Key Laboratory for Advanced Materials, Shanghai Key Laboratory of Functional Materials Chemistry, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China.
Key Laboratory of Pollution Exposure and Health Intervention of Zhejiang Province, College of Biology and Environmental Engineering, Zhejiang Shuren University, Hangzhou 310015, P. R. China.
ACS Sens. 2024 May 24;9(5):2421-2428. doi: 10.1021/acssensors.4c00103. Epub 2024 Apr 21.
A core-shell nanostructure of gold nanoparticles@covalent organic framework (COF) loaded with palladium nanoparticles (AuNPs@COF-PdNPs) was designed for the rapid monitoring of catalytic reactions with surface-enhanced Raman spectroscopy (SERS). The nanostructure was prepared by coating the COF layer on AuNPs and then in situ synthesizing PdNPs within the COF shell. With the respective SERS activity and catalytic performance of the AuNP core and COF-PdNPs shell, the nanostructure can be directly used in the SERS study of the catalytic reaction processes. It was shown that the confinement effect of COF resulted in the high dispersity of PdNPs and outstanding catalytic activity of AuNPs@COF-PdNPs, thus improving the reaction rate constant of the AuNPs@COF-PdNPs-catalyzed hydrogenation reduction by 10 times higher than that obtained with Au/Pd NPs. In addition, the COF layer can serve as a protective shell to make AuNPs@COF-PdNPs possess excellent reusability. Moreover, the loading of PdNPs within the COF layer was found to be in favor of avoiding intermediate products to achieve a high total conversion rate. AuNPs@COF-PdNPs also showed great catalytic activities toward the Suzuki-Miyaura coupling reaction. Taken together, the proposed core-shell nanostructure has great potential in monitoring and exploring catalytic processes and interfacial reactions.
一种金纳米粒子@共价有机框架（COF）负载钯纳米粒子（AuNPs@COF-PdNPs）的核壳纳米结构被设计用于通过表面增强拉曼光谱（SERS）快速监测催化反应。该纳米结构是通过在 AuNPs 上包覆 COF 层，然后在 COF 壳内原位合成 PdNPs 制备的。由于 AuNP 核和 COF-PdNPs 壳的各自 SERS 活性和催化性能，该纳米结构可直接用于催化反应过程的 SERS 研究。结果表明，COF 的限域效应导致 PdNPs 高度分散和 AuNPs@COF-PdNPs 的出色催化活性，从而使 AuNPs@COF-PdNPs 催化的加氢还原反应的速率常数提高了 10 倍以上，高于 Au/Pd NPs 获得的速率常数。此外，COF 层可用作保护壳，使 AuNPs@COF-PdNPs 具有出色的可重复使用性。此外，发现将 PdNPs 负载在 COF 层内有利于避免中间产物以实现高总转化率。AuNPs@COF-PdNPs 对 Suzuki-Miyaura 偶联反应也表现出很高的催化活性。总之，所提出的核壳纳米结构在监测和探索催化过程和界面反应方面具有很大的潜力。
