Metal–Organic Framework-Enabled Trapping of Volatile Organic Compounds into Plasmonic Nanogaps for Surface-Enhanced Raman Scattering Detection

Utilizing electromagnetic hotspots within plasmonic nanogaps is a promising approach to create ultrasensitive surface-enhanced Raman scattering (SERS) substrates. However, it is difficult for many molecules to get positioned in such nanogaps. Metal-organic frameworks (MOFs) are commonly used to absorb and concentrate diverse molecules. Herein, we combine these two strategies by introducing MOFs into plasmon-coupled nanogaps, which has so far remained experimentally challenging. Ultrasensitive SERS substrates are fabricated through the construction of nanoparticle-on-mirror structures, where Au nanocrystals are encapsulated with a zeolitic imidazolate framework-8 (ZIF-8) shell and then coupled to a gold film. The ZIF-8 shell, as a spacer that separates the Au nanocrystal and the Au film, can be adjusted in thickness over a wide range, which allows the electric field enhancement and plasmon resonance wavelength to be varied. By trapping Raman-active molecules within the ZIF-8 shell, we show that our plasmon-coupled structures exhibit a superior SERS detection performance. A range of volatile organic compounds at the concentrations of 10-2 mg m-3 can be detected sensitively and reliably. Our study therefore offers an attractive route for synergistically combining plasmonic electric field enhancement and MOF-enabled molecular enrichment to design and create SERS substrates for ultrasensitive detection.