Building Asymmetric Zn−N ₃ Bridge between 2D Photocatalyst and Co‐catalyst for Directed Charge Transfer toward Efficient H ₂ O ₂ Synthesis

Abstract Two‐dimensional (2D) polymeric semiconductors are a class of promising photocatalysts; however, it remains challenging to facilitate their interlayer charge transfer for suppressed in‐plane charge recombination and thus improved quantum efficiency. Although some strategies, such as π–π stacking and van der Waals interaction, have been developed so far, directed interlayer charge transfer still cannot be achieved. Herein, we report a strategy of forming asymmetric Zn−N 3 units that can bridge nitrogen (N)‐doped carbon layers with polymeric carbon nitride nanosheets (C 3 N 4 −Zn−N(C)) to address this challenge. The symmetry‐breaking Zn−N 3 moiety, which has an asymmetric local charge distribution, enables directed interfacial charge transfer between the C 3 N 4 photocatalyst and the N‐doped carbon co‐catalyst. As evidenced by femtosecond transient absorption spectroscopy, charge separation can be significantly enhanced by the interfacial asymmetric Zn−N 3 bonding bridges. As a result, the designed C 3 N 4 −Zn−N(C) catalyst exhibits dramatically enhanced H 2 O 2 photosynthesis activity, outperforming most of the reported C 3 N 4 ‐based catalysts. This work highlights the importance of tailoring interfacial chemical bonding channels in polymeric photocatalysts at the molecular level to achieve effective spatial charge separation.