發(fā)布時(shí)間：2018-05-25 13:18

  本文選題：金屬有機(jī)框架材料 + 導(dǎo)電劑　； 參考：《鄭州大學(xué)》2017年博士論文

【摘要】：金屬有機(jī)框架材料(Metal-organic frameworks)是由無機(jī)金屬中心與有機(jī)配體組成。MOFs具有比表面積大、孔徑可調(diào)、孔容適中和孔隙率高等優(yōu)勢,適合作電化學(xué)傳感器增敏劑。然而,多數(shù)MOFs由于配位鍵的可逆本性導(dǎo)致穩(wěn)定性差;許多合成的MOFs屬于微米級材料,致使MOFs和傳感器表面結(jié)合不牢;大部分MOFs的導(dǎo)電性差。MOFs的固有缺陷限制了其在傳感器上的廣泛應(yīng)用。為解決上述問題,本文合成了穩(wěn)定性好的納米級MOFs材料;在構(gòu)筑傳感器時(shí),引入了導(dǎo)電劑XC-72、Mo S2和多壁碳納米管(MWCNT),與MOFs組合在一起,制備的MOFs/導(dǎo)電劑復(fù)合材料具有大的比表面積、好的電子傳遞性能和強(qiáng)的吸附能力。本文基于復(fù)合材料構(gòu)筑的高靈敏和高選擇性的傳感器,有利于增加目標(biāo)分析物的吸附位點(diǎn),可以用來檢測三聚氰胺(Mel)、氯霉素(CAP)、抗壞血酸(AA)、多巴胺(DA)和尿酸(UA);通過引入分子印跡技術(shù)(MIP),制備的MIP電化學(xué)傳感器可以提高槲皮素(Qu)和沒食子酸(GA)的選擇性�；贛OFs/導(dǎo)電劑復(fù)合材料構(gòu)筑的傳感器具有價(jià)格便宜、操作簡單、適中的線性濃度范圍和低的檢測限等優(yōu)勢;構(gòu)筑的傳感器同時(shí)具有高的重現(xiàn)性、穩(wěn)定性、靈敏性和選擇性;傳感器應(yīng)用在實(shí)際樣品中目標(biāo)分子的檢測,具有好的回收率。此外,針對不同傳感器檢測不同的目標(biāo)分析物,提出相關(guān)機(jī)理也是本文的重點(diǎn)研究對象。論文的主要具體工作如下:(1)基于MIL-53/XC-72納米復(fù)合材料修飾的玻碳電極,制備高靈敏和高選擇性的傳感器,用來檢測Mel。利用水熱合成方法制備MIL-53,然后與XC-72摻雜在一起,制備了MIL-53/XC-72納米復(fù)合材料。MIL-53、XC-72和MIL-53/XC-72材料和制備的傳感器分別用物理方法和電化學(xué)方法進(jìn)行表征。MIL-53/XC-72-Nafion/GCE傳感器具有高靈敏性和高選擇性,是MIL-53高的比表面積和XC-72好的導(dǎo)電性協(xié)同作用、以及Mel和MIL-53間氫鍵共同作用的結(jié)果。在優(yōu)化條件下,該傳感器在0.7 V電位和0.1 M HCl溶液中,對Mel具有好的電化學(xué)響應(yīng)。Mel的線性濃度范圍為0.04-10μM,線性回歸系數(shù)為0.998,檢測限為0.005μM。而且,該傳感器具有優(yōu)異的重現(xiàn)性、穩(wěn)定性和選擇性。將其用在牛奶樣品Mel的檢測中,具有好的回收率。(2)基于MIL-101(Cr)/XC-72修飾的玻碳電極構(gòu)筑的傳感器,用來檢測CAP。MIL-101(Cr)、XC-72和MIL-101(Cr)/XC-72用傅里葉變換紅外光譜(FTIR)、X射線粉末衍射儀(XRD)、比表面分析儀(BET)和掃描透射電鏡(SEM)方法來表征。電化學(xué)傳感器由三種材料構(gòu)筑而成,電化學(xué)性能用循環(huán)伏安法(CV)和差示脈沖溶出伏安法(DPV)詳細(xì)考察。與在裸電極、MIL-101(Cr)/GCE和XC-72/GCE傳感器相比,CAP在MIL-101(Cr)/XC-72/GCE傳感器上(電解液為磷酸緩沖溶液,PBS)具有一對好的氧化還原峰。詳細(xì)考察了MIL-101(Cr)與XC-72的配比、富集時(shí)間、掃描速率和p H值等影響因素。在優(yōu)化條件下,傳感器對CAP有好的電化學(xué)響應(yīng)。CAP的線性濃度范圍為0.01-20μM(R2=0.985),最低檢測限為0.0015μM(S/N=3)。而且,MIL-101(Cr)/XC-72/GCE傳感器成功用來檢測實(shí)際樣品,取得了令人滿意的回收率。(3)UIO-66-NO_2/XC-72納米復(fù)合物是由水熱合成的UIO-66-NO_2與XC-72摻雜組成的。材料的官能團(tuán)、結(jié)構(gòu)、織構(gòu)性能和形貌分別由FTIR、XRD、BET、SEM和TEM手段進(jìn)行系統(tǒng)表征。UIO-66-NO_2/XC-72修飾的玻碳電極傳感器成功地用來同時(shí)檢測AA、DA和UA。由于UIO-66-NO_2具有大的比表面,XC-72具有好的導(dǎo)電性,加上MOFs和目標(biāo)分析物間的氫鍵作用,制備的UIO-66-NO_2/XC-72/GCE傳感器在優(yōu)化條件下,對AA、DA和UA具有好的電化學(xué)響應(yīng)。AA、DA和UA的檢測范圍分別為0.2-3.5μM、0.03-2.0μM和0.75-22μM,檢測限分別為0.12μM、0.005μM和0.03μM。而且,本實(shí)驗(yàn)中的傳感器具有高的重現(xiàn)性和穩(wěn)定性;該傳感器成功地用來檢測鹽酸注射液中DA的含量,和人體中UA的含量。(4)制備了一種基于MIL-101(Cr)/Mo S2納米復(fù)合材料修飾的玻碳電極,隨后在Qu和吡咯存在條件下進(jìn)行電聚合的傳感器。物理表征和電化學(xué)表征手段分別用來考察材料的特性和傳感器的導(dǎo)電性。采用DPV法檢測Qu的含量。詳細(xì)考察了吡咯的體積、電聚合圈數(shù)、電解液的p H值、富集時(shí)間等影響因素。在優(yōu)化條件下,槲皮素在MIP/MIL-101(Cr)/Mo S2/GCE傳感器上有兩個(gè)線性濃度范圍,分別是0.1-10.5μM和10.5-700μM,檢測限為0.02μM(S/N=3)。而且,該傳感器具有好的重現(xiàn)性、穩(wěn)定性和選擇性,并成功地應(yīng)用在蜂蜜樣品中Qu含量的測定。(5)采用MIP技術(shù)制備了高靈敏和高選擇性的沒食子酸傳感器。MIP/Fe-MIL-88/MWCNT/GCE傳感器首先由Fe-MIL-88/MWCNT復(fù)合材料修飾玻碳電極,接著在GA和吡咯存在條件下,電聚合制備而成的。Fe-MIL-88、MWCNT和Fe-MIL-88/MWCNT材料用FTIR、XRD、BET和TEM等方法用來表征,制備的電化學(xué)傳感器用電化學(xué)阻抗(EIS)來表征。采用DPV方法檢測GA時(shí),利用K3[Fe(CN)6]/K4[Fe(CN)6]作為電活性探針間接測定GA含量。在優(yōu)化條件下,GA在該分子印跡傳感器上的電流響應(yīng)與其濃度呈較好的線性關(guān)系。檢測范圍為0.05-24μM(R2=0.998),檢測限為0.022μM(S/N=3)。該分子印跡傳感器具好的重現(xiàn)性、穩(wěn)定性和選擇性,將其應(yīng)用在橙汁、綠茶和紅茶的GA檢測中,實(shí)際樣品的RSD范圍為3.8%-4.3%(n=3),回收率為97.2%-98.9%。
