催化剂的快速质谱表征研究

发布时间：2018-03-11 09:51

本文选题：纸喷雾电离源　切入点：催化剂　出处：《西安石油大学》2017年硕士论文　论文类型：学位论文

【摘要】：现代化学工程的快速发展高度依赖于新型催化剂的开发,选择合适的催化剂对于反应体系至关重要。尽管传统的催化剂表征方法如电子显微镜、物理化学吸附、X射线衍射、热分析、电子能谱、核磁共振、红外光谱等已被广泛应用于催化剂的表征研究,但由于如上方法操作步骤繁琐,不适合催化剂的快速筛选研究。质谱技术由于具有灵敏度高、选择性好、特异性强等特点,现已被广泛应用于食品科学、环保、化工、生命科学等诸多领域的分析检测,然而在催化剂的筛选方面鲜有报道。本论文以催化剂的快速质谱表征为目标,通过纸喷雾电离源-质谱分析技术对不同类型铜催化剂的系统研究,发展了一种快速筛选催化剂的质谱分析方法。具体研究工作包括如下几方面:为了采用纸喷雾电离源-质谱分析方法系统比较不同类型催化剂的催化性能,发展了一种简易式催化剂涂覆于纸基质的新方法,采用该方法可将不同固体催化剂均匀地涂覆在纸基质表面,同时该方法具有操作简单、价格低廉、重复性好等特点。对于水不溶性催化剂利用如上方法可将不同类型固体催化剂均匀地涂覆在纸基质表面,而对于水溶性催化剂本研究采用溶液均匀浸渍法将其负载在纸基质表面。为了系统考察制备条件和质谱分析条件对催化剂筛选的影响,本论文详细研究了催化剂涂覆浓度、延滞时间、反应溶剂与喷雾溶剂等参数对催化剂涂覆纸稳定性和催化性能的影响。采用如上建立的纸喷雾电离源-质谱分析方法系统考察了不同类型铜催化剂对苯硼酸-氨水反应体系中生成苯胺的影响。分别利用催化剂涂覆纸基质法、Drop-Cast法和传统溶液反应法对苯硼酸-氨水体系中不同类型的铜催化剂进行了筛选,发现在相同反应时间条件下,三种方法筛选出的最优催化剂均不相同。为了深入探究各种方法之间的差异,本论文深入考察了三种方法的反应动力学曲线并得到各种方法的最佳反应时间,发现在最佳反应时间条件下,催化剂涂覆纸基质法与传统溶液反应法筛选出的最优催化剂结果一致。同时也探讨了最佳反应时间下Drop-Cast方法与催化剂涂覆纸基质法筛选出的最优催化剂结果不一致的具体原因。深入研究了利用纸喷雾电离源-质谱分析方法对4-联苯硼酸-氨水反应体系中各种铜催化剂的筛选。采用催化剂涂覆纸基质法和传统溶液反应法,通过不同铜催化剂对4-联苯硼酸-氨水体系反应效率的研究,探究了如上两种方法的反应动力学曲线并得到相应的最佳反应时间,发现在最佳时间条件下催化剂涂覆纸基质法与传统溶液反应法筛选出的最优催化剂结果一致,说明了催化剂涂覆纸基质法是一种快速催化剂筛选评价方法。探究了催化剂涂覆纸基质的重复利用率以及催化剂混合价态对催化反应的影响。系统考察了涂覆纸基质在催化剂重复利用过程中的最优洗脱溶剂及洗脱效率,探讨了反应溶液和洗脱溶剂对水不溶性催化剂如Cu2O和水溶性催化剂如CuCl2涂覆纸基质表面颜色变化的影响。重点研究了不同铜催化剂活性随循环利用次数的变化情况,通过纸喷雾电离源-质谱分析方法对催化剂重复利用率的分析和X射线光电子能谱技术对催化剂物理化学性能的表征,发现在Cu催化剂催化过程中有一部分发生了价态的转变,如Cu2O转化为CuO。为了进一步证实如上结论,本论文针对苯硼酸-氨水反应体系,分别比较了CuO/Cu2O、CuBr2/CuBr和CuCl2/CuCl混合价态催化体系和单一价态的CuO、Cu2O、CuBr2、CuBr、CuCl2和CuCl的催化性能,发现混合价态催化剂(铜(II)/铜(I))明显优于单一价态催化剂(铜(II)或铜(I))的催化性能。
[Abstract]:The development of the rapid development of modern chemical engineering are highly dependent on the new catalyst, choose a suitable catalyst is essential for the reaction system. Although the traditional characterization methods such as electron microscope, physical and chemical adsorption, X ray diffraction, thermal analysis, electron spectroscopy, nuclear magnetic resonance, infrared spectroscopy characterization has been widely used in catalyst but because of the above methods, the operation is complicated, is not suitable for the rapid screening of catalysts. Mass spectrometry technology has high sensitivity, good selectivity and specificity, it has been widely used in food science, environmental protection, chemical analysis, life sciences and other fields, but in the selection of the catalyst. This is rarely reported based on the characterization of the catalyst by the rapid mass as the goal, through the system research paper spray ionization mass spectrometry analysis of different types of copper catalysts, development A rapid screening catalyst by mass spectrometry analysis method. The specific research work are as follows: in order to use paper spray ionization mass spectrometry system analysis method of different types of catalyst catalytic performance, a new method of developing a simple type catalyst coated on paper substrate, the method can be used with different solid catalyst uniformly the paper is coated on the surface of the matrix, and the method has the advantages of simple operation, low price, good reproducibility. The water insoluble catalyst by using the above methods can be of different types of solid catalyst uniformly coated on paper substrate surface, and the water soluble catalyst in this study, the load on the surface of a paper substrate using uniform impregnation solution in order to study law. The