An Unlocked Two‐Dimensional Conductive Zn‐MOF on Polymeric Carbon Nitride for Photocatalytic H2O2 Production

Developing highly efficient catalytic sites for O2 reduction to H2 O2 , while ensuring the fast injection of energetic electrons into these sites, is crucial for artificial H2 O2 photosynthesis but remains challenging. Herein, we report a strongly coupled hybrid photocatalyst comprising polymeric carbon nitride (CN) and a two-dimensional conductive Zn-containing metal-organic framework (Zn-MOF) (denoted as CN/Zn-MOF(lc)/400; lc, low crystallinity; 400, annealing temperature in °C), in which the catalytic capability of Zn-MOF(lc) for H2 O2 production is unlocked by the annealing-induced effects. As revealed by experimental and theoretical calculation results, the Zn sites coordinated to four O (Zn-O4 ) in Zn-MOF(lc) are thermally activated to a relatively electron-rich state due to the annealing-induced local structure shrinkage, which favors the formation of a key *OOH intermediate of 2e- O2 reduction on these sites. Moreover, the annealing treatment facilitates the photoelectron migration from the CN photocatalyst to the Zn-MOF(lc) catalytic unit. As a result, the optimized catalyst exhibits dramatically enhanced H2 O2 production activity and excellent stability under visible light irradiation.