新型硫化物的制备及其在有机光合成中的研究

发布时间：2018-05-31 09:59

本文选题：CdIn_2S_4 + 耦合体系　；参考：《淮北师范大学》2017年硕士论文

【摘要】：以乙二醇作为溶剂,由氯化铟(InCl3.4H2O),硝酸镉[Cd(NO3)2.4H2O],硫代乙酰胺(TAA)作为前驱物在溶剂热条件下制得CdIn2S4光催化剂。所制得的样品通过扫描电子显微镜(SEM),透射显微镜(TEM),X射线粉末衍射(XRD),紫外可见漫反射光谱(DRS),氮吸附脱附BET,X射线光电子能谱(XPS),电化学测试等表征技术来确定样品的结构和光学性质。在芳香醇和硝基苯耦合体系中,我们通过计算芳香醇和硝基苯的转化率,生成物芳香醛和苯胺的产率来研究不同时间合成的CdIn2S4光催化剂的活性。随着实验探索的深入,我们同时研究了在芳香醇-硝基苯耦合体系中一步法发生席夫碱反应生成亚胺类化合物的反应规律。结果表明,不同时间合成的CdIn2S4光催化剂选择性氧化苯甲醇还原硝基苯活性相似。当光照时间为6h时,苯甲醇和硝基苯的转化率分别约为74%,57%;苯甲醛和苯胺的产率分别约为65%,11%。在一步法生成C=N化合物研究中,光照8h时,席夫碱产物的产率达到32%,反应过程中生成的水分子会抑制反应的进行。通过捕获剂(三乙醇胺和CCl4)实验证明耦合体系中空穴(h+)和电子(e-)起决定性作用,氧化芳香醇的反应首先发生,还原硝基苯的反应不能单独发生,需要e-和氧化反应脱去的H质子参与。通过同位素对比实验研究反应机理,证明了氮气氛围下芳香醇到芳香醛脱去的2个H质子,1个来源于-CH2-的H质子,1个来源于-OH的H质子。我们还通过对比同条件下合成的CdIn2S4,CdS,In2S3在氧气氛围下氧化苯甲醇到苯甲醛的活性,分析结果发现光催化剂CdIn2S4催化活性最佳。因此,溶剂热法合成的CdIn2S4催化剂催化活性高,稳定性好,在有机光合成中具有很好的研究前景。
[Abstract]:Using ethylene glycol as solvent, CdIn2S4 photocatalyst was prepared by indium chloride (InCl3.4H2O), cadmium nitrate [Cd (NO3) 2.4H2O] and thioacetamide (TAA) as precursors in solvothermal conditions. The obtained samples were obtained by scanning electron microscopy (SEM), transmission microscope (TEM), X ray powder diffraction (XRD), ultraviolet visible diffuse reflectance spectroscopy (DRS), nitrogen adsorption desorption. BET, X ray photoelectron spectroscopy (XPS), electrochemical testing and other characterization techniques are used to determine the structure and optical properties of the samples. In the coupling system of aromatic alcohols and nitrobenzene, we study the yield of aromatic aldehydes and aniline by calculating the conversion of aromatic alcohols and nitrobenzene and the yield of aromatic aldehydes and aniline, and the activity of the CdIn2S4 photocatalyst at different time. At the same time, we also studied the reaction rule of the synthesis of imide by one step Schiff base reaction in the aromatic alcohol nitrobenzene coupling system. The results showed that the selective oxidation of benzyl alcohol to nitrobenzene by CdIn2S4 photocatalyst at different time was similar to that of benzyl alcohol at different time. When the light time was 6h, benzyl alcohol and nitro (nitrobenzene) were used. The conversion rate of benzene is about 74%, 57%, and the yield of benzaldehyde and aniline is about 65%, respectively. In the one step process of producing C=N compounds 11%., the yield of the Schiff base product reached 32% when light 8h was illuminated. The water molecules produced during the reaction process could inhibit the reaction. The cavities in the coupling system (h+) were proved by the capture agent (triethanolamine and CCl4). And the electron (e-) plays a decisive role, the reaction of oxidation aromatic alcohols first occurs, the reaction of reducing nitrobenzene can not occur alone, and the e- and the H protons removed from the oxidation reaction are required to participate. The reaction mechanism is studied by isotopic contrast experiments, and the 2 H protons from aromatic alcohols to aromatic aldehydes in nitrogen atmosphere and 1 H protons derived from -CH2- are proved. 1 H protons derived from -OH. We also compare the activity of benzyl alcohol to benzaldehyde by oxidation of CdIn2S4, CdS, and In2S3 under the same atmosphere under the same conditions. The results show that the photocatalyst CdIn2S4 has the best catalytic activity. Therefore, the solvent thermal synthesis of CdIn2S4 catalyst has high catalytic activity, good stability, and in organic light synthesis. Good research prospects.
【学位授予单位】：淮北师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36;O621.3

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