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Developing Photosensitizer-Cobaloxime Hybrids for Solar-Driven H2 Production in Aqueous Aerobic Conditions
Published on: October 5, 2019
Benzothiadiazole covalent organic framework photocatalysis with an electron transfer mediator for selective aerobic
Xia Li1, Yuexin Wang2, Fulin Zhang2
1Ministry of Education Key Laboratory for the Green Preparation and Application of Functional Materials, School of Materials Science and Engineering, Hubei University, Wuhan 430062, China; Sauvage Center for Molecular Sciences, Hubei Key Lab on Organic and Polymeric Optoelectronic Materials, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.
Abstract:
Covalent organic frameworks (COFs) are promising visible light photocatalysts for aerobic oxidation reactions. However, COFs usually suffer from the assault of reactive oxygen species, leading to hindered electron transfer. This scenario could be addressed by integrating a mediator to promote photocatalysis. Starting with 4,4'-(benzo-2,1,3-thiadiazole-4,7-diyl)dianiline (BTD) and 2,4,6-triformylphloroglucinol (Tp), TpBTD-COF is developed as a photocatalyst for aerobic sulfoxidation. Adding an electron transfer mediator 2,2,6,6-tetramethylpiperidine-1‑oxyl (TEMPO), the conversions are radically accelerated, over 2.5 times of that without TEMPO. Moreover, the robustness of TpBTD-COF is preserved by TEMPO. Remarkably, TpBTD-COF could endure multiple cycles of sulfoxidation, even with higher conversions than the fresh one. TpBTD-COF photocatalysis with TEMPO implements diverse aerobic sulfoxidation by an electron transfer pathway. This work highlights that benzothiadiazole COFs are an avenue for tailor-made photocatalytic transformations.
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