A High-Density Nanoporous SERS Substrate Prepared by Facile One-Step Anodization for P-Hydroxybenzoic Acid Detection

Compared with mass spectrometry or high-performance liquid chromatography (HPLC), surface-enhanced Raman scattering (SERS) is a promising alternative technique for inspection of preservatives in food safety. However, conventional SERS substrates based on metallic nanoparticles commonly suffer from complicated fabrication processes, long processing times, and high costs. Therefore, we propose a high-density porous anodic aluminum oxide (AAO) substrate prepared by one-step anodization process combined with pore widening to increase number of SERS hotspots on template. Through a rapid one-step anodization process conducted at 25 °C, the processing time and efficiency are greatly improved compared to conventional low temperature of 0–10 °C and two-step anodization method. By lowering the anodization voltage to 20 V, a high-density porous substrate is achieved, effectively enhancing the SERS signal intensity. Furthermore, we demonstrated that SERS signal intensities are affected by multiple correlated structural factors and significantly improved by lower anodization voltage with pore widening. The analytical enhancement factor is calculated as 1.18 × 105 to 1.44 × 107 on an AAO substrate prepared at 20 V with pore-widening process for 1000 and 0.1 ppm p-hydroxybenzoic acid, respectively. For the preservative detection of p-hydroxybenzoic acid, a detection limit of 100 ppb is achieved by a high-density AAO substrate prepared at 20 V, which is far below the regulatory limit of 600 ppm.