Abstract
Sensitivity is crucially important for surface-enhanced Raman spectroscopy (SERS) application to detect trace-level polycyclic aromatic hydrocarbons (PAHs) in the seawater. In this study, a high sensitivity three-dimensional (3-D) SERS substrate composed with syringe filter, glycidyl methacrylate-ethylene dimethacrylate (GMA-EDMA) porous material and optimal parameters (57 nm, pH 13) gold nanoparticles (AuNPs) was developed for the detection of PAHs in water. The enhancement effect and repeatability of this 3-D substrate were also explored. The Raman intensity of pyrene using 3-D SERS substrate is about 8 times higher than that of substrate only using pH 13 gold colloid solution and about 12 times higher than that of substrate using natural AuNPs and GMA-EDMA porous material, which means both the pH 13 AuNPs and the GMA-EDMA porous material are important factors for the sensitivity of this 3-D SERS substrate. Good repeatability of this optimal 3-D substrate was obtained. The relative standard deviation (RSD) is less than 8.66% on the same substrate and less than 3.69% on other different substrates. Four kinds of PAHs, i.e., phenanthrene, pyrene, benzo(a)pyrene, benzo(k)fluoranthene and their mixture, were detected at the different concentrations. Their limits of detection (LODs) are 8.3×10−10 (phenanthrene), 2.1×10−10 (pyrene), 3.8×10−10 (benzo(a)pyrene) and 1.7×10−10mol L−1 (benzo (k)fluoranthene), respectively. In addition, these four PAHs were also detected by fluorescence spectroscopy to evaluate the sensitivity of SERS technology using this optimal 3-D SERS substrate. The results showed that the sensitivity of SERS based on the 3-D SERS substrate even using the portable Raman system was closed to that of fluorescence spectroscopy. Therefore, the SERS technology using this optimal 3-D substrate is expected to be an in-situ method for the detection of environmental PAHs.
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Acknowledgements
This research was supported by the National Natural Science Foundation of China (No. 41476081), the Major Research and Development Project in Shandong Province (Nos. 2016GSF115020, 2019GHY112027) and the Shandong Provincial Natural Science Foundation (No. ZR2015DM007).
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Shi, X., Yan, X., Zhang, X. et al. Ultrasensitive Detection of Polycyclic Aromatic Hydrocarbons (PAHs) in Water Using Three-Dimensional SERS Substrate Based on Porous Material and pH 13 Gold Nanoparticles. J. Ocean Univ. China 18, 1523–1531 (2019). https://doi.org/10.1007/s11802-019-3911-9
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DOI: https://doi.org/10.1007/s11802-019-3911-9