Molecularly imprinted 3D SERS sensor with inorganic frameworks for specific and recyclable SERS sensing application

Poor selectivity and reusability of Au/Ag nanostructures are the main challenges for surface-enhanced Raman spectroscopy (SERS) in real sample detection. Herein, a novel specific and reusable three-dimensional (3D) SERS sensor with dual functions of selective trapping and photocatalytic degradation was designed. Firstly, Au-Ag bimetallic nanoparticles decorated silicon nanowires array (SiNWs-AuAg) were prepared as 3D SERS substrate. Then, silicon-based inorganic-framework molecularly imprinted TiO₂ (TiO₂@SiMIP) was synthesized and immobilized on SiNWs-AuAg by using rhodamine 6G (R6G) as template molecule. Owing to the excellent SERS performance of SiNWs-AuAg and the specific affinity of TiO₂@SiMIP to template molecule, the prepared SERS sensor enables sensitive and selective detection of R6G in food samples with a limit of detection (LOD) of 0.27 nM. In addition, due to the photocatalysis of TiO₂ and the stability of silicon-based inorganic framework, the residual templates in TiO₂@SiMIP can be completely removed by UV irradiation, and the imprinted cavity of regenerated sensors still maintained good selectivity after regeneration by UV irradiation.