Mechanistic insight into the charge carrier separation and molecular oxygen activation of manganese doping BiOBr...

High-efficiency separation of photogenerated charges and molecular oxygen activation is very important for photocatalytic removal of organic pollutants. However, the current understanding of the effect mechanism of metal substitution for the separation of photo-generated charges and molecular oxygen activation is still poor. Herein, efficient manganese (Mn)-doped BiOBr hollow microspheres synthesis, systematic characterizations, and theoretical calculation discovered that Mn-doping could not only induce produce oxygen vacancies (OVs), but also can act as active sites for catalytic reactions. The induced production of OVs and Mn²⁺/Mn³⁺ by Mn optimal doping introduced into BiOBr can synergistic promote the separation of photogenerated charges and molecular oxygen activation leads to significantly enhances degradation of crystal violet (CV). Upon analysis, Mn-doping introducing unsaturated d-orbital with bridging O^2- formation π-donation accelerated the separation of photo-generated charges. Meanwhile, the larger overlap of Mn-3d orbitals with O₂-2p orbitals forms a π-donation bond with charge transfer from metal to O₂ leading to the oxygen-oxygen (OO) bond length and molecular oxygen activation. Finally, we proposed a possible mechanism to explain the highly efficient photocatalytic degradation performance of the acquired photocatalysts. This study provides not only a novel strategy for the rational design of highly active photocatalysts, but also in-depth insights into the separation of photo-generated charges and molecular oxygen activation.