Green synthesis of large-scale highly ordered core@shell nanoporous Au@Ag nanorod arrays as sensitive and reproducible 3D SERS substrates.

We present a simple green synthetic approach to large-scale and highly ordered arrays of vertical nanoporous Au nanorods, with an ultrathin Ag-layer in situ electrodeposited on each nanoporous Au nanorod (denoted as core@shell nanoporous Au@Ag nanorod). As both the nanopores within each nanorod and the gaps between the neighboring nanorods create three-dimensional (3D) "hot spots" homogeneously distributed throughout the whole substrate, the core@shell nanoporous Au@Ag nanorod arrays were proved to be sensitive and reproducible surface-enhanced Raman scattering (SERS) substrates. Not only universal probe molecules (rhodamine 6G, R6G) but also nonadsorbing molecules (polychlorinated biphenyls, PCBs) have been detected by using the substrates. After mono-6-thio-β-cyclodextrin (HS-β-CD) was modified to efficiently capture more PCBs molecules, the detection limit of PCBs was further reduced to 5.35 × 10(-7) M. As a trial of practical application, R6G and PCBs with different molar ratios in their mixed solutions were identified, and two congeners of PCBs in their mixture could also be distinguished, showing great potentials in real-time simultaneous detection of multiple pollutants.