新型化學(xué)修飾電極的構(gòu)建及其在COD檢測(cè)中的應(yīng)用和碳量子點(diǎn)的制備及其性質(zhì)研究
發(fā)布時(shí)間：2018-11-15 19:58
【摘要】：化學(xué)需氧量(COD)是評(píng)價(jià)水體污染程度的重要綜合指標(biāo)之一,指一定條件下,水體中的還原性物質(zhì)被強(qiáng)氧化劑氧化消耗的氧化劑所對(duì)應(yīng)的氧的濃度。隨著我國(guó)工農(nóng)業(yè)的快速發(fā)展和城市化進(jìn)程的日益加劇,環(huán)境污染問題日益嚴(yán)重。目前,我國(guó)測(cè)定COD的標(biāo)準(zhǔn)方法主要是重鉻酸鉀法,該方法準(zhǔn)確度高、重現(xiàn)性好,應(yīng)用最為廣泛。但是重鉻酸鹽法操作過程耗時(shí)長(zhǎng),測(cè)定成本高,二次污染較嚴(yán)重；受回流裝置的限制,難以同時(shí)分析大批量樣品。為了改進(jìn)以上缺點(diǎn),縮短分析時(shí)間,實(shí)現(xiàn)COD的在線監(jiān)測(cè),研發(fā)快速、靈敏、簡(jiǎn)便的環(huán)境監(jiān)測(cè)新方法和新技術(shù)顯得十分重要。運(yùn)用納米材料,如納米碳材料、納米金屬和金屬氧化物材料、有機(jī)聚合膜及其相關(guān)的復(fù)合材料作為修飾電極是當(dāng)前化學(xué)修飾電極發(fā)展的新方向,對(duì)于提高分析方法的靈敏度和選擇性具有重要意義。基于此,本文構(gòu)建了兩種新型的化學(xué)修飾電極,可以靈敏、快速、簡(jiǎn)便地電化學(xué)檢測(cè)COD并成功應(yīng)用于地表水COD的檢測(cè)分析,具體的內(nèi)容與結(jié)果如下： 1、以Co(NO3)2為前驅(qū)體,利用恒電位氧化技術(shù)在玻碳電極表面原位制備出納米鈷氧化物敏感膜。直接以湖水水樣為研究對(duì)象,考察了沉積電位、沉積介質(zhì)、沉積時(shí)間以及Co2+的濃度對(duì)COD響應(yīng)信號(hào)的影響規(guī)律并成功調(diào)控了納米鈷氧化物敏感膜的形貌,結(jié)果表明納米鈷氧化物敏感膜能顯著提高COD的電化學(xué)響應(yīng)信號(hào),建立了一種簡(jiǎn)便、靈敏、快速測(cè)定COD的電化學(xué)方法,在COD值為1.7mgL-1到170mg L-1的范圍內(nèi),其響應(yīng)信號(hào)與COD值呈現(xiàn)良好的線性關(guān)系。該方法的檢出限為1.1mg L-1。為驗(yàn)證鉆氧化物敏感膜的實(shí)際應(yīng)用,將新方法應(yīng)用于不同湖泊水水樣的COD值測(cè)定,測(cè)定結(jié)果與重鉻酸鉀法測(cè)定結(jié)果有很好的一致性。 2、以Co(NO3)2和CuCl2為前驅(qū)體通過電化學(xué)沉積法在金電極表面原位制備出了微納米銅鉆合金敏感膜。在此基礎(chǔ)上,以葡萄糖為電化學(xué)測(cè)定COD的標(biāo)準(zhǔn)物,系統(tǒng)考察了改變Cu2+、Co2+離子濃度比、沉積電流、沉積介質(zhì)以及沉積時(shí)間對(duì)響應(yīng)信號(hào)的影響規(guī)律并成功調(diào)控了微納米Cu-Co敏感膜的形貌。結(jié)果表明,所制備的微納米Cu-Co敏感膜能顯著提高COD的電化學(xué)響應(yīng)信號(hào),并利用安培檢測(cè)法實(shí)現(xiàn)了COD的快速電化學(xué)測(cè)定,其線性范圍為1.92mg L1-768mgL-1,基于3倍信噪比的檢出限為0.609mg L-。將此方法用于實(shí)際水樣COD的測(cè)定,重復(fù)性高,并與國(guó)標(biāo)方法進(jìn)行了對(duì)比,測(cè)定結(jié)果與國(guó)標(biāo)方法結(jié)果相吻合。 3、熒光碳量子點(diǎn)(Carbon dots)作為一種新型的碳納米材料,在近年來引起了廣泛關(guān)注。碳量子點(diǎn)的粒徑一般小于10nm。碳量子點(diǎn)相對(duì)于傳統(tǒng)熒光染料和半導(dǎo)體量子點(diǎn)往往表現(xiàn)出良好的熒光強(qiáng)度、較強(qiáng)的穩(wěn)定性、可調(diào)控的發(fā)射波長(zhǎng)、較高的溶解性、很好的生物相容性等特點(diǎn),因此越來越被廣泛應(yīng)用于細(xì)胞成像,藥物傳輸、小分子傳感檢測(cè)、生命科學(xué)等。本文第四章以葡萄糖和葉酸為前驅(qū)體通過熱解法合成了高量子產(chǎn)率的磷摻雜碳量子點(diǎn)(量子產(chǎn)率為21.82%)。該碳量子點(diǎn)可被Fe3+選擇性淬滅,基于此,建立了檢測(cè)Fe3+的熒光體系,研究了磷酸鹽溶液濃度、磷酸鹽溶液pH、熱解時(shí)間及熱解溫度對(duì)碳量子點(diǎn)熒光強(qiáng)度及Fe3+檢測(cè)能力的影響。將此新方法應(yīng)用于人血清Fe3+的測(cè)定,測(cè)定結(jié)果與火焰原子吸收光譜法測(cè)定結(jié)果相一致性。最后將制備的熒光碳量子點(diǎn)應(yīng)用于細(xì)胞成像,結(jié)果顯示高分化的大鼠腎上腺嗜鉻細(xì)胞瘤細(xì)胞(PC12細(xì)胞)在藍(lán)光下受激發(fā)發(fā)出明亮、均勻的藍(lán)色熒光。
[Abstract]:The chemical oxygen demand (COD) is one of the important comprehensive indexes to evaluate the degree of water pollution. With the rapid development of industry and agriculture in China and the increasing process of urbanization, the problem of environmental pollution is becoming more and more serious. At present, the standard method for the determination of COD in China is mainly the potassium dichromate method. The method has the advantages of high accuracy, good reproducibility and wide application. but the process of the dichromate method has the advantages of long operation time, high measurement cost and serious secondary pollution, and is difficult to analyze large batch samples at the same time by the restriction of the reflux device. In order to improve the above disadvantages, it is very important to shorten the analysis time, realize the on-line monitoring of COD, and develop a new method and new technology for rapid, sensitive and simple environment monitoring. The use of nano-materials, such as nano-carbon materials, nano-metal and metal oxide materials, organic polymer films and related composite materials as modified electrodes, is a new direction for the development of the current chemical modification electrode, and is of great significance for improving