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多组分金属有机框架显著提高可见光驱动的析氢与选择性有机氧化耦合性能。

Multi-Component Metal-Organic Frameworks Significantly Boost Visible-Light-Driven Hydrogen Production Coupled with Selective Organic Oxidation.

作者信息

Li Hanning, Yang Yang, Jing Xu, He Cheng, Duan Chunying

机构信息

State Key Laboratory of Fine Chemicals, Zhang Dayu College of Chemistry, Dalian University of Technology, Dalian, 116024, P. R. China.

出版信息

Chem Asian J. 2021 May 17;16(10):1237-1244. doi: 10.1002/asia.202100194. Epub 2021 Apr 6.

Abstract

Visible-light-driven hydrogen production coupled with selective organic oxidation has attracted increasing attention, as it not only provides clean and renewable energy, but also utilizes the other half reaction to achieve some value-added organic chemicals. Metal-organic frameworks based on metal clusters and organic ligands self-assembly give a perspective on the formation of multifunctional heterogeneous photocatalyst to significantly boost visible-light photocatalytic activities under mild conditions. By incorporating two types of photoactive units, tricarboxytriphenylamine (H TCA) and tris(4-(pyridinyl)phenyl)amine (NPy ), into a single metal-organic frameworks, a multi-component MOF Co-MIX was obtained. With the redox active metal centers enabling the photoexcitation reduction of protons into hydrogen and the photogenerated holes promoting considerable oxidation of substrates, the resulting Co-MIX exhibits high catalytic activity for the photocatalytic hydrogen production coupled with selective oxidation of benzylamine or 1,2,3,4-tetrahydroisoquinoline. Importantly, the photocatalytic experiments of single-component Co-TCA and Co-NPy verified the positive synergistic effects on stability and photocatalytic ability of the two ligands (H TCA and NPy ) in one single MOF, revealing that the multi-component strategy is very important for the efficient charge separation and excellent photocatalytic activity of the catalyst.

摘要

可见光驱动的产氢与选择性有机氧化相结合引起了越来越多的关注,因为它不仅提供清洁和可再生能源,还利用另一半反应来制备一些增值有机化学品。基于金属簇和有机配体自组装的金属有机框架为多功能非均相光催化剂的形成提供了一个视角,以在温和条件下显著提高可见光光催化活性。通过将两种光活性单元,即三羧基三苯胺(H TCA)和三(4-(吡啶基)苯基)胺(NPy),引入到单个金属有机框架中,得到了一种多组分MOF Co-MIX。由于氧化还原活性金属中心能够将质子光激发还原为氢气,且光生空穴促进底物的显著氧化,所得的Co-MIX在光催化产氢与苄胺或1,2,3,4-四氢异喹啉的选择性氧化耦合反应中表现出高催化活性。重要的是,单组分Co-TCA和Co-NPy的光催化实验证实了两种配体(H TCA和NPy)在单个MOF中对稳定性和光催化能力的正协同效应,表明多组分策略对于催化剂的有效电荷分离和优异光催化活性非常重要。

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