石墨烯复合材料的制备及萃取性能研究

发布时间：2018-01-03 19:32

本文关键词：石墨烯复合材料的制备及萃取性能研究　出处：《河南工业大学》2015年硕士论文　论文类型：学位论文

【摘要】：石墨烯(Graphene,G)具有比表面积大、疏水性、热稳定性和化学稳定性等性质,而且它含有丰富的π电子体系,有望成为良好的吸附剂材料广泛应用于分离分析领域。但是,G的层与层间距小,范德华力和π-π相互作用力较强,极易发生团聚现象,这使其在水中或者有机溶剂中的分散性差。对G进行功能化能赋予它更新更好的特点,使它的应用范围进一步扩大。本文制备了G复合材料,探讨它对环境中有机污染物的萃取性能及应用。利用1-乙烯基-3-己基咪唑溴盐与氧化石墨烯之间的静电吸引力将其附着于氧化石墨烯表面,然后经聚合、还原制备了聚合离子液体-G复合材料(Poly(VHIm+Br-)-G),利用扫描电子显微镜、傅里叶变换红外光谱和紫外光谱等对Poly(VHIm+Br-)-G复合材料进行了表征。首次将Poly(VHIm+Br-)-G复合材料用于SPE的吸附剂,结合HPLC,研究了该新型吸附剂对环境水样中4种有机磷农药(OPPs)的萃取性能。对影响SPE效率的参数(吸附剂量、上样体积、上样流速、洗脱剂和洗脱剂体积)进行了优化。在优化条件下,杀螟松、对硫磷、倍硫磷和辛硫磷在5-200μg L-1有良好的线性关系,相关系数(r2)为0.9908-0.9995。将建立的方法应用于环境水样中OPPs的测定,加标回收率在80.0%-110.0%之间,RSD(n=3)小于4.5%。结果表明,与G相比,Poly(VHIm+Br-)-G复合材料作为SPE吸附剂,能降低萃取过程中的团聚现象,对目标分析物的萃取效能更高;建立的方法Poly(VHIm+Br-)-G-SPE-HPLC-UV适用于实际水样中OPPs残留的测定。利用氧化石墨烯与硫酸亚铁之间的氧化还原性以及在碱性条件下Fe2+和Fe3+可以共沉淀形成Fe3O4,自组装G与Fe3O4形成三维磁性石墨烯复合材料(3D-G-Fe3O4),利用傅利叶变换红外光谱、透射电子显微镜、热重分析和比表面积及孔径分析等对其进行结构表征。将3D-G-Fe3O4复合材料用作MSPE的吸附剂,结合HPLC,研究其对水样中PAHs的萃取性能。对影响MSPE效率的参数(吸附剂量、样品体积、吸附时间、解析剂、解吸剂量及时间和盐浓度)进行了优化。在优化的条件下,萘在0.1-40.0μg L-1、联苯在0.05-20.0μg L-1、菲在0.6-100.0μg L-1、蒽在0.2-100.0μg L-1有良好的线性关系,相关系数(r2)为0.9994-0.9997。将建立的方法应用于环境水样中PAHs的测定,加标回收率在84.2%-107.0%之间,RSD(n=3)小于5.8%。与其它测定PAHs的方法比较,该方法测定环境水样中的PAHs有好的重复性和宽的线性范围,吸附剂用量少,减少了成本,且萃取时间短,加快了分析速率。建立的方法3D-G-Fe3O4-MSPE-HPLC-UV适用于检测水样中的PAHs残留。为了进一步探讨3D-G-Fe3O4对不同种类分析物的吸附效能以及吸附机理,将3D-G-Fe3O4用作吸附剂材料,以3种多环芳烃(萘、菲和荧蒽)、3种氨基甲酸酯类(甲萘威、仲丁威和异丙威)和3种酚类(对硝基苯酚、甲萘酚和双酚A)为目标分析物,研究了其在3D-G-Fe3O4上的吸附等温线和动力学行为。结果表明,分析物结构不同,与3D-G-Fe3O4上活性位点的相互作用不同,导致不同的吸附行为。3D-G-Fe3O4对甲萘威、对硝基苯酚、甲萘酚和双酚A的吸附符合Langmuir吸附模型,而对萘、菲、荧蒽、仲丁威和异丙威的吸附符合Freundlich吸附模型。所有目标分析物的吸附过程均遵循二级吸附动力学模型。
[Abstract]:Shi Moxi (Graphene, G) with a large surface area, hydrophobicity, thermal stability and chemical stability and other properties, and it contains rich pi electron system, is expected to be widely used in the separation and analysis of good adsorbent material. However, the G layer and the layer spacing is small, van Edward and PI pi interaction the force is strong, easy to agglomerate phenomenon, which makes it in water or organic solvent in dispersion. The G function can give it the better, to further expand the scope of its application. The G composite material was prepared in this paper, it discusses on the extraction performance of organic pollutants in the environment and application by the electrostatic attraction between 1- vinyl -3- hexyl imidazolium bromide and graphene oxide will be attached to the surface of graphene oxide, then prepared by polymerization, reduction of ionic liquid polymer -G composites (Poly (VHIm+Br-) -G), by using scanning electric The electron microscope, Fourier transform infrared spectroscopy and UV spectra of Poly (VHIm+Br-) -G composites were characterized for the first time. Poly (VHIm+Br-) -G composite adsorbent for SPE, combined with HPLC, the research of the new adsorbent of 4 organophosphorus pesticides in environmental water samples (OPPs) extraction performance. The parameters affecting the efficiency of SPE (adsorption dosage, sample volume, sample flow rate, eluent and elution volume) were optimized. Under the optimized conditions, fenitrothion, parathion, fenthion