the sensitivity and selectivity of the analytical method. On the basis of this, two new chemical modification electrodes are constructed, which can be sensitive, rapid, and can be used for the detection and analysis of COD in surface water. The specific contents and results are as follows: 1. Prior to Co (NO3) 2 in situ preparation of nano-cobalt oxide in that surface of a glass-carbon electrode by using a constant-potential oxidation technique The effect of the deposition potential, the deposition medium, the deposition time and the concentration of Co2 + on the response signal of COD was studied. The influence of the concentration of Co2 + on the response signal of COD was studied. The results show that the nano-cobalt oxide-sensitive film can obviously improve the electrochemical response signal of COD, and a simple, sensitive and rapid electrochemical method for measuring COD is established. The response signal and the COD value show a good linearity in the range of COD value of 1. 7mgL-1 to 170mg L-1. The detection limit of the method is 1. 1mg L.-1. In order to verify the practical application of the oxide-sensitive membrane, the new method is applied to the determination of COD in water samples of different lakes. The results of the determination and the potassium dichromate method are very good. The micro-nano-copper drill was prepared in situ on the surface of the gold electrode by electrochemical deposition using Co (NO3) 2 and CuCl2 as the precursor. The influence of Cu 2 +, Co2 + ion concentration ratio, deposition current, deposition medium and deposition time on the response signal was investigated by using glucose as the standard for electrochemical measurement of COD, and the micro-nano Cu-Co-sensitive was successfully controlled. The results show that the prepared micro-nano Cu-Co sensitive film can obviously improve the electrochemical response signal of COD, and the rapid electrochemical measurement of COD is realized by the Ampere detection method. The linear range of the micro-nano Cu-Co-sensitive film is 1. 922mg L1-768mgL-1, and the detection limit based on the 3-times signal-to-noise ratio is 0.60. The method is used for the determination of COD in the real water sample, the repeatability is high, and compared with the national standard method, the determination result and the national standard method The result is in agreement with. 3. Carbon Dots is a new type of carbon nano-material, in recent years to give rise to a wide range of concerns. The carbon quantum dots are generally less than 10nm. The carbon quantum dots tend to exhibit good fluorescence intensity, strong stability, controllable emission wavelength, high solubility, good biocompatibility and the like with respect to the conventional fluorescent dye and the semiconductor quantum dot, cellular imaging, drug delivery, small molecular sensing, In the fourth chapter, a high quantum yield of phosphorus-doped carbon quantum dots (quantum yield) is synthesized by thermal decomposition with glucose and folic acid as the precursor. The carbon quantum dot can be selectively quenched by Fe3 +, and based on this, a fluorescence system for detecting the Fe3 + is established, the concentration of phosphate solution, the pH of the phosphate solution, the pyrolysis time and the pyrolysis temperature on the fluorescence intensity of the carbon quantum dot and the Fe3 + are studied. and the effect of the new method on the determination of the human serum Fe3 +, the determination result and the flame atomic absorption spectrum method, The results showed that the high-differentiated rat adrenal pheochromocytoma cells (PC12 cells) were stimulated by excitation under the blue light.
