类水滑石复合材料的制备及其对鲁米诺化学发光体系的催化研究

发布时间：2018-06-06 05:43

本文选题：化学发光 + 鲁米诺　；参考：《山东农业大学》2015年硕士论文

【摘要】：化学发光分析因反应灵敏、线性范围宽、测试速度快,在生物工程、食品分析、环境监测、药物分析、临床诊断等多领域有重要应用。鲁米诺-H2O2是常用的化学发光体系之一,具有结构简单、性质稳定、不污染环境的优点。但因其反应速率低,常用金属离子、纳米粒子催化以加快反应进行。类水滑石是一类具有层状结构的无机双金属氢氧化物材料,对鲁米诺-H2O2体系的化学发光有一定的增敏作用,但以往研究多集中在类水滑石层间的阴离子,为确定片层金属组成及类水滑石片层与纳米粒子的协同作用,本论文设计如下:采用原位沉淀还原法制备了银负载的Mg-Al类水滑石纳米粒子,采用混合共沉淀法合成了系列过渡金属Cr3+、Co2+和Cu2+掺杂的类水滑石,研究了所得材料对鲁米诺-H2O2体系化学发光性能的影响;间苯二酚对鲁米诺-H2O2体系的发光强度有明显的抑制作用,以此探索类水滑石增敏的鲁米诺-H2O2体系能否实现对间苯二酚的灵敏性检测。本论文主要由以下四部分内容组成:1.采用共沉淀法合成Mg-Al水滑石前驱体,然后原位沉淀还原,将银纳米粒子负载到类水滑石上。利用X射线衍射(XRD)和透射电镜(TEM)对所得材料进行了表征,用流动注射法对负载银纳米粒子的类水滑石材料进行了催化性能研究,结果表明合成的负载型纳米催化剂具有类水滑石片状结构,且对鲁米诺化学发光体系具有良好的催化活性。催化效果受鲁米诺、LDHs-Ag及NaOH浓度影响,最优催化条件为NaOH浓度0.05mol/L,鲁米诺浓度2.0×10-4 mol/L,LDHs-Ag浓度1g/L。最优条件下,在H2O2浓度为1×10-5-1×10-3 mol/L范围内,H2O2浓度与体系的发光强度具有良好的线性关系:I=22.24+5289.22 c(×103 mol/L)(相关系数R2=0.9965),检测限为7.7×10-6 mol/L(S/N=3),因此该法可以用于微量H2O2的定量分析,具有一定的应用研究价值。2.采用混合共沉淀的方法将过渡金属Cr3+引入类水滑石层板中,得到了Cr-Mg-Al-LDHs。利用红外光谱(FTIR)、X射线衍射(XRD)和透射电镜(TEM)等手段对样品进行表征,结果表明Cr3+的掺杂对类水滑石的层状结构没有影响,仅降低了类水滑石的结晶度。利用流动注射分析(FIA)研究了Cr-Mg-Al-LDHs对鲁米诺-H2O2化学发光体系催化作用。在最优条件为pH 10.5,鲁米诺浓度1.0×10-4 mol/L,LDHs浓度1 g/L,H2O2浓度在1×10-5-1×10-3 mol/L范围内,Cr-Mg-Al-LDHs催化的化学发光体系的发光强度与H2O2浓度间存在线性方程:I=-101.80+203.57c(×105 mol/L)(相关系数R2=0.9918),检测限为7.5×10-6 mol/L(S/N=3)。3.采用混合共沉淀的方法将Co2+引入类水滑石层板中,得到了Co-Mg-Al-LDHs。利用红外光谱(FTIR)、X射线衍射(XRD)和透射电镜(TEM)等手段对样品进行表征,结果表明Co2+的掺杂对类水滑石的层状结构和结晶度等物理性质基本没有影响。利用流动注射分析(FIA)研究了Co-Mg-Al-LDHs对鲁米诺-H2O2化学发光体系催化作用,研究表明Co2+能够极大地改善类水滑石材料的催化性能,且催化效果与过渡金属的含量有关,Co-Mg-Al-LDHs中Co(II)含量越高,其催化活性就越高。最优测试条件为p H 10.5,鲁米诺浓度1.0×10-4 mol/L,LDHs浓度1 g/L。在最优条件下,当H2O2在浓度在1×10-6-1×10-3mol/L范围内,Co-Mg-Al-LDHs催化的发光体系的信号强度与H2O2浓度间存在线性方程:I=-231.53+894.83c(×106 mol/L)(相关系数R2=0.9954),检测限为3.2×10-7mol/L(S/N=3)。4.采用混合共沉淀法得到了Cu-Mg-Al-LDHs。利用红外光谱(FTIR)、X射线衍射(XRD)和透射电镜(TEM)等手段对Cu-Mg-Al-LDHs进行表征,并利用流动注射分析(FIA)研究了Cu-Mg-Al-LDHs对鲁米诺-H2O2化学发光体系催化作用。对鲁米诺-H2O2体系的最优催化条件为:鲁米诺浓度1×10-4 mol/L,pH 11.0,LDHs浓度2 g/L时,H2O2在1×10-6-1.2×10-4 mol/L范围内,与发光强度间线性方程为:I=-422.85+230.30 c(×106 mol/L)(相关系数R2=0.9998),检测限为3.8×10-7 mol/L(S/N=3)。将间苯二酚加入Cu-Mg-Al-LDHs增敏的鲁米诺-H2O2化学发光体系,化学发光强度受到明显的抑制,在1×10-9-1×10-3 g/L浓度范围内,体系的发光强度I与间苯二酚浓度的对数lgc呈良好的线性关系:I=3772-303.14lgc(相关系数R2=0.9972),检测限为3.7×10-10 g/L(S/N=3)。该检测方法具有灵敏度高,检测限低,线性范围宽,操作简单,成本低等优点,可作为定量检测间苯二酚的简便方法。
[Abstract]:Chemiluminescence analysis has important applications in many fields, such as biological engineering, food analysis, environmental monitoring, drug analysis and clinical diagnosis. Luminol -H2O2 is one of the commonly used chemiluminescence systems, which has the advantages of simple structure, stable properties and no pollution to the environment. Using metal ions and nanoparticles as a catalyst to accelerate the reaction. Hydrotalcite like hydrotalcite is a class of inorganic bimetal hydroxides with layered structure. It has a certain sensitization effect