Electron transfer via homogeneous phosphorus bridges enabling boosted photocatalytic generation of H2 and H2O2 from pure water with stoichiometric ratio

We report efficient and simultaneous production of H 2 and H 2 O 2 from photocatalytic pure water splitting over a novel heterojunction photocatalyst made of red phosphorus (RP) and Co x P co-modified P-doped g-C 3 N 4 (PCN). The success relies on the formation of RP as an intermediate to link Co x P and PCN, introducing atomic-level homogeneous P-P/P-P bonds in the heterojunction. The crafted P-P/P-P bridges as unique channels enable controllable and smooth charge flow via strong electronic coupling between each component in the composite photocatalyst, endowing a boosted carrier kinetics. More significantly, RP also facilities a Z-scheme charge transfer that induces two-electron photocatalytic H 2 and H 2 O 2 production from pure water in 1:1 stoichiometry. The highest activity reaches 15.26 μmol h -1 for bifunctional chemical evolution under simulated solar light irradiation, with the apparent quantum efficiencies (AQE) of 6.2% at 366 nm and 3.6% at 425 nm, without using any noble metals on 50 mg of photocatalyst. The new insights of phosphorus bridges can be applied to other composite photocatalysts for reinforced reaction kinetics towards value-added chemicals generation. • Red phosphorus (RP) and Co x P modified P-doped g-C 3 N 4 (PCN) is prepared. • The heterojunction enables efficient photocatalytic pure water splitting • Water is split into stoichiometric H 2 and H 2 O 2 via a two-electron mechanism. • RP bridges Co x P and PCN leading to the formation of P-P/P-P homogeneous bond. • The P-P/P-P bond as unique channel facilitates rapid and smooth charge flow.