【學(xué)位授予單位】：華中科技大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：R123
[Abstract]:The chemical oxygen demand (COD) is one of the important comprehensive indexes to evaluate the degree of water pollution. With the rapid development of industry and agriculture in China and the increasing process of urbanization, the problem of environmental pollution is becoming more and more serious. At present, the standard method for the determination of COD in China is mainly the potassium dichromate method. The method has the advantages of high accuracy, good reproducibility and wide application. but the process of the dichromate method has the advantages of long operation time, high measurement cost and serious secondary pollution, and is difficult to analyze large batch samples at the same time by the restriction of the reflux device. In order to improve the above disadvantages, it is very important to shorten the analysis time, realize the on-line monitoring of COD, and develop a new method and new technology for rapid, sensitive and simple environment monitoring. The use of nano-materials, such as nano-carbon materials, nano-metal and metal oxide materials, organic polymer films and related composite materials as modified electrodes, is a new direction for the development of the current chemical modification electrode, and is of great significance for improving the sensitivity and selectivity of the analytical method. On the basis of this, two new chemical modification electrodes are constructed, which can be sensitive, rapid, and can be used for the detection and analysis of COD in surface water. The specific contents and results are as follows: 1. Prior to Co (NO3) 2 in situ preparation of nano-cobalt oxide in that surface of a glass-carbon electrode by using a constant-potential oxidation technique The effect of the deposition potential, the deposition medium, the deposition time and the concentration of Co2 + on the response signal of COD was studied. The influence of the concentration of Co2 + on the response signal of COD was studied. The results show that the nano-cobalt oxide-sensitive film can obviously improve the electrochemical response signal of COD, and a simple, sensitive and rapid electrochemical method for measuring COD is established. The response signal and the COD value show a good linearity in the range of COD value of 1. 7mgL-1 to 170mg L-1. The detection limit of the method is 1. 1mg L.-1. In order to verify the practical application of the oxide-sensitive membrane, the new method is applied to the determination of COD in water samples of different lakes. The results of the determination and the potassium dichromate method are very good. The micro-nano-copper drill was prepared in situ on the surface of the gold electrode by electrochemical deposition using Co (NO3) 2 and CuCl2 as the precursor. The influence of Cu 2 +, Co2 + ion concentration ratio, deposition current, deposition medium and deposition time on the response signal was investigated by using glucose as the standard for electrochemical measurement of COD, and the micro-nano Cu-Co-sensitive was successfully controlled. The results show that the prepared micro-nano Cu-Co sensitive film can obviously improve the electrochemical response signal of COD, and the rapid electrochemical measurement of COD is realized by the Ampere detection method. The linear range of the micro-nano Cu-Co-sensitive film is 1. 922mg L1-768mgL-1, and the detection limit based on the 3-times signal-to-noise ratio is 0.60. The method is used for the determination of COD in the real water sample, the repeatability is high, and compared with the national standard method, the determination result and the national standard method The result is in agreement with. 3. Carbon Dots is a new type of carbon nano-material, in recent years to give rise to a wide range of concerns. The carbon quantum dots are generally less than 10nm. The carbon quantum dots tend to exhibit good fluorescence intensity, strong stability, controllable emission wavelength, high solubility, good biocompatibility and the like with respect to the conventional fluorescent dye and the semiconductor quantum dot, cellular imaging, drug delivery, small molecular sensing, In the fourth chapter, a high quantum yield of phosphorus-doped carbon quantum dots (quantum yield) is synthesized by thermal decomposition with glucose and folic acid as the precursor. The carbon quantum dot can be selectively quenched by Fe3 +, and based on this, a fluorescence system for detecting the Fe3 + is established, the concentration of phosphate solution, the pH of the phosphate solution, the pyrolysis time and the pyrolysis temperature on the fluorescence intensity of the carbon quantum dot and the Fe3 + are studied. and the effect of the new method on the determination of the human serum Fe3 +, the determination result and the flame atomic absorption spectrum method, The results showed that the high-differentiated rat adrenal pheochromocytoma cells (PC12 cells) were stimulated by excitation under the blue light.
【學(xué)位授予單位】：華中科技大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：R123
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