on the chemiluminescence of the luminol -H2O2 system. However, the previous studies focused on the detachment of the hydrotalcite like layers to determine the composition of lamellar metals and the hydrotalcite like slices. The synergistic effect of layer and nanoparticle is as follows: in this paper, the silver loaded Mg-Al hydrotalcite nanoparticles were prepared by in situ precipitation reduction method. A series of transition metals, Cr3+, Co2+ and Cu2+ doped hydrotalcite were synthesized by the mixed coprecipitation method. The effects of the materials on the chemiluminescence properties of the luminol -H2O2 system were studied. The photoluminescence of the Lumino -H2O2 system has a significant inhibitory effect on the sensitivity of the Lumino -H2O2 system sensitized by hydrotalcite like to realize the sensitivity detection of resorcinol. This paper is mainly composed of the following four parts: 1. the precursor of Mg-Al hydrotalcite is synthesized by coprecipitation method, and then in situ precipitation and reduction, and Silver The nanoparticles were loaded on the hydrotalcite. X ray diffraction (XRD) and transmission electron microscopy (TEM) were used to characterize the obtained materials. The flow injection method was used to study the catalytic properties of the hydrotalcite like nanoparticles loaded with silver nanoparticles. The results showed that the synthesized loaded nanoscale was composed of a hydrotalcite like structure and to luminol. The luminescent system has good catalytic activity. The catalytic effect is influenced by the concentration of Lumino, LDHs-Ag and NaOH. The optimal catalytic condition is NaOH concentration 0.05mol/L, Lumino concentration 2 x 10-4 mol/L, LDHs-Ag concentration 1g/L. optimum condition, H2O2 concentration is 1 x 10-5-1 x 10-3 mol/L range, H2O2 concentration is good with the luminous intensity of the system. Linear relation: I=22.24+5289.22 C (x 103 mol/L) (correlation coefficient R2=0.9965), the detection limit is 7.7 x 10-6 mol/L (S/N=3), so this method can be used for quantitative analysis of trace H2O2. The value.2. uses mixed coprecipitation method to introduce the transition metal Cr3+ into the hydrotalcite like laminates, and obtains Cr-Mg-Al-LDHs. utilization red. The samples were characterized by external spectrum (FTIR), X ray diffraction (XRD) and transmission electron microscopy (TEM). The results showed that the doping of Cr3+ had no effect on the layered structure of hydrotalcite, and only reduced the crystallinity of the hydrotalcite. The catalytic effect of Cr-Mg-Al-LDHs on the luminol -H2O2 chemiluminescence system was studied by flow injection analysis (FIA). The conditions are pH 10.5, Lumino concentration is 1 x 10-4 mol/L, LDHs concentration is 1 g/L, H2O2 concentration is within the range of 1 x 10-5-1 x 10-3 