Ultrasensitive Detection of Polycyclic Aromatic Hydrocarbons(PAHs) in Water Using Three-Dimensional SERS Substrate Based on Porous Material and pH 13 Gold Nanoparticles  

作　　者：SHI Xiaofeng YAN Xia ZHANG Xinmin MA Lizhen ZHANG Xu WANG Chunyan MA Jun 

机构地区：[1]Optics and Optoelectronics Laboratory,Ocean University of China,Qingdao 266100,China [2]Department of Physics and Electronic Science,Weifang University,Weifang 261061,China

出　　处：《Journal of Ocean University of China》2019年第6期1523-1531,共9页中国海洋大学学报（英文版）

基　　金：supported by the National Natural Science Foundation of China (No. 41476081);the Major Research and Development Project in Shandong Province (Nos. 2016GSF115020, 2019GHY112027);the Shandong Provincial Natural Science Foundation (No. ZR2015DM007)

摘　　要：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(Au NPs)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 p H 13 gold colloid solution and about 12 times higher than that of substrate using natural Au NPs and GMA-EDMA porous material,which means both the pH 13 AuN Ps 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^-10 mol 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.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（Au NPs） 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 p H 13 gold colloid solution and about 12 times higher than that of substrate using natural Au NPs and GMA-EDMA porous material, which means both the pH 13 AuN Ps 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 1.7×10-10 mol 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.

关 键 词：surface-enhanced Raman scattering(SERS) POLYCYCLIC aromatic hydrocarbons(PAHs) THREE-DIMENSIONAL SERS SUBSTRATE fluorescence spectroscopy 

分 类 号：O65[理学—分析化学]