BiOBr/COF S-scheme photocatalyst for H2O2 production via concerted two-electron pathway.

• A novel organic/inorganic TpPaCl 2 /BiOBr S-scheme heterojunction photocatalysts were constructed. • The porous TpPaCl 2 endows TpPaCl 2 /BiOBr nanocomposites with high surface area, abundant active sites, and excellent visible light absorption. • The S-scheme mechanism and the pathway of H 2 O 2 formation were supported by both experimental characterization and DFT calculation. • The S-scheme heterojunction facilitates carrier separation and transfer in space and enhances redox power. • The unique surface properties of TpPaCl 2 promote O 2 -to-H 2 O 2 conversion via the concerted two-electron pathway. Constructing step-scheme (S-scheme) heterojunctions has become a popular strategy for efficient photocatalytic H 2 O 2 generation. Herein, we in situ grew BiOBr nanosheets (NSs) on a Schiff-base covalent organic framework (COF) with large π-conjugated structures to prepare S-scheme BiOBr/COF photocatalysts for H 2 O 2 synthesis. The highest photocatalytic H 2 O 2 production performance of the composite sample constituting the S-scheme heterojunction is 3749 µmol g⁻¹ h⁻¹, which was 1.85 and 27 times the rates of COF and BiOBr, respectively. The construction of S-scheme heterojunction contributed to efficient carrier transfer and separation in space and enhanced redox power. Moreover, the lying-down O 2 -adsorption configuration on the COF surface favors the concerted two-electron O 2 reduction process, which greatly reduced the reduction potential requirement for O 2 -to-H 2 O 2 conversion. The synergy between the S-scheme heterojunction and the unique O 2 –COF interaction boosted photocatalytic H 2 O 2 production activity. [Display omitted] [ABSTRACT FROM AUTHOR]