Graphene Oxide Nanoprisms for Sensitive Detection of Environmentally Important Aromatic Compounds with SERS

Recent advances in graphene-based sensors have shown that heavily oxidized (GO) and reduced graphene oxide (rGO) are attractive materials for environmental sensing due to their unique chemical and physical properties. We describe here the fabrication of nanostructured GO assemblies with Ag nanoprisms for improved detection with surface enhanced Raman scattering (SERS). Specifically, 100-μm-sized, periodic-nanoprism-array domains were fabricated on top of the GO layers by GO-assisted lithography (GOAL). The atomically thin GO underlayers are shown to attract cyclic aromatic molecules to the surface, likely via π-π stacking interactions. The close proximity of the analyte to GO and nanoprism (NP) tips effectively suppresses fluorescent background and affords a plausible tertiary enhancement of photon emissions via an electron charge transfer (CT) process. The adsorption of analyte to rGO-NP leads to the appearance and/or shift of several Raman bands, which provided a means to gain molecular insights into the graphene-enhanced scattering process. The analytical merits were characterized with model compound Rhodamine 6G, where the detection limit could reach subnanomolar concentrations. The nanoprism GO substrates also prove effective for SERS multiplex measurement of several legacy aromatic pollutants. Three tetrachlorobiphenyl isomers could be identified from a mixture using their autonomous nonoverlapping molecular fingerprints, and the substrate offers remarkable trace detection of 2,2',3,3'-tetrachlorobiphenyl (PCB-77).