[Abstract]:Metal organic frame material (Metal-organic frameworks) is composed of inorganic metal center and organic ligand, which has the advantages of large specific surface area, adjustable pore size, moderate pore volume and high porosity. It is suitable for electrochemical sensor sensitizer. However, most MOFs has poor stability due to the reversible nature of coordination bonds; many synthetic MOFs genera. In micron grade materials, the surface of MOFs and sensor is unbound, and the inherent defects of most MOFs's poor conductive.MOFs restrict its wide application on the sensor. In order to solve the above problems, this paper has synthesized a good stable nano scale MOFs material. In the construction of sensors, the conductive agent XC-72, Mo S2, and multi walled carbon nanotubes (MWC) were introduced. NT), with the combination of MOFs, the prepared MOFs/ conductive composite has large specific surface area, good electron transfer performance and strong adsorption capacity. The highly sensitive and highly selective sensors based on composite materials are beneficial to increase the adsorption sites of target analytes and can be used for the detection of melamine (Mel), chloramphenicol (CAP). Ascorbic acid (AA), dopamine (DA) and uric acid (UA); by introducing molecular imprinting technology (MIP), the preparation of MIP electrochemical sensors can improve the selectivity of quercetin (Qu) and gallic acid (GA). Sensing devices based on MOFs/ conductive composite materials are cheap, easy to operate, moderate linear concentration range and low detection limit. The sensor has high reproducibility, stability, sensitivity and selectivity at the same time; the sensor has a good recovery rate for the detection of the target molecules in the actual sample. In addition, the relevant mechanism is also the key object of this paper to detect the different target analytes for different sensors. The following are as follows: (1) a highly sensitive and highly selective sensor based on MIL-53/XC-72 nano composite modified glassy carbon electrode was prepared to detect Mel. using hydrothermal synthesis to prepare MIL-53, and then doped with XC-72 to prepare the MIL-53/XC-72 nanocomposite.MIL-53, XC-72 and MIL-53/XC-72 materials and the prepared sensors, respectively. The.MIL-53/XC-72-Nafion/GCE sensor characterized by physical method and electrochemical method has high sensitivity and high selectivity. It is a synergistic effect of high specific surface area of MIL-53 and good conductivity of XC-72, as well as the interaction of hydrogen bonds between Mel and MIL-53. Under optimal conditions, the sensor has a 0.7 V potential and a 0.1 M HCl solution to Mel. The linear concentration range of.Mel with good electrochemical response is 0.04-10 M, the linear regression coefficient is 0.998, the detection limit is 0.005 M., and the sensor has excellent reproducibility, stability and selectivity. It has good recovery rate in the detection of Mel in milk samples. (2) construction based on MIL-101 (Cr) /XC-72 modified glassy carbon electrode The sensor is used to detect CAP.MIL-101 (Cr), XC-72 and MIL-101 (Cr) /XC-72 with Fu Liye transform infrared spectroscopy (FTIR), X ray powder diffractometer (XRD), surface analyzer (BET) and scanning transmission electron microscopy (SEM). Electrochemical sensors are constructed from three materials, and the electrochemical properties are dissolved by cyclic voltammetry (CV) and differential pulse. The volt ampere method (DPV) is detailed. Compared with the bare electrodes, MIL-101 (Cr) /GCE and XC-72/GCE sensors, CAP has a pair of good redox peaks on the MIL-101 (Cr) /XC-72/GCE