Selective Cocatalyst Decoration of Narrow-Bandgap Broken-Gap Heterojunction for Directional Charge Transfer and High Photocatalytic Properties.

Narrow-bandgap semiconductors are promising photocatalysts facing the challenges of low photoredox potentials and high carrier recombination. Here, a broken-gap heterojunction Bi/Bi 2 S 3 /Bi/MnO 2 /MnO x , composed of narrow-bandgap semiconductors, is selectively decorated by Bi, MnO x nanodots (NDs) to achieve robust photoredox ability. The Bi NDs insertion at the Bi 2 S 3 /MnO 2 interface induces a vertical carrier migration to realize sufficient photoredox potentials to produce O 2 •- and • OH active species. The surface decoration of Bi 2 S 3 /Bi/MnO 2 by Bi and MnO x cocatalysts drives electrons and holes in opposite directions for optimal photogenerated charge separation. The selective cocatalysts decoration realizes synergistic surface and bulk phase carrier separation. Density functional theory (DFT) calculation suggests that Bi and MnOx NDs act as active sites enhancing the absorption and reactants activation. The decorated broken-gap heterojunction demonstrates excellent performance for full-light driving organic pollution degradation with great commercial application potential.