Conjugated microporous polymers (CMPs) are cost-effective photocatalysts in organic transformations, while they are usually limited by the insufficient separation of photogenerated charges. Here we reported a polarization strategy through molecular...
Constructing photocatalyst systems to functionalize the inert C−H bonds has attracted extensive research interest. However, purposeful modulation of interfacial charge transfer in heterostructures remains a challenge, as it usually suffers from sluggish kinetics. Reported herein is an easy strategy to construct the heteroatom‐induced interface for developing the titanium‐organic frameworks (MOF‐902) @ thiophene‐based covalent triazine frameworks (CTF‐Th) nanosheets S‐scheme heterojunctions with controllable oxygen vacancies (OVs). Specifically, Ti atoms were first anchored onto the heteroatom site of CTF‐Th nanosheets, and then grown into MOF‐902 via an interfacial Ti−S linkage, generating OVs. Using in situ X‐ray photoelectron spectroscopy (XPS), extended X‐ray absorption fine structure (EXAFS) spectroscopy and density functional theory (DFT) calculations, the enhanced interfacial charge separation and transfer induced by moderate OVs in the pre‐designed S‐scheme nanosheets was validated. The heterostructures exhibited an improved efficiency in photocatalytic C3‐acylation of indoles under mild conditions with a yield 8.2 times larger than pristine CTF‐Th or MOF‐902 and enabled an extended scope of substrates (15 examples). This performance is superior to state‐of‐the‐art photocatalyst and can be retained, without significant loss, after 12 consecutive cycles.
The development of new photocatalytic platforms using novel semiconductor material is an important challenge. Herein, a sp2 carbon‐conjugated covalent triazine polymer (sp2c‐CTP‐4), featuring a vinylene bridge and extended π‐conjugation, is prepared as a highly efficient photocatalyst for degradation of methylene blue. sp2c‐CTP‐4 exhibits substantial semiconducting properties such as enhanced charge transfer and prolonged lifetime of carriers compared to its counterparts with CN or CC connections, likely due to its extended π‐delocalization with an unencumbered CC bridge. Moreover, benefiting from its high chemical stability, the as‐made catalyst can be recycled five times with good retention of photocatalytic activity. This study provides a new pathway for constructing a robust platform for efficient photocatalysis and gives insight into the structure–property relationship of conjugated polymers.
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