Plasmon-Driven Interfacial Catalytic Reactions in Plasmonic MOF Nanoparticles

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 p-aminothiophenol to 4,4'-dimercaptoazobenzene (trans-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 (NaBH₄) or oxidant (H₂O₂). Also, the situ SERS spectra also point out that plasmonic MOF (AgNP@ZIF-8) nanoparticles exhibit much better catalytic performance in the H₂O₂ 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.