Artificial photosynthesis converting carbon dioxide into chemical fuels with a high added value is a promising solution to both fossil fuel shortage/pollution and global climate change; however, the development of highly efficient photocatalysts toward this goal is still largely bereft of fresh ideas. Herein, we propose a “cascade electron transfer” strategy through spurring both interfacial and inner electron transfer rates for a 0D/2D photocatalyst of CsPbBr3/CuTCPP metal organic framework (MOF). Upon photoexcitation, the heterojunction structure with an appropriate band alignment facilitates an ultrafast interfacial electron transfer rate of 1.4 ps from CsPbBr3 segment to CuTCPP MOF and subsequent ultrafast internal electron transfer of 21 ps from CuTCPP ligand to the Cu node within the enlarged 2D framework. The efficient electron transfer ensures efficient charge separation favorable for photocatalytic reactions: The photocatalyst exhibits an outstanding yield of 47.2 μmol g−1 h−1 (CO and CH4 combined) superior to previous reports. Rational design of hierarchical heterojunctions with matching electronic bandgap not only expedites cascade charge transfer but also prevents holes from recombining with electrons or oxidizing the photocatalysts without the necessity of sacrificial reagents. This work thus provides useful insight for boosting photocatalytic efficacy from a dynamic perspective.
The development of sp2‐carbon‐linked covalent organic frameworks (sp2c‐COFs) as artificial photocatalysts for solar‐driven conversion of CO2 into chemical feedstock has captured growing attention, but catalytic performance has been significantly limited by their intrinsic organic linkages. Here, a simple, yet efficient approach is reported to improve the CO2 photoreduction on metal‐free sp2c‐COFs by rationally regulating their intrinsic π‐conjugation. The incorporation of ethynyl groups into conjugated skeletons affords a significant improvement in π‐conjugation and facilitates the photogenerated charge separation and transfer, thereby boosting the CO2 photoreduction in a solid‐gas mode with only water vapor and CO2. The resultant CO production rate reaches as high as 382.0 µmol g−1 h−1, ranking at the top among all additive‐free CO2 photoreduction catalysts. The simple modulation approach not only enables to achieve enhanced CO2 reduction performance but also simultaneously gives a rise to extend the understanding of structure‐property relationship and offer new possibilities for the development of new π‐conjugated COF‐based artificial photocatalysts.
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