發(fā)布時(shí)間：2019-03-13 17:05

【摘要】：多環(huán)芳烴(PAHs)是持久性有機(jī)污染物中危害性很大的一類,傳統(tǒng)的檢測方法由于預(yù)處理時(shí)間長和不便于原位檢測的缺點(diǎn)不足以滿足快速檢測需求。新型分析技術(shù)中表面增強(qiáng)拉曼(SERS)提供了可用于高靈敏度檢測的振動光譜,成為了環(huán)境分析領(lǐng)域中新型的檢測手段,擁有巨大的應(yīng)用潛力。本文制備了3種SERS增強(qiáng)基底,對多環(huán)芳烴中常見的萘、蒽、菲、芘和它們的混合物進(jìn)行檢測。本文首先以金屬溶膠法制備了SERS活性基底并進(jìn)行了參數(shù)優(yōu)化。通過調(diào)節(jié)加入檸檬酸鈉的量,合成了平均粒徑約15~150nm的五種粒徑的金溶膠。用這五種粒徑的金溶膠作為基底,通過激發(fā)光785 nm的液體拉曼系統(tǒng),檢測了對對巰基苯甲酸的檢出限均達(dá)到10-8 mol/L,并計(jì)算了金溶膠的SERS增強(qiáng)因子(EF),其中平均粒徑為41nm和72nm的金溶膠特征峰強(qiáng)度較好,與之前的EF計(jì)算結(jié)果吻合。然后選擇粒徑為41nm的金溶膠檢測10-5mol/L的芘,發(fā)現(xiàn)特征峰不明顯。通過濃縮的方法增大納米金密度后,對不同濃度的萘、蒽、菲、芘溶液進(jìn)行了單獨(dú)的SERS光譜探測,測得檢出限均達(dá)到10-7 mol/L。對四種PAHs混合物的檢測發(fā)現(xiàn)特征峰會由于峰重疊與競爭吸附等關(guān)系有所變化和減弱。以不同芘的濃度和特征峰強(qiáng)度為研究對象進(jìn)行線性擬合,線性相關(guān)系數(shù)均在0.985以上�？梢杂糜诎攵繖z測。為了進(jìn)一步提高PAHs的檢測靈敏度,本文通過將金溶膠、不同比例甲醇溶膠和檢測物混合后將沉積物濃縮烘干的方式,在激發(fā)光為633nm的顯微拉曼儀上進(jìn)行了以多環(huán)芳烴中芘為檢測物的檢測。研究了這種檢測方式下金溶膠制備的最佳時(shí)間為30min。檢測的最佳粒徑為72 nm。這與之前的液體拉曼檢測有所區(qū)別,可能與激發(fā)光波長、基底的尺寸和形貌有關(guān)。本文研究了p H值、氯離子等對納米粒子的聚集作用,以及聚集作用對SERS檢測的影響,通過對比,當(dāng)p H=12,氯離子的最終濃度為0.75μmol/L時(shí)檢測效果最好,說明OH-離子和Cl-能更好的促進(jìn)金溶膠和分析物的聚集。實(shí)驗(yàn)用優(yōu)化條件后的金顆�；诇y定芘的檢出限達(dá)到了10-8 mol/L。上述第一種方法中,為獲得良好的檢測效果,需要對剛合成的金溶膠純化濃縮,增加了制備的復(fù)雜性;第二種方法雖然信號得到進(jìn)一步增強(qiáng),但是基底的重復(fù)性不易保證。因此,論文最后探索性地采用易獲得的毛玻璃、砂紙和以砂紙為模板制備的PDMS結(jié)構(gòu),并在表面濺射金做為SERS的增強(qiáng)基底,用激發(fā)光633 nm的顯微拉曼系統(tǒng),檢測了它們SERS背景值,并用砂紙、砂紙翻的PDMS和毛玻璃檢測了芘。
[Abstract]:Polycyclic aromatic hydrocarbons (PAHs) are one of the most harmful persistent organic pollutants (pops). The traditional detection methods can not meet the needs of rapid detection due to the disadvantages of long pretreatment time and inconvenient in-situ detection. Surface-enhanced Raman (SERS) (SERS) can be used to detect vibration spectra with high sensitivity. It has become a new detection method in the field of environmental analysis and has great potential for application. Three SERS-enhanced substrates were prepared for the determination of naphthalene anthracene phenanthrene pyrene and their mixtures in polycyclic aromatic hydrocarbons (PAHs). In this paper, SERS active substrates were prepared by metal sol method and the parameters were optimized. Five kinds of gold sol with average diameter about 15~150nm were synthesized by adjusting the amount of sodium citrate added. The detection limits of p-mercaptobenzoic acid were all up to 10 渭 8 mol/L, using the gold sol as the substrate and the liquid Raman system with excitation light of 785 nm. The SERS enhancement factor (EF), of the gold sol was calculated. The characteristic peak strength of gold sol with average particle size of 41nm and 72nm is better, which is in good agreement with the previous EF calculation results. Then the pyrene of 10-5mol/L was detected by gold sol with the particle size of 41nm, and the characteristic peak was not obvious. The SERS spectra of naphthalene, anthracene, phenanthrene and pyrene with different concentrations were detected by concentration method. The detection limits were all up to 10 ~ 7 mol/L.. The detection of four PAHs mixtures showed that the characteristic summit changed and weakened due to the relationship between peak overlap and competitive adsorption. The linear correlation coefficients of different pyrene concentration and characteristic peak intensity were above 0.985. It can be used for semi-quantitative detection. In order to further improve the detection sensitivity of PAHs, the sediment was concentrated and dried by mixing gold sol, methanol sol in different proportion with the detector. Pyrene in polycyclic aromatic hydrocarbons (PAHs) was detected by micro-Raman spectroscopy (633nm). The optimal preparation time of gold sol was 30 min. The optimum particle size is 72 nm.. This is different from the previous liquid Raman detection, which may be related to the excitation wavelength, the size and morphology of the substrate. In this paper, the effects of pH value, chloride ion and other ions on the aggregation of nanoparticles and the effect of aggregation on the detection of SERS were studied. By comparison, when the final concentration of chloride ion was 0.75 渭 mol / L, the detection effect was the best. The results show that OH- ion and Cl- can promote the aggregation of gold sol and analyte. The detection limit of pyrene was up to 10 ~ 8 mol/L. by using the optimized conditions for the determination of pyrene on the substrate of gold particles. In the first method, in order to obtain a good detection effect, it is necessary to purify and concentrate the newly synthesized gold sol, which increases the complexity of preparation, and the second method, although the signal is further enhanced, is not easy to guarantee the repeatability of the substrate. Therefore, in the end of the thesis, we use easily obtained wool glass, sandpaper and PDMS structure based on sandpaper as template, and sputtering gold on the surface as the reinforced substrate of SERS. The background values of SERS are measured by using the microscope Raman system of excited light 633 nm. Pyrene was detected by sand paper, PDMS and wool glass.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：X830

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