preparation conditions and mass spectrometry conditions on catalyst selection, this thesis makes a detailed study on the catalyst coating concentration, reaction time delay. Effects of solvent and solvent spray parameters on the catalyst coated paper stability and catalytic performance. The paper established above - spray ionization mass spectrometry analysis method to investigate the effect of different types of copper catalysts for ammonia aniline boronic acid in the reaction system. Using the catalyst coated paper matrix method, Drop-Cast method and reaction method the traditional solution were screened for different types of copper catalysts of benzene boric acid ammonia system, in the same reaction time, the optimal catalyst with three screened methods are not the same. In order to further explore the differences between the various methods, the best reaction time this thesis examines the kinetic curves of three kinds of methods and get all kinds of methods, found in the best condition of reaction time, the reaction catalyst optimal catalyst coated paper matrix method and the traditional solution selected a . it also discusses the specific reasons for the optimal catalyst reaction time Drop-Cast method and catalyst coated paper matrix method to filter out inconsistent results. The paper studied spray ionization mass spectrometry analysis method of 4- biphenyl boric acid in the reaction system of copper - ammonia catalyst screening by reaction catalyst coated. Paper matrix method and traditional solution, through the research of different copper catalysts on 4- biphenyl boric acid ammonia system reaction efficiency, to explore the kinetics curves above two methods and get the best reaction time corresponding, found consistent results in the best time optimal catalyst under the condition of reaction catalyst coated paper matrix method and traditional solution selected the catalyst coated paper, the matrix method is a rapid screening of catalyst evaluation methods. To explore the catalyst coated paper substrate to reuse rate Effect of mixed valence and catalyst on the catalytic reaction system was investigated. The coating of paper matrix in the reuse of the catalyst in the process of optimal elution efficiency and elution solvent, the effects of reaction solution and elution solvent insoluble catalyst such as Cu2O and the effect of water soluble catalysts such as CuCl2 coated paper substrate surface color change to focus on water. The catalytic activity of copper with different recycling times changes, the paper spray ionization mass spectrometry analysis method on the catalyst reuse analysis and X ray photoelectron spectroscopy characterization of the rate of energy on the physical and chemical properties of the catalyst, found some changes in the valence of Cu catalyst in the process of transformation, such as Cu2O CuO. in order to further confirm the above conclusions, this paper ammonia reaction system of phenylboronic acid, respectively CuO/Cu2O, CuBr2/CuBr and CuCl2/CuCl mixed valence catalysis The catalytic properties of CuO, Cu2O, CuBr2, CuBr, CuCl2 and CuCl in the system and single valence state show that the mixed valence catalyst (Cu (II) / Cu (I)) is obviously superior to the catalytic performance of single valence catalyst (Cu (II) or Cu (I)).

【学位授予单位】：西安石油大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ426;O657.63

【相似文献】