Nanostructured Raman substrates for the sensitive detection of submicrometer-sized plastic pollutants in water

Highlights: • AuNSs@Ag@AAO substrates were prepared for microplastic detection in water. • Nanosized Raman substrates sensitively detected submicrometer-sized particles. • Numerical analysis supported strong electromagnetic enhancements of AuNSs@Ag • A 0.4 μm polystyrene sample could be quantified with a detection limit of ∼0.005 %. • Enhanced Raman spectroscopy provided a fast detection of nanosized plastics. We prepared novel Raman substrates for the sensitive detection of submicron-sized plastic spheres in water. Anisotropic nanostar dimer-embedded nanopore substrates were prepared for the efficient identification of submicron-sized plastic spheres by providing internal hot spots of electromagnetic field enhancements at the tips of nanoparticles. Silver-coated gold nanostars (AuNSs@Ag) were inserted into anodized aluminum oxide (AAO) nanopores for enhanced microplastic (MP) detection. We found that surface-enhanced Raman scattering (SERS) substrates of AuNSs@Ag@AAO yielded stronger signals at the same weight percentages for polystyrene MP particles with diameters as small as 0.4 μm, whereas such behaviors could not be observed for larger MPs (diameters of 0.8 μm, 2.3 μm, and 4.8 μm). The detection limit of the submicrometer-sized 0.4 μm in our Raman measurements were estimated to be 0.005% (∼0.05 mg/g =50 ppm) along with a fast detection time of only a few min without any sample pretreatments. Our nano-sized dimensional matching substrates may provide a useful tool for the application of SERS substrates for submicrometer MP pollutants in water.