Structurally Locked High-Crystalline Covalent Triazine Frameworks Enable Remarkable Overall Photosynthesis of Hydrogen Peroxide

The development of green and efficient hydrogen peroxide (H 2 O 2 ) production is of great interest but remains challenging. Herein, we develop a new and simple strategy via locking the coplanarity in highly crystalline covalent triazine frameworks (CTFs) to remarkably boost direct photosynthesis of H 2 O 2 from oxygen and water. The exfoliated ultrathin 2D-CTF nanosheets exhibit excellent photocatalytic H 2 O 2 evolution with an ultrahigh solar-to-chemical efficiency of 0.91% and a superb apparent quantum yield of 16.8% at 420 nm, surpassing all previous CTFs and most of the metal-free photocatalysts ever reported. Our detailed experimental and theoretical studies reveal that the spatially locked structure in the crystalline CTF photocatalyst can not only greatly enhance the separation and transfer of photoexcited charge-carriers for promoting H 2 O 2 photogeneration but also alter the local electronic structures that unexpectedly turn water oxidation from a four-electron route to a two-electron pathway, resulting in a 100% atom utilization efficiency. This work provides valuable insights into the designed synthesis of highly efficient metal-free photocatalysts and precise control over photocatalytic reaction pathways in organic materials.