Fullerene C(70)-Encapsulated Tetrathiafulvalene-Co Porphyrin Covalent Organic Framework: Driving Multistep Charge Transfer to Boost CO(2) Photoreduction

富勒烯C70包覆的四硫富瓦烯-钴卟啉共价有机框架:驱动多步电荷转移以增强CO2光还原

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Abstract

Constructing an efficient charge transfer system can significantly enhance photocatalytic CO(2) reduction, yet efficient construction strategies remain to be explored. In this work, fullerene C(70) is encapsulated into the tetrathiafulvalene-Co porphyrin (TTF-CoTPP) COF to fabricate an efficient photocatalyst C(70)@COF. Transient absorption (TA) spectra indicate that C(70) significantly promotes photogenerated charge separation (0.3 ps), subsequently driving multistep charge transfer within the composite system. This process ultimately yields a long-lived charge-separated state, TTF(•+)-CoTPP-C(70) (•-) (>5 ns). Density functional theory (DFT) calculation reveals that the encapsulation of C(70) forms a new electron transfer pathway and reduces the energy barrier for (*)COOH intermediate formation. The C(70)@COF exhibits a remarkable CO production rate of 4963.24 µmol g h(-1), a 1.95-fold enhancement over the pristine COF. This work highlights the potential of fullerene in boosting photocatalytic CO(2) reduction performance and offers a facile strategy to design novel COF-based photocatalysts.

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