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共轭聚合物点中通过共价连接的分子催化剂可在中性条件下促进光催化醇氧化反应。

Covalently linked molecular catalysts in conjugated polymer dots boost photocatalytic alcohol oxidation in neutral condition.

作者信息

Wang Sicong, Pavliuk Mariia V, Zou Xianshao, Huang Ping, Cai Bin, Svensson Orpita M, Tian Haining

机构信息

Department of Chemistry - Ångström Laboratory, Uppsala University, 751 20, Uppsala, Sweden.

Qingdao Innovation and Development Base, Harbin Engineering University, Qingdao, CN-266 000, China.

出版信息

Nat Commun. 2024 Aug 8;15(1):6765. doi: 10.1038/s41467-024-51097-z.

Abstract

As a new class of organic photocatalysts, polymer dots show a potential application in photocatalytic hydrogen peroxide production coupled with chemical oxidation such as methanol oxidation. However, the poor methanol oxidation ability by polymer dots still inhibits the overall photocatalytic reaction occurring in the neutral condition. In this work, an organic molecular catalyst 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl radical is covalently linked to a fluorene unit in a polymer skeleton, eventually enabling photocatalytic hydrogen peroxide production coupled with methanol oxidation in the neutral condition. By conducting various spectroscopic measurements, charge transfer between components in this molecular catalyst-immobilized polymer dots system is studied and found to be very efficient for hydrogen peroxide production coupled with alcohol oxidation. This work proves a strategy for designing polymer dots photocatalysts with molecular catalysts, facilitating their future development and potential applications in other fields such as water splitting, CO reduction, photoredox catalysis and photodynamic therapy.

摘要

作为一类新型的有机光催化剂,聚合物量子点在光催化过氧化氢生产与化学氧化(如甲醇氧化)耦合方面显示出潜在应用。然而,聚合物量子点对甲醇的氧化能力较差,这仍然抑制了在中性条件下发生的整体光催化反应。在这项工作中,一种有机分子催化剂4-氨基-2,2,6,6-四甲基哌啶-1-氧基自由基与聚合物骨架中的芴单元共价连接,最终实现了在中性条件下光催化过氧化氢生产与甲醇氧化的耦合。通过进行各种光谱测量,研究了这种固定有分子催化剂的聚合物量子点体系中各组分之间的电荷转移,发现其对于过氧化氢生产与醇氧化的耦合非常有效。这项工作证明了一种用分子催化剂设计聚合物量子点光催化剂的策略,促进了它们未来的发展以及在其他领域(如水分解、CO还原、光氧化还原催化和光动力疗法)的潜在应用。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d767/11310486/a666c7f04943/41467_2024_51097_Fig1_HTML.jpg

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