Regulating π-Conjugation in sp² -Carbon-Linked Covalent Organic Frameworks for Efficient Metal-Free CO₂...

The development of sp² -carbon-linked covalent organic frameworks (sp² c-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 sp² c-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.