本文選題：農(nóng)藥多殘留分析 + 石墨烯　； 參考：《中國農(nóng)業(yè)大學(xué)》2016年博士論文

【摘要】：常見的碳材料包括活性炭、石墨、石墨化炭黑、碳纖維、金剛石、富勒烯、碳納米管和石墨烯。作為一種新穎的、環(huán)境友好的碳納米材料,石墨烯具有優(yōu)異的結(jié)構(gòu)、熱學(xué)、力學(xué)、電學(xué)和光學(xué)方面的性能,而石墨烯的應(yīng)用極有可能掀起一場席卷全球的顛覆性新技術(shù)新產(chǎn)業(yè)革命。石墨烯的比表面積巨大,其蜂窩狀的六元環(huán)結(jié)構(gòu)能使六個碳原子形成離域大π鍵。這些特性使石墨烯對有機物的富集能力很強,因此,石墨烯在污染物痕量分析檢測與吸附降解領(lǐng)域的應(yīng)用備受關(guān)注。本論文制備了石墨烯粉末、石墨烯衍生物一氨基修飾石墨烯、以及類石墨烯結(jié)構(gòu)的碳材料一石墨型氮化碳。針對農(nóng)藥殘留分析樣品前處理過程中待測物的濃度很低、基質(zhì)背景干擾嚴重的問題,把石墨烯系列材料作為分散固相萃取劑,應(yīng)用于多種樣品的農(nóng)藥殘留分析的樣品前處理技術(shù)中。改良后的分析方法符合樣品前處理技術(shù)向“省時、省力、價格低廉、減少有機溶劑、減少環(huán)境污染”方向發(fā)展的要求。主要研究結(jié)果包括：(1)制備了石墨烯,并采用拉曼光譜和X射線衍射手段進行表征。石墨烯與PSA、GCB的混合材料作為分散固相凈化劑,用于韭菜、洋蔥、大蒜的24種農(nóng)藥多殘留分析。在研究過程中,優(yōu)化了石墨烯的用量,證明了石墨烯的使用有助于凈化背景干擾物,并驗證了方法回收率、檢出限、定量限、基質(zhì)效應(yīng)等,方法的平均回收率為70.1-109.7%,相對標準偏差低于15.6%。該方法也適用于市場樣品的常規(guī)檢測。(2)制備了三種不同鏈長的氨基官能團修飾的石墨烯,并對其進行傅里葉紅外光譜、X射線光電子能譜、X射線衍射和掃描電子顯微鏡分析。甲胺修飾石墨烯作為分散固相凈化劑,用于油菜籽、花生、大豆、芝麻中的31種農(nóng)藥多殘留分析。實驗證明了甲胺修飾石墨烯與PSA、MWCNTs等固相萃取劑相比,具有更加出色的背景干擾物凈化能力。研究優(yōu)化了甲胺修飾石墨烯的用量,驗證了方法回收率、檢出限、定量限、基質(zhì)效應(yīng)等,并對方法創(chuàng)新性進行了討論。方法的平均回收率為70.5-100%,相對標準偏差≤13%。(3)制備了類石墨烯多孔結(jié)構(gòu)的石墨型氮化碳,并進行透射電子顯微鏡、傅里葉紅外光譜、X射線衍射和比表面積分析。建立了石墨型氮化碳作為分散固相吸附劑,用于果汁中的苯甲酰苯脲類農(nóng)藥的殘留分析方法。研究優(yōu)化了影響“萃取-解吸附”過程的多個影響因素,并通過“萃取-解吸附-再生”實驗證明了石墨型氮化碳能被多次重復(fù)利用。研究驗證了方法回收率、檢出限、定量限、基質(zhì)效應(yīng)等,方法的平均回收率為70.4-96.4%,相對標準偏差≤13.9%,該方法適用于市場樣品的常規(guī)檢測。(4)測定了吸附平衡時間和溶液pH值對吸附效果的影響,利用Langmiur和Freundlich模型對吸附等溫線進行擬合,并討論了π-π相互作用和雜原子作用對吸附的影響。在斯德哥爾摩公約中,有機氯農(nóng)藥被列為持久性環(huán)境污染物,能在生物體內(nèi)蓄積,對其后代產(chǎn)生致癌致畸形至突變作用。DDT是有機氯農(nóng)藥的代表,本論文選取了DDT的兩個化學(xué)結(jié)構(gòu)片段一三氯甲烷和氯苯,制備了活性炭負載的雙金屬催化體系,對三氯甲烷和氯苯進行脫氯降解研究。相對DDT而言,三氯甲烷和氯苯結(jié)構(gòu)更為簡單、產(chǎn)物單一,有利于深入探索催化劑的作用機理,為有機氯農(nóng)藥的降解提供研究基礎(chǔ)。本論文制備了Pd/Fe-AC、Pd/AC、Pd/Fe三種催化劑,進行了比表面積測定、CO化學(xué)吸附測定Pd分散度以及ICP-MS技術(shù)測定Pd總量的表征,并用于水中有機污染物的吸附-脫氯降解�；钚蕴繉θ燃淄榈奈椒峙浔仁�2800 L/kg,對氯苯的吸附分配比是35000 L/kg。以三氯甲烷和氯苯為催化降解對象,Pd的催化活性均是Pd/Fe-AC Pd/AC Pd/Fe, Pd/Fe-AC對三氯甲烷的催化脫氯率達94.3%,對氯苯的脫氯率為100%。對Pd/Fe-AC體系表現(xiàn)出優(yōu)異催化性能的原因進行了探索,發(fā)現(xiàn)活性炭的吸附效應(yīng)、Fe-和Pd間的電流作用、Fe0腐蝕產(chǎn)生的H2是促使Pd/Fe-AC快速高效降解三氯甲烷和氯苯的主要原因。Pd/Fe-AC對氯苯是完全脫氯,對三氯甲烷是不完全脫氯,因此,可以推測Pd/Fe-AC對DDT的脫氯降解亦為不完全脫氯反應(yīng),1,1,1-三氯甲基上的氯較難完全去除,但總的脫氯效率較高。
[Abstract]:Common carbon materials include activated charcoal, graphite, graphitized carbon black, carbon fiber, diamond, fullerene, carbon nanotube and graphene. As a novel, environmentally friendly carbon nanomaterial, graphene has excellent structural, thermal, mechanical, electrical and optical properties, and the application of graphene is likely to set off a sweeping sweep of the world. The subversive new technology and new industrial revolution. The specific surface area of graphene is huge, and its honeycomb six membered ring structure can make six carbon atoms form large off domain PI bonds. These properties make graphene rich in organic matter. Therefore, the application of graphene in the field of trace analysis and adsorption degradation of pollutants has attracted much attention. Graphene powder, graphene derivative monoamine modified graphene, and graphite like carbon material of graphene structure have been prepared. The graphene series material is used as a dispersible solid phase extractant in the process of pretreatment of pesticide residues. In the sample pretreatment technology of pesticide residue analysis, the improved analysis method accords with the requirements of sample pretreatment technology to "save time, labor, low price, reduce organic solvents and reduce environmental pollution". The main research results include: (1) the preparation of stonene and using Raman and X ray diffraction methods Characterization. The mixture of graphene and PSA, GCB as a dispersive solid phase purifier, used in the analysis of 24 kinds of pesticide residues in leek, onion and garlic. During the study, the amount of graphene was optimized. It was proved that the use of graphene could help to purify the background interferon, and verified the recovery rate, detection limit, quantitative limit, matrix effect and so on. The average recovery rate of the method is 70.1-109.7% and the relative standard deviation is lower than 15.6%.. The method is also suitable for the routine