基于納米材料修飾電極的酚類污染物電化學(xué)傳感器研究
發(fā)布時(shí)間：2019-06-08 06:54
【摘要】：隨著經(jīng)濟(jì)的發(fā)展,酚類物質(zhì)被大量應(yīng)用于工業(yè)領(lǐng)域,對(duì)土壤和水環(huán)境造成了污染,且其在環(huán)境中很難降解,不斷累積的酚類污染物會(huì)通過(guò)食物鏈進(jìn)入到人體中。由于酚類物質(zhì)的較大毒性,即使在濃度很低時(shí)都會(huì)造成人體機(jī)能紊亂甚至致癌,因此,發(fā)展一種對(duì)環(huán)境中的酚類污染物進(jìn)行快速、準(zhǔn)確測(cè)定的方法,有著十分重要的現(xiàn)實(shí)意義。目前檢測(cè)酚類物質(zhì)的方法較多,電化學(xué)方法具有成本低、快速方便、靈敏度和準(zhǔn)確度高、檢測(cè)的濃度范圍寬等優(yōu)點(diǎn),廣泛應(yīng)用于酚類物質(zhì)的檢測(cè)。在電化學(xué)分析中,可通過(guò)將電極表面附著上一些功能性的物質(zhì)制備化學(xué)修飾電極,來(lái)增加電極的電流響應(yīng)、提高檢測(cè)的靈敏度。本文通過(guò)構(gòu)建了四種納米材料修飾電極,對(duì)不同種的酚類物質(zhì)進(jìn)行了測(cè)定。主要研究?jī)?nèi)容如下:1.基于離子液體功能化類水滑石的雙酚A電化學(xué)傳感器研究采用共沉淀法合成了氨基功能化離子液體(1-胺丙基-3-甲基咪唑四氟硼酸鹽)修飾的鋅鋁類水滑石(ILs-LDH),通過(guò)滴涂法將ILs-LDH修飾在玻碳電極表面,制得ILs-LDH/GCE修飾電極,并將其用于雙酚A的測(cè)定。實(shí)驗(yàn)結(jié)果表明,該修飾電極可加快雙酚A的電化學(xué)氧化進(jìn)程,使其氧化峰電流明顯增加,氧化過(guò)電位明顯降低。在最優(yōu)實(shí)驗(yàn)條件下,采用DPV進(jìn)行測(cè)定,雙酚A在0.02~3μM的濃度范圍內(nèi)與其氧化峰電流值呈線性關(guān)系,其檢出限為4.6 nM(S/N=3)。此外,將其應(yīng)用于實(shí)際水樣中的雙酚A檢測(cè),回收率在94.9%到102.0%之間。2.基于超薄類水滑石納米片的雙酚A電化學(xué)傳感器研究超薄Ni_2Al類水滑石納米片(ELDH)在水溶介質(zhì)中用L-天冬酰胺剝離,剝離的納米片直徑約為200 nm,厚度小于3 nm。制備超薄類水滑石納米片修飾電極對(duì)雙酚A進(jìn)行檢測(cè),結(jié)果顯示修飾電極呈現(xiàn)優(yōu)良的電化學(xué)性能,雙酚A具有較低的氧化電位(0.489 V)。差分脈沖伏安法對(duì)雙酚A檢測(cè)呈現(xiàn)較寬的線性檢測(cè)范圍(0.02~1.51μM)和較低的檢出限(6.8 nM)。此外,將其應(yīng)用于實(shí)際牛奶樣品的檢測(cè),結(jié)果滿意。3.基于離子液體結(jié)構(gòu)化的氮化碳納米片電化學(xué)傳感器用于2,4-二氯酚的檢測(cè)用正溴丁烷與質(zhì)子化已剝離的氮化碳反應(yīng),得到離子液體結(jié)構(gòu)化的氮化碳納米片。將其修飾到電極表面,制備IL-eC3N4/GCE,結(jié)果表明該修飾電極對(duì)2,4-DCP的電化學(xué)氧化有較強(qiáng)的催化活性,2,4-二氯酚的氧化峰電位明顯負(fù)移。電流-時(shí)間曲線顯示2,4-DCP的濃度在0.02~160μM之間,峰電流與濃度成正比且檢出限為6.67 nM。此外,將其應(yīng)用于湖水和礦物水中鄰苯二酚的檢測(cè),加標(biāo)回收率在97%~106%之間。4.基于碳量子點(diǎn)-銀復(fù)合物的鄰苯二酚電化學(xué)傳感器的研究一步水熱法合成了氮硫摻雜的碳量子點(diǎn),然后用碳量子點(diǎn)原位還原硝酸銀制備了碳量子點(diǎn)-銀納米復(fù)合物(N-S-CQDs-Ag),將N-S-CQDs-Ag修飾到玻碳電極表面構(gòu)建檢測(cè)鄰苯二酚的電化學(xué)傳感器。分析結(jié)果表明,該傳感器明顯降低了鄰苯二酚的氧化還原峰電位差(ΔEp),線性檢測(cè)范圍為0.2~180μM,檢出限為0.013μM,實(shí)現(xiàn)了對(duì)鄰苯二酚的高靈敏和高效分析。此外,將其應(yīng)用于湖水和自來(lái)水中鄰苯二酚的檢測(cè),加標(biāo)回收率在97%~107%之間。
[Abstract]:With the development of economy, the phenolic substances are widely used in the industrial field, and the soil and the water environment are polluted, and the phenolic contaminants are difficult to degrade in the environment, and the continuously accumulated phenolic contaminants can enter into the human body through the food chain. Because of the great toxicity of the phenolic substances, even when the concentration is low, the human body function disorder is even carcinogenic, therefore, the method for rapidly and accurately measuring the phenolic contaminants in the environment is of great practical significance. The method for detecting the phenolic substance is more, the electrochemical method has the advantages of low cost, high speed, high sensitivity and accuracy, wide detection concentration range and the like, and is widely applied to the detection of the phenolic substances. In the electrochemical analysis, a chemical modification electrode can be prepared by attaching some of the functional materials to the surface of the electrode to increase the current response of the electrode and improve the detection sensitivity. In this paper, four kinds of nano-material modified electrodes were constructed, and different kinds of phenolic compounds were measured. The main contents of the study are as follows:1. The