonal boron nitride (h-BN). Our results clearly demonstrate that the existence of point defects is necessary to activate the h-BN plane for photocatalytic dissociation of the C-F bond. Specifically, we show that vacancies create strong Lewis acid or base sites (B or N vacancy, respectively) that facilitate the activation of the C(sp3)-F bond considerably. Furthermore, this study presents vivid theoretical evidence for the significant role of oxygen dopants, which mitigate the strength of the active sites and promote PFCA degradation over h-BN. Our calculations suggest that while the very stable intermediates generated during the reaction, in the case of h-BN with B or N vacancies, practically poison the catalyst, oxygen dopants make the degradation much more plausible and controllable. This work thus provides both an explanation for recently observed photocatalytic activity of h-BN to decompose PFCAs and valuable insights for exploring defected two-dimensional materials for activating and removing the fluorine-containing contaminants from water and soil.
Keywords: hexagonal boron nitride; oxygen dopant; perfluorocarboxylic acids; photocatalytic degradation; vacancies.