In Situ Growth Large Area Silver Nanostructure on Metal Phenolic Network Coated NAAO Film and Its SERS Sensing Application for Monofluoroacetic Acid.

Abstract

Rapid screening monofluoroacetic acid (FAcOH) is responsible for preventing chemical poisoning and food safety events. Whereas surface enhanced Raman scattering (SERS) spectra is an effective tool for detecting forbidden chemicals, it is difficult to directly detect FAcOH due to its small Raman scattering cross section as well as weak adsorption on SERS substrates. In this work, the metal phenolic supramolecular networks (MPNs, i.e., the tannic acid and Fe3+ complex) were fabricated on the commercial nanoanodic aluminum oxide film (NAAO) for assisting in situ chemical deposition highly uniform Ag nanostructure over large areas (the NAAO@AgNS). The low cost and simple fabrication process made the NAAO@AgNS a single-use consumable. For FAcOH detection, a specific derivative reaction between FAcOH and thiosalicylic acid (TSA) was introduced. By taking TSA as the Raman probe, its SERS signal attenuated constantly with the increasing amount of FAcOH. For improving quantitative accuracy, thiocyanate (SCN-) was introduced on the NAAO@AgNS as an internal standard; thus, the characteristic peak intensity ratios associated with TSA and SCN- (I1035/I2125) were fitted to the concentration of FAcOH. It was demonstrated that the SERS assay achieved good sensitivity and selection toward FAcOH with the limit of quantitation (LOD) as low as 50 nmol L-1. The NAAO@AgNS featured with highly sensitive, uniform, and consistent SERS performances could easily extend to wide SERS applications.