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通过仿生隔离-传导策略在共组装中实现同时增强光致发光和光催化的精确超分子纳米结构设计

Precise Supramolecular Nanoarchitectonics for Simultaneous Enhanced Photoluminescence and Photocatalysis in a Co-Assembly by a Biomimetic Isolation-Conduction Strategy.

作者信息

Gao Zhao, Sun Jianxiang, Shi Lulu, Yuan Wei, Yan Hongxia, Tian Wei

机构信息

Shaanxi Key Laboratory of Macromolecular Science and Technology, Xi'an Key Laboratory of Hybrid Luminescent Materials and Photonic Device, MOE Key Laboratory of Material Physics and Chemistry under Extraordinary Conditions, School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi'an, 710072, P. R. China.

Department of Chemistry, National University of Singapore 3, Science Drive 3, Singapore, 117543, Singapore.

出版信息

Angew Chem Int Ed Engl. 2025 Mar 17;64(12):e202423174. doi: 10.1002/anie.202423174. Epub 2025 Jan 3.

Abstract

Limited by the two mutually exclusive physicochemical processes of separation and recombination of photogenerated carriers, achieving photoluminescence and photocatalysis simultaneously is extremely challenging but essential for ever-growing complex issues and specialized scenarios. Here we proposed a biomimetic isolation-conduction strategy induced by an arene-perfluoroarene (A-P) interaction for enabling photoluminescence and photocatalytic hydrogen evolution reaction (HER) activity in the co-assembly of aromatic monomers and octafluoronapthalene (OFN). Inspired by the isolation-conduction effect of periodic isolation of myelin sheaths on the axons of vertebrate nerve fibers by node of Ranvier, we use OFN as a molecular isolator embedded in the aromatic monomers array to block the singlet-to-triplet pathway, while the enlarged intermolecular dipoles resulting from the A-P interactions facilitate the conduction of photogenerated carriers in the isolated regions. The resultant co-assembly exhibits an enhanced monomeric green emission compared to the corresponding monocomponent self-assembly with weak red emission. Meanwhile, it also has an enhanced photocatalytic HER performance with a rate of 2.45 mmol g h, which is 15.2 times more than the self-assembled one. On this basis, a sequential fluoric wastewater reuse system that includes real-time fluorescence detection/removal of perfluorooctanoic acids and photocatalytic HER device is constructed.

摘要

受光生载流子分离与复合这两个相互排斥的物理化学过程限制,同时实现光致发光和光催化极具挑战性,但对于日益复杂的问题和特定场景而言至关重要。在此,我们提出了一种由芳烃 - 全氟芳烃(A - P)相互作用诱导的仿生隔离 - 传导策略,以在芳香族单体与八氟萘(OFN)的共组装中实现光致发光和光催化析氢反应(HER)活性。受脊椎动物神经纤维轴突上髓鞘通过郎飞结进行周期性隔离的隔离 - 传导效应启发,我们将OFN用作嵌入芳香族单体阵列中的分子隔离器,以阻断单重态到三重态的途径,而由A - P相互作用产生的增大的分子间偶极有利于光生载流子在隔离区域内的传导。与具有微弱红色发射的相应单组分自组装相比,所得共组装表现出增强的单体绿色发射。同时,它还具有增强的光催化HER性能,速率为2.45 mmol g h,是自组装体系的15.2倍。在此基础上,构建了一个包括实时荧光检测/去除全氟辛酸和光催化HER装置的顺序式含氟废水回用系统。

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