Programmed Charge Transfer in Conjugated Polymers with Pendant Benzothiadiazole Acceptor for Simultaneous Photocatalytic H 2 O 2 Production and Organic Synthesis.

While being important candidate for heterogeneous photocatalyst, conjugated polymer typically exhibits random charge transfers between the alternating donor and acceptor units, which severely limits its catalytic efficiency. Herein, inspired by natural photosystem, the concept of guiding the charge migration to specific reaction sites is employed to significantly boost photocatalytic performance of linear conjugated polymers (LCPs) with pendant functional groups via creating programmed charge-transfer channels from the backbone to its pendant moiety. The pendant benzothiadiazole, as revealed in both in situ X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations, can act as electron "reservoir" that aggregates electrons at the active sites. Moreover, the presence of charge-transfer channels, evidenced by transient absorption spectroscopy (TAS), accelerates the electron transfer, preventing the recombination of electrons and holes. As a result, in this elaborately-designed architecture, the photogenerated electron can move smoothly towards the reduction sites, facilitating the reduction of O ₂ into H ₂ O ₂ , while remaining holes are directed to oxidation centers, simultaneously oxidizing furfuryl alcohol to furoic acid. The optimized photocatalyst LCP-BT demonstrates a competitive catalytic performance with H ₂ O ₂ productivity of 868.3 μmol L ^-1  h ^-1 (9.8 times higher than conventional random charge-transfer polymer LCP-1) and furfuryl alcohol conversion over 95 % after 6 h.
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