and phoxim had a good linear relationship in the range of 5-200 g L-1, the correlation coefficient (R2) method for the determination of 0.9908-0.9995. the application to OPPs in environmental water samples, the recoveries were 80.0%-110.0%, RSD (n=3) is less than 4.5%.. The results showed that compared with G, Poly (VHIm+Br-) -G composite material as SPE adsorbent can reduce the agglomeration of the extraction process of target analyte The extraction efficiency is high; the Poly method (VHIm+Br- -G-SPE-HPLC-UV) was applied to the determination of OPPs residues in real water samples. The oxidation between graphene oxide and ferrous sulfate reduction and Fe2+ under alkaline conditions and Fe3+ can form Fe3O4 co precipitation, and the formation of Fe3O4 self assembled G 3D magnetic graphene composites (3D-G-Fe3O4) and by using Fourier transform infrared spectroscopy, transmission electron microscopy, thermogravimetric analysis and specific surface area and pore size distribution and characterized. The 3D-G-Fe3O4 composites used as adsorbent, MSPE combined with HPLC, the research of PAHs in water extraction performance. The parameters influencing the efficiency of the MSPE (the adsorption dose. The sample volume, time of adsorption, desorption agent, desorption time and dose and salt concentration) were optimized. Under the optimized conditions, the 0.1-40.0 g L-1 of naphthalene, biphenyl in 0.05-20.0 g L-1 0.6-100.0 g L-1, phenanthrene, anthracene There is a good linear relationship in the range of 0.2-100.0 g L-1, the correlation coefficient (R2) method for the determination of the 0.9994-0.9997. will be built based on PAHs in environmental water samples, the recoveries were 84.2%-107.0%, RSD (n=3) is less than 5.8%. and the other PAHs determination method, the determination method of PAHs is good repeatability and wide linear range, adsorbent dosage, lower cost, and shorter extraction time, speed up the rate of analysis. The 3D-G-Fe3O4-MSPE-HPLC-UV method is suitable for the detection of residues in water samples by PAHs. In order to further explore the effectiveness of different types of 3D-G-Fe3O4 on the adsorption of the analyte and the adsorption mechanism of 3D-G-Fe3O4, will be used as an adsorbent material to 3 kinds of PAHs (naphthalene, phenanthrene and fluoranthene), 3 carbamates (carbaryl, fenobucarb, Isoprocarb) and 3 kinds of phenols (p-nitrophenol, 1-naphthol and bisphenol A) as the target analyte was studied The 3D-G-Fe3O4 in the adsorption isotherm and kinetics analysis. The results show that the structure is different, different interactions with the 3D-G-Fe3O4 active site, resulting in different adsorption behavior of.3D-G-Fe3O4 for carbaryl, p-nitrophenol, phenol and bisphenol A adsorption accords with Langmuir adsorption model and of naphthalene, phenanthrene, fluoranthene, adsorption fenobucarb and Isoprocarb with Freundlich adsorption model. The adsorption process of all the objectives were to follow two adsorption kinetic model.

【学位授予单位】：河南工业大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ127.11;TB33

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