Xie Xin, Zhang Yaoyao, Zhang Lingjun, Zheng Jiangen, Huang Yingzhou, Fa Huanbao
State Key Laboratory of Coal Mine Disaster Dynamics and Control, Chongqing Key Laboratory of Soft Condensed Matter Physics and Smart Materials, College of Physics, Chongqing University, Chongqing 400044, China.
National-municipal Joint Engineering Laboratory for Chemical Process, Intensification and Reaction, School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, PR China.
Anal Chem. 2021 Oct 5;93(39):13219-13225. doi: 10.1021/acs.analchem.1c02272. Epub 2021 Sep 21.
Benefiting from the noble metal nanoparticle core and organic porous nanoshell, plasmonic metal-organic frameworks (MOFs) become a nanostructure with great enhancement of the electromagnetic field and a high density of reaction sites, which has fantastic optical properties in surface plasmon-related fields. In this work, the plasmon-driven interfacial catalytic reactions involving -aminothiophenol to 4,4'-dimercaptoazobenzene (-DMAB) in both the liquid and gaseous phases are studied in plasmonic MOF nanoparticles, which consist of a Ag nanoparticle core and an organic shell (ZIF-8). The surface-enhanced Raman spectroscopy (SERS) spectra recorded at the plasmonic MOF in an aqueous environment demonstrate that the reversible plasmon-driven interfacial catalytic reactions could be modulated by a reductant (NaBH) or oxidant (HO). Also, the situ SERS spectra also point out that plasmonic MOF (AgNP@ZIF-8) nanoparticles exhibit much better catalytic performance in the HO solution compared to pure Ag nanoparticles for the anti-oxidation caused by the MOF shell. It is surprising that although there is greater SERS enhancement obtained at pure Ag nanoparticles, the plasmon-driven interfacial catalytic reactions only occur at plasmonic AgNP@ZIF-8 nanoparticles in the gaseous phase. This interesting phenomenon is further confirmed and analyzed by simulated electromagnetic field distributions, which could be understood by the effective capture of gaseous molecules by the organic porous nanoshell. Our work not only explores the plasmonic MOF nanoparticles with unique optical properties but also strengthens the understanding of plasmon-driven interfacial catalytic reactions.
得益于贵金属纳米颗粒核和有机多孔纳米壳，等离子体金属有机框架（MOF）成为一种具有极大增强的电磁场和高密度反应位点的纳米结构，在表面等离子体相关领域具有出色的光学性质。在这项工作中，研究了在由银纳米颗粒核和有机壳（ZIF-8）组成的等离子体MOF纳米颗粒中，涉及对氨基苯硫酚到4,4'-二巯基偶氮苯（-DMAB）的等离子体驱动的界面催化反应，该反应在液相和气相中均有发生。在水环境中在等离子体MOF处记录的表面增强拉曼光谱（SERS）光谱表明，可逆的等离子体驱动的界面催化反应可以通过还原剂（NaBH）或氧化剂（HO）进行调节。此外，原位SERS光谱还指出，与纯银纳米颗粒相比，等离子体MOF（AgNP@ZIF-8）纳米颗粒在HO溶液中由于MOF壳的作用在抗氧化方面表现出更好的催化性能。令人惊讶的是，尽管在纯银纳米颗粒处获得了更大的SERS增强，但等离子体驱动的界面催化反应仅在气相中的等离子体AgNP@ZIF-8纳米颗粒上发生。通过模拟电磁场分布进一步证实和分析了这一有趣现象，这可以通过有机多孔纳米壳对气态分子的有效捕获来理解。我们的工作不仅探索了具有独特光学性质的等离子体MOF纳米颗粒，还加强了对等离子体驱动的界面催化反应的理解。