testing of the market samples. (2) three kinds of amino functional group modified graphene with different chain length are prepared, and their Fourier infrared spectroscopy, X ray photoelectron spectroscopy, X ray diffraction and scanning electron microscope analysis. Methylamine modification. As a dispersed solid phase purifier, graphene is used for the analysis of 31 kinds of pesticide residues in rapeseed, peanut, soybean and sesame. The experiment has proved that methylamine modified graphene has a better purifying ability of background interferon than PSA, MWCNTs and other solid phase extractants. The study optimized the amount of methylamine modified graphene and verified the recovery rate of the method. The detection limit, the quantitative limit, the matrix effect and the method innovation are discussed. The average recovery rate of the method is 70.5-100%, the graphite like carbon nitride of the porous structure of graphene like structure is prepared by the relative standard deviation less than 13%. (3), and the transmission electron microscope, the Fu Liyehong external spectrum, the X ray diffraction and the specific surface area analysis are carried out. Carbon nitride is used as a dispersible solid phase adsorbent for the analysis of benzylbenzourea pesticide residues in juice. Several factors affecting the "extraction desorption" process are studied and optimized. Through the "extraction desorption regeneration" experiment, it is proved that graphite type carbon nitride can be reused many times. Rate, detection limit, quantitative limit, matrix effect and so on, the average recovery rate of the method is 70.4-96.4%, the relative standard deviation is less than 13.9%. This method is suitable for the routine testing of the market samples. (4) the adsorption equilibrium time and the effect of the solution pH value on the adsorption effect are measured. The adsorption isotherms are fitted by Langmiur and Freundlich models, and the pion is discussed. In the Stockholm convention, organochlorine pesticides are listed as persistent environmental pollutants in the Stockholm convention. They can accumulate in organisms and produce carcinogenic deformities to their descendants to be the representative of organochlorine pesticides. In this paper, two chemical fragments of DDT were selected, and chloroform and trichloromethane were selected. Chlorobenzene, preparation of activated carbon loaded bimetallic catalytic system, dechlorination of chloroform and chlorobenzene dechlorination study. Relative to DDT, trichloromethane and chlorobenzene structure is more simple, the product is single, it is beneficial to explore the mechanism of the catalyst and provide the basis for the degradation of organochlorine pesticides. This paper has prepared Pd/Fe-AC, Pd/AC, Pd/Fe three catalysts were used to determine the specific surface area, CO chemisorption, Pd dispersion and ICP-MS technology for the determination of Pd total. It was used for adsorption dechlorination of organic pollutants in water. The adsorption distribution ratio of activated carbon to trichloromethane was 2800 L/kg, and the ratio of chlorobenzene to chlorobenzene was 35000 L/kg. with Trichloromethane and chlorobenzene as the ratio of chlorobenzene. The catalytic activity of Pd is Pd/Fe-AC Pd/AC Pd/Fe, the catalytic dechlorination rate of Pd/Fe-AC to trichloromethane is 94.3%. The reason that the dechlorination rate of chlorobenzene is 100%. to Pd/Fe-AC system has been explored. The adsorption effect of activated carbon, the action of the current between Fe- and Pd, H2 of Fe0 corrosion are promoted. The main reason for the rapid and efficient degradation of chlorobenzene and Chlorobenzene by Pd/Fe-AC.Pd/Fe-AC is completely dechlorinated and chloroform is not completely dechlorinated. Therefore, it is possible to speculate that the dechlorination degradation of DDT by Pd/Fe-AC is also incomplete dechlorination, and the chlorine on 1,1,1- three chloromethyl chloride is difficult to completely remove, but the total dechlorination efficiency is higher.
【學(xué)位授予單位】：中國農(nóng)業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：X592;S481.8
，

本文編號：1906148