mol/L. There is a linear equation between the luminescence intensity and H2O2 concentration of Cr-Mg-Al-LDHs catalyzed chemiluminescence system: I=-101.80+203.57c (x 105 mol/L) (correlation series R2=0.9918), and the detection limit is 7.5 x 10-6. Co2+ was introduced into the hydrotalcite like laminates by the method of co precipitation. The samples were characterized by Co-Mg-Al-LDHs. using infrared spectroscopy (FTIR), X ray diffraction (XRD) and transmission electron microscopy (TEM). The results showed that the doping of Co2+ had no effect on the physical properties of the layered structure and crystallinity of the hydrotalcite. FIA) studied the catalytic effect of Co-Mg-Al-LDHs on the Lumino -H2O2 chemiluminescence system. The study shows that Co2+ can greatly improve the catalytic performance of the hydrotalcite like material, and the catalytic effect is related to the content of the transition metal. The higher the content of Co (II) in Co-Mg-Al-LDHs, the higher the catalytic activity. The optimum test condition is p H 10.5, and the Lumino concentration is 1. X 10-4 mol/L, LDHs concentration 1 g/L. under the optimal conditions, when H2O2 is in the range of 1 x 10-6-1 * 10-3mol/L, there is a linear equation between the signal intensity of the luminescent system and H2O2 concentration catalyzed by Co-Mg-Al-LDHs: I=-231.53+894.83c (x 106 mol/L) (R2=0.9954), and the detection limit of 3.2 * 10-7mol/L is obtained by a mixed coprecipitation method. Cu-Mg-Al-LDHs. was used to characterize Cu-Mg-Al-LDHs by means of infrared spectroscopy (FTIR), X ray diffraction (XRD) and transmission electron microscopy (TEM). The catalytic effect of Cu-Mg-Al-LDHs on the Lumino -H2O2 chemiluminescence system was studied by flow injection analysis (FIA). The optimum conditions for the Lumino -H2O2 system were as follows: Lumino concentration was 1 x 10-4 mol/L. When the concentration of pH 11 and LDHs is 2 g/L, H2O2 is within the range of 1 x 10-6-1.2 10-4 mol/L, and the linear equation between the luminescence intensity and the luminescence intensity is I=-422.85+230.30 C (x 106 mol/L) (correlation coefficient R2=0.9998), and the detection limit is 3.8 x 10-7 mol/L (S/N=3). In the 1 * 10-9-1 x 10-3 g/L concentration range, the luminescence intensity I of the system has a good linear relationship with the logarithmic LGC of the resorcinol concentration: I=3772-303.14lgc (correlation coefficient R2=0.9972) and the detection limit of 3.7 * 10-10 g/L (S/N=3). The detection method has the advantages of high sensitivity, low detection limit, wide linear range, simple operation and low cost, etc. It can be used as a simple method for quantitative detection of resorcinol.
【学位授予单位】：山东农业大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB33;O643.36

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