sensor (the electrolyte is phosphoric acid buffer solution, PBS). Under conditions, the linear concentration range of the sensor with good electrochemical response to CAP.CAP is 0.01-20 mu M (R2=0.985), and the minimum detection limit is 0.0015 mu M (S/N=3). Moreover, MIL-101 (Cr) /XC-72/GCE sensor has been successfully used to detect the actual samples and obtained satisfactory recovery. (3) the UIO-66-NO_2/XC-72 nanocomposite is a hydrothermal synthesis of UIO-66-N. O_2 and XC-72 doping. The functional group, structure, texture, texture, and morphology of the materials are characterized by FTIR, XRD, BET, SEM, and TEM, respectively. The.UIO-66-NO_2/XC-72 modified glassy carbon electrode sensor is successfully used to detect AA, DA and UA. because of the large specific surface of the UIO-66-NO_2. The UIO-66-NO_2/XC-72/GCE sensor has good electrochemical response to AA, DA and UA, and the detection range of DA and UA is 0.2-3.5 u M, 0.03-2.0 um M and 0.75-22 micron, respectively. The detection limits are 0.12 micron, 0.005 Mu and 0.03 micron respectively, and the sensors in this experiment have high reproducibility. The sensor was successfully used to detect the content of DA in hydrochloric acid injection and the content of UA in human body. (4) a kind of glassy carbon electrode modified based on MIL-101 (Cr) /Mo S2 nanocomposites was prepared, and the sensor of electropolymerization under the presence of Qu and pyrrole. Physical characterization and electrochemical characterization were used to investigate respectively. The properties of the material and the conductivity of the sensor. The content of Qu was detected by DPV. The volume of pyrrole, the number of electropolymerization, the P H value of the electrolyte, the concentration time and other factors were investigated in detail. Under the optimum conditions, quercetin had two linear concentration ranges on the MIP/MIL-101 (Cr) /Mo S2/GCE sensor, which were 0.1-10.5 micron M and 10.5-700 micron, respectively. The measurement limit is 0.02 M (S/N=3). Moreover, the sensor has good reproducibility, stability and selectivity, and has been successfully applied to the determination of Qu content in honey samples. (5) the high sensitive and highly selective.MIP/Fe-MIL-88/MWCNT/GCE sensor of gallic acid sensor was prepared by MIP technology, and the glassy carbon was first modified by Fe-MIL-88/MWCNT composite. The electrodes, followed by the presence of GA and pyrrole, are used to characterize the.Fe-MIL-88, MWCNT, and Fe-MIL-88/MWCNT materials prepared by electropolymerization with FTIR, XRD, BET, and TEM. The electrochemical sensors prepared are characterized by electrochemical impedance (EIS). The DPV method is used to detect the GA as an indirect measurement of the electroactive probe. GA content. Under optimal conditions, the current response of GA on the molecularly imprinted sensor has a good linear relationship with its concentration. The detection range is 0.05-24 mu M (R2=0.998), and the detection limit is 0.022 mu M (S/N=3). The molecular imprinting sensor has good reproducibility, stability and selectivity, and applies it to the GA detection of orange juice, green tea and black tea. The RSD range of the sample is 3.8%-4.3% (n=3) and the recovery is 97.2%-98.9%..
【學(xué)位授予單位】：鄭州大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O657.1
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本文編號：1933258