zinc-aluminum hydrotalcite (ILs-LDH) modified by amino-functional ionic liquid (1-aminopropyl-3-methyl-4-fluoroborate) was synthesized by co-precipitation method based on the study of the ionic liquid-functionalized hydrotalcite-based bisphenol A electrochemical sensor. The ILs-LDH was modified on the surface of the glassy carbon electrode by a drop coating method, and the ILs-LDH/ GCE modified electrode was prepared and used in the determination of bisphenol A. The experimental results show that the modified electrode can accelerate the electrochemical oxidation process of bisphenol A, and the oxidation peak current of the modified electrode is obviously increased, and the oxidation potential is obviously reduced. Under the optimum experimental conditions, DPV was used to determine the concentration of bisphenol A in the concentration range of 0.02 to 3. m u.M, and the detection limit was 4.6 nM (S/ N = 3). In addition, it is applied to the detection of bisphenol A in the real water sample, and the recovery rate is between 94.9% and 102.0%. In this paper, an ultra-thin Ni _ 2Al hydrotalcite-like nano-sheet (ELDH) is separated by L-triammine in a water-soluble medium based on an ultra-thin hydrotalcite-like nano-sheet, and the peeled nano-sheet has a diameter of about 200 nm and a thickness of less than 3 nm. The result showed that the modified electrode exhibited excellent electrochemical performance and bisphenol A had a lower oxidation potential (0.489 V). The differential pulse voltammetry showed a wide linear detection range (0.02-1.51. mu.M) and a lower detection limit (6.8 nM) for bisphenol A detection. In addition, it is applied to the detection of real milk samples, and the results are satisfactory. The ion-liquid-structured carbon nitride nanosheet electrochemical sensor is used for the detection of 2,4-dichlorophenol, and the n-bromobutane is reacted with the deprotonated carbon nitride to obtain the ionic liquid-structured carbon nitride nanosheet. The results show that the modified electrode has strong catalytic activity to the electrochemical oxidation of 2,4-DCP, and the oxidation peak potential of 2,4-dichlorophenol is obviously negative. The current-time curve shows that the concentration of 2,4-DCP is between 0.02 and 160. m u.M, the peak current is proportional to the concentration and the detection limit is 6.67 nM. In addition, the method is applied to the detection of the catechol in the lake water and the mineral water, and the recovery rate of the spike is between 97% and 106%. A carbon quantum dot-silver nano-composite (N-S-CQDs-Ag) is prepared by a step-by-step hydrothermal method of a pyrocatechol electrochemical sensor based on a carbon quantum dot-silver complex, And the N-S-CQDs-Ag is modified to the surface of the glassy carbon electrode to construct an electrochemical sensor for detecting the catechol. The results of the analysis show that the oxidation-reduction peak potential difference (OEp) of the pyrocatechol is obviously reduced, the linear detection range is 0.2-180. m u.M, the detection limit is 0.013. m u.M, and the high-sensitivity and high-efficiency analysis of the catechol is realized. In addition, the method is applied to the detection of the catechol in the lake water and the tap water, and the recovery rate of the spike is between 97% and 107%.
