Programmed Charge Transfer in Conjugated Polymers with Pendant Benzothiadiazole Acceptor for Simultaneous Photocatalytic H2O2 Production and Organic Synthesis

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 14, 2024

Abstract 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, concept of guiding migration to specific reaction sites is employed significantly boost photocatalytic performance linear polymers (LCPs) with pendant functional groups via creating programmed charge‐transfer channels from backbone moiety. The benzothiadiazole, as revealed in both situ X‐ray photoelectron spectroscopy (XPS) density theory (DFT) calculations, can act electron “reservoir” that aggregates electrons at active sites. Moreover, presence channels, evidenced transient absorption (TAS), accelerates transfer, preventing recombination holes. As a result, this elaborately‐designed architecture, photogenerated move smoothly towards reduction sites, facilitating O 2 into H , while remaining holes are directed oxidation centers, simultaneously oxidizing furfuryl alcohol furoic acid. optimized photocatalyst LCP‐BT demonstrates competitive productivity 868.3 μmol L −1 h (9.8 times higher than conventional LCP‐1) conversion over 95 % after 6 h.

Language: Английский

Programmed Charge Transfer in Conjugated Polymers with Pendant Benzothiadiazole Acceptor for Simultaneous Photocatalytic H2O2 Production and Organic Synthesis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 14, 2024

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, concept of guiding migration to specific reaction sites is employed significantly boost photocatalytic performance linear polymers (LCPs) with pendant functional groups via creating programmed charge-transfer channels from backbone moiety. The benzothiadiazole, as revealed in both situ X-ray photoelectron spectroscopy (XPS) density theory (DFT) calculations, can act electron "reservoir" that aggregates electrons at active sites. Moreover, presence channels, evidenced transient absorption (TAS), accelerates transfer, preventing recombination holes. As a result, this elaborately-designed architecture, photogenerated move smoothly towards reduction sites, facilitating O

Language: Английский