Atomically dispersed Ni active sites on covalent organic frameworks for heterogeneous metallaphotocatalytic C–N cross-coupling

IF 20.2 1区 化学 Q1 CHEMISTRY, PHYSICAL
Zhuwei Li , Yaning Li , Huijie Cheng , Yurou Song , Yuye Jiao , Shaobo Shi , Junfeng Gao , Licheng Sun , Jungang Hou
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Abstract

Covalent organic frameworks (COFs) have been acknowledged as a potential platform for heterogeneous photoredox cross-coupling due to their excellent chemical stability, admirable controllability, and extremely prominent surface area. However, synthesizing COFs with bidentate ligand units and utilizing active sites remain a grand challenge. Herein, we report a promising new family of 2,6-pyridinedicarboxaldehyde-bis-(p-aminophenylimine)-based two-dimensional (2D) COFs (PP-COF) using an amine monomer and classic tri-aldehydes. On this basis, dispersed Ni single-atom sites were immobilized on three-types imine-based bi-coordinated 2D COFs (Ni SAS-PP-COF) as heterogeneous dual photoredox catalysts for photo/Ni dual-catalyzed C–N cross-coupling between aryl bromides and alkyl/sulfo amines. Under solar energy irradiation, PP-COF could absorb light to generate electrons and holes, then the photogenerated electrons are transferred to Ni sites to reduce divalent nickel to monovalent nickel. Monovalent nickel is necessary to drive the nickel catalytic cycle. Due to the increased charge separation and abundant active sites, the state-of-the-art Ni SAS-PP-COFs catalyst achieves excellent catalytic performance in comparison of pristine PP-COF. The heterogeneous Ni SAS-PP-COF catalytic system not only confirms the prospect of COFs as potential photoredox/transition-metal dual catalysts, but also provides in-depth insights into the synthesis of functional COFs toward practical metallaphotocatalytic application.

Abstract Image

共价有机框架上原子分散的镍活性位点用于异构金属触媒催化 C-N 交叉偶联
共价有机框架(COFs)因其出色的化学稳定性、令人赞叹的可控性和极其突出的比表面积,已被公认为异质光氧化交叉偶联的潜在平台。然而,合成具有双齿配体单元的 COF 并利用活性位点仍然是一项巨大的挑战。在此,我们利用胺单体和经典的三醛,报道了一种前景广阔的基于 2,6-吡啶二甲醛-双(对氨基苯基亚胺)的二维(2D)COF(PP-COF)新家族。在此基础上,分散的镍单原子位点被固定在三种亚胺基双配位二维 COFs(镍 SAS-PP-COF)上,作为异相双光氧化催化剂,用于光/镍双催化芳基溴和烷基/磺胺之间的 C-N 交叉偶联。在太阳能照射下,PP-COF 可以吸收光产生电子和空穴,然后将光生电子转移到镍位点,将二价镍还原为一价镍。一价镍是驱动镍催化循环所必需的。由于增加了电荷分离和丰富的活性位点,最先进的镍 SAS-PP-COFs 催化剂与原始 PP-COF 相比具有优异的催化性能。异质镍 SAS-PP-COF 催化体系不仅证实了 COFs 作为潜在的光氧化/过渡金属双催化剂的前景,还为合成功能 COFs 以实现金属光催化的实际应用提供了深入的见解。
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来源期刊
Applied Catalysis B: Environmental
Applied Catalysis B: Environmental 环境科学-工程:化工
CiteScore
38.60
自引率
6.30%
发文量
1117
审稿时长
24 days
期刊介绍: Applied Catalysis B: Environment and Energy (formerly Applied Catalysis B: Environmental) is a journal that focuses on the transition towards cleaner and more sustainable energy sources. The journal's publications cover a wide range of topics, including: 1.Catalytic elimination of environmental pollutants such as nitrogen oxides, carbon monoxide, sulfur compounds, chlorinated and other organic compounds, and soot emitted from stationary or mobile sources. 2.Basic understanding of catalysts used in environmental pollution abatement, particularly in industrial processes. 3.All aspects of preparation, characterization, activation, deactivation, and regeneration of novel and commercially applicable environmental catalysts. 4.New catalytic routes and processes for the production of clean energy, such as hydrogen generation via catalytic fuel processing, and new catalysts and electrocatalysts for fuel cells. 5.Catalytic reactions that convert wastes into useful products. 6.Clean manufacturing techniques that replace toxic chemicals with environmentally friendly catalysts. 7.Scientific aspects of photocatalytic processes and a basic understanding of photocatalysts as applied to environmental problems. 8.New catalytic combustion technologies and catalysts. 9.New catalytic non-enzymatic transformations of biomass components. The journal is abstracted and indexed in API Abstracts, Research Alert, Chemical Abstracts, Web of Science, Theoretical Chemical Engineering Abstracts, Engineering, Technology & Applied Sciences, and others.
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