亚胺菲罗啉Cu-Pd双金属自组装膜的制备及催化性质

发布时间：2018-05-08 23:40

本文选题：亚胺菲罗啉 + 铜钯双金属催化剂　；参考：《郑州大学》2017年硕士论文

【摘要】：双金属之间协同催化作用,使双金属催化剂与相应的单金属催化剂相比,往往显示出优异的催化活性、选择性和稳定性。双金属催化剂是一类重要的催化剂,它可以通过调控不同反应中关键中间体的稳定性来构建不同的化学键,进而提高其催化活性,因此,双金属催化剂的得到了广泛的关注。本文合成了L1和L2两种邻菲罗啉衍生物配体,并通过了核磁和红外对其进行了结构表征。利用自组装膜技术,在亲水载体表面制备了含有菲罗啉和亚胺结构的新型双金属自组装膜催化剂Si-Cu-Pd,并通过水接触角法(WCA)、紫外可见光谱(UV-vis)、电化学阻抗(EIS)、拉曼光谱(Raman)、X-射线光电子能谱(XPS)、X射线衍射(XRD)、扫描电子显微镜(SEM)和电感耦合等离子体原子发射光谱(ICP-AES)等手段对催化剂进行了表征,对其催化“Click”反应的催化性能、循环性能以及反应机理进行了深入研究,具体研究内容如下:1.邻菲罗啉衍生物配体的合成(L