MOF-Derived hierarchical porous 3D ZnO/Ag nanostructure as a reproducible SERS substrate for ultrasensitive detection of multiple environmental pollutants

The three-dimensional (3D) surface-enhanced Raman scattering (SERS) substrate for trace molecule detection has recently attracted considerable interest; however, these substrates generally either show poor sensitivity or require a complex preparation process. In this work, we have fabricated a 3D ZnO/Ag substrate using porous zeolite imidazole frameworks (ZIF-8) derived ZnO nanoparticles (NPs) followed by evaporation-induced self-assembly of Ag NPs over it, which can detect multiple environmental pollutants by a facile and cost-effective method. This 3D porous substrate showed an ultra-sensitivity for detecting various types of molecules, e.g., rhodamine 6G (R6G), crystal violet (CV), tetracycline, and thiram, simultaneously suggesting its generality. Notably, the lowest detectable concentration (LDC) attained for R6G is 10-13 M, and the enhancement factor (EF) reaches up to 1.8 × 108. The most important reason for ultra-sensitivity is that ZnO derived from ZIF-8 has a hierarchical porous structure and large surface area to provide more "hot spots" and absorb more probe molecules. Consequently, the ZnO/Ag nanostructures show excellent photocatalytic performance. The detected probe molecules could be completely degraded in situ within a short UV exposure time (<30 min), thereby enabling outstanding reusability of this substrate. Finite-different time-domain (FDTD) simulations were used to understand the underlying mechanism of the substrate by calculating electric fields and hot spot distributions. The simulations suggested that the widespread hot spots structures on the substrate are the main reason for its SERS ultra-sensitivity.