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Vinylene-Linked Covalent Organic Frameworks With Multi-Intramolecular Coupling-Promoted Photocatalytic CO2-to-CO Conversion
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DOI：10.1002/adfm.76915.png)
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Abstract
En 中文
Covalent organic frameworks (COFs) offer significant potential for solar energy conversion, but their sluggish intrinsic charge-transfer kinetics inherently restrict the activation of stable CO2. Herein, we developed a new electron-deficient monomer 6,6′-dimethyl-3,3′-bipyridazine (DPz), which can undergo Knoevenagel condensation with triformyl polyphenylenes to construct a new type of π-conjugated COFs. Their in-plane backbones are patterned with a repeated donor-π-acceptor–acceptor-π-donor (D-π-A–A-π-D) moiety by vinylene-linking of a bipyridazine core with two (bi-)phenyl terminals, which are vertically packed into a hexagonal lattice in an AA-stacking mode, yielding high specific surface areas and well-defined nanochannels. The quadrupolar structure strengthened by bipyridazine as the dual acceptors, endowed these COFs with exceptional semiconducting performance. In particular, analysis of femtosecond transient absorption (fs-TA) spectra revealed outstanding intramolecular charge transfer. Meanwhile, the substantial 1,2-diazine units might dominate either the highest occupied molecular orbital or lowest unoccupied molecular orbital energy levels of these COFs, thereby promoting hybrid orbital-coupled electron transfer, as also evaluated by theoretical calculations. Accordingly, the neat as-prepared COFs exhibit promising photoinduced charge-transfer dynamics. Using [Ru(bpy)3]Cl2 as a photosensitizer, the system achieved CO production rates of up to 1594 µmol g−1 h−1, with a selectivity of more than 97%, among the highest values for all COF-based photocatalysts reported to date.
Keywords:
active sites
bipyridazine (1,2-diazine) units
quadrupolar architecture
ultrafast electron dynamics
vinyl-linked COFs
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19
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3.4W
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32.1W
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