Metal–Organic Frameworks as Surface Enhanced Raman Scattering Substrates with High Tailorability

Surface enhanced Raman scattering (SERS) is a widely used analytical technique for detecting trace-level molecules based on an indispensable SERS substrate. SERS substrates with high tailorability are assumed to be attractive and desirable for SERS detection, because the substrates match the need for the selective detection of different species. Nevertheless, the rational design of such SERS substrates is rather challenging for both noble-metal and semiconductor substrates. Herein, expanding beyond conventional SERS substrates, we demonstrate that metal-organic framework (MOF) materials can serve as a type of SERS substrate with molecular selectivity, which are rarely realized for SERS detection without any special pretreatment. A salient structural characteristic of MOF-based SERS substrates benefiting the SERS selectivity is their high tailorability. By controlling the metal centers, organic ligands, and framework topologies of our MOF-based SERS substrates, we show that the electronic band structures of MOF-based SERS substrate can be purposively manipulated to match those of the target analytes, thus resulting in different detectable species. Going further, the SERS enhancement factors (EFs) of the MOF-based SERS substrates can be greatly enhanced to as high as 106 with a low detection limit of 10-8 M by pore-structure optimization and surface modification, which is comparable to the EFs of noble metals without "hot spots" and recently reported semiconductors. This selective enhancement is interpreted as being due to the controllable combination of several resonances, such as the charge-transfer, interband and molecule resonances, together with the ground-state charge-transfer interactions. Our study opens a new venue for the development of SERS substrates with high-design flexibility, which is especially important for selective SERS detection toward specific analytes.