【學(xué)位授予單位】：青島科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O657.1
本文編號(hào)：2495088
[Abstract]:With the development of economy, the phenolic substances are widely used in the industrial field, and the soil and the water environment are polluted, and the phenolic contaminants are difficult to degrade in the environment, and the continuously accumulated phenolic contaminants can enter into the human body through the food chain. Because of the great toxicity of the phenolic substances, even when the concentration is low, the human body function disorder is even carcinogenic, therefore, the method for rapidly and accurately measuring the phenolic contaminants in the environment is of great practical significance. The method for detecting the phenolic substance is more, the electrochemical method has the advantages of low cost, high speed, high sensitivity and accuracy, wide detection concentration range and the like, and is widely applied to the detection of the phenolic substances. In the electrochemical analysis, a chemical modification electrode can be prepared by attaching some of the functional materials to the surface of the electrode to increase the current response of the electrode and improve the detection sensitivity. In this paper, four kinds of nano-material modified electrodes were constructed, and different kinds of phenolic compounds were measured. The main contents of the study are as follows:1. The zinc-aluminum hydrotalcite (ILs-LDH) modified by amino-functional ionic liquid (1-aminopropyl-3-methyl-4-fluoroborate) was synthesized by co-precipitation method based on the study of the ionic liquid-functionalized hydrotalcite-based bisphenol A electrochemical sensor. The ILs-LDH was modified on the surface of the glassy carbon electrode by a drop coating method, and the ILs-LDH/ GCE modified electrode was prepared and used in the determination of bisphenol A. The experimental results show that the modified electrode can accelerate the electrochemical oxidation process of bisphenol A, and the oxidation peak current of the modified electrode is obviously increased, and the oxidation potential is obviously reduced. Under the optimum experimental conditions, DPV was used to determine the concentration of bisphenol A in the concentration range of 0.02 to 3. m u.M, and the detection limit was 4.6 nM (S/ N = 3). In addition, it is applied to the detection of bisphenol A in the real water sample, and the recovery rate is between 94.9% and 102.0%. In this paper, an ultra-thin Ni _ 2Al hydrotalcite-like nano-sheet (ELDH) is separated by L-triammine in a water-soluble medium based on an ultra-thin hydrotalcite-like nano-sheet, and the peeled nano-sheet has a diameter of about 200 nm and a thickness of less than 3 nm. The result showed that the modified electrode exhibited excellent electrochemical performance and bisphenol A had a lower oxidation potential (0.489 V). The differential pulse voltammetry showed a wide linear detection range (0.02-1.51. mu.M) and a lower detection limit (6.8 nM) for bisphenol A detection. In addition, it is applied to the detection of real milk samples, and the results are satisfactory. The ion-liquid-structured carbon nitride nanosheet electrochemical sensor is used for the detection of 2,4-dichlorophenol, and the n-bromobutane is reacted with the deprotonated carbon nitride to obtain the ionic liquid-structured carbon nitride nanosheet. The results show that the modified electrode has strong catalytic activity to the electrochemical oxidation of 2,4-DCP, and the oxidation peak potential of 2,4-dichlorophenol is obviously negative. The current-time curve shows that the concentration of 2,4-DCP is between 0.02 and 160. m u.M, the peak current is proportional to the concentration and the detection limit is 6.67 nM. In addition, the method is applied to the detection of the catechol in the lake water and the mineral water, and the recovery rate of the spike is between 97% and 106%. A carbon quantum dot-silver nano-composite (N-S-CQDs-Ag) is prepared by a step-by-step hydrothermal method of a pyrocatechol electrochemical sensor based on a carbon quantum dot-silver complex, And the N-S-CQDs-Ag is modified to the surface of the glassy carbon electrode to construct an electrochemical sensor for detecting the catechol. The results of the analysis show that the oxidation-reduction peak potential difference (OEp) of the pyrocatechol is obviously reduced, the linear detection range is 0.2-180. m u.M, the detection limit is 0.013. m u.M, and the high-sensitivity and high-efficiency analysis of the catechol is realized. In addition, the method is applied to the detection of the catechol in the lake water and the tap water, and the recovery rate of the spike is between 97% and 107%.
【學(xué)位授予單位】：青島科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O657.1
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相關(guān)期刊論文 前2條
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