Integration of bulk-surface charge polarization and active site manipulation for highly efficient photocatalytic aerobic oxidation of sulfides

Photocatalytic selective aerobic oxidation in organic synthesis is a green and sustainable approach to producing valuable chemicals. However, the sluggish charge dynamics and limited active sites for O2 activation tremendously hinder catalytic activity. Herein, we address these challenges by developing a novel polarization photocatalyst composed of atomically dispersed Ni sites with S-doped Bi4O5BrI (Ni/Bi4O5BrI-S), which demonstrates bulk-surface charge polarization and active site manipulation. Specifically, this bulk-surface charge polarization, resulting from a cascade of the bulk electric field (BEF) and local surface electric field (LSEF), induces efficient separation of bulk and surface charge carriers. Moreover, the atomically dispersed Ni sites substantially augment active sites for O2 activation, further accelerating charge transfer and increasing the generation of photogenerated holes (h+) and superoxide radical (•O2−) active species for triggering efficient aerobic oxidation of sulfide. This study presents a collaborative strategy for manipulating charge behavior with potential applications in renewable energy and green chemistry.