Phosphate Modification Promoted Photocatalytic Singlet Oxygen Generation and Carbamazepine Degradation of (010) Facet-Exposed Biocl

Abstract

1O2 generation over (001) or (010) facet exposed BiOCl (B001 or B010) with/without phosphate modification were studied from the aspects of excitons involved energy transfer route, the •O2- oxidation based charge transfer route and the H2O2 oxidation by HClO. Phosphate modification not only enhance charge separation thus result in H2O2 oxidation by HClO to release 1O2 but also weaken excitonic effect in the confined layer of BiOCl accordingly affect 1O2 generation via energy transfer. Considering [001] orientation favors the formation of excitons than that of [010] direction over BiOCl, excitons loss was hardly compensated by the H2O2 oxidation by HClO for 1O2 generation over phosphate modified B001. Nevertheless, limited excitonic effect makes the •O2- oxidation by h+ via charge transfer as dominant route for 1O2 yielding over B010, the extra H2O2 oxidation with HClO after phosphate modification significantly enhance 1O2 generation over B010 followed with 2.1 times higher carbamazepine photodegradation activity. The initial attack of C=C bond via 1O2 to form epoxide played important roles on carbamazepine degradation. This study demonstrated that the facet-specific phosphate modification of photocatalysts can finely tune reactive 1O2 species for superior pharmaceuticals degradations.

Keywords: Singlet oxygen generation, bismuth oxychloride, facet engineering, phosphate modification, carbamazepine