Hydrophobic plasmonic silver membrane as SERS-active catcher for rapid and ultrasensitive Cu(II) detection

The rapid and selective identification of heavy metal ions is crucial for environmental water safety. In this study, a novel surface-enhanced Raman scattering (SERS)-active catcher was designed for Cu(II) detection using a hydrophobic hydroxyoxime-mediated plasmonic silver membrane (HOX@Ag-PVDF). Uniformly dispersed Ag nanoparticles (ca. 80 nm) and hydroxyoxime molecules were synchronously decorated on the skeleton of the polyvinylidene fluoride membrane via an in situ interfacial assembly strategy. HOX@Ag-PVDF shows excellent SERS activity (EF = 2.5 × 10⁷), high reproducibility (~8% RSD), and long-term stability (50 days) for detecting 4-nitrothiophenol (4-NTP). Moreover, HOX@Ag-PVDF can serve as a new platform for rapid and dry-free SERS detection of Cu(II) owing to its strong affinity and surface hydrophobicity. Cu(II) ions can be rapidly captured in 5 s and selectively recognized by SERS signals without interference from other metal ions. HOX@Ag-PVDF exhibits linear SERS response signals at low concentrations ranging from 10^-6 to 10^-10 mol/L Cu(II) (R² = 0.9893) with a low detection limit (LOD) of 52.0 pmol/L. This hydrophobic plasmonic membrane, with its simple sampling and rapid SERS response characteristics, provides ultrasensitive recognition and heavy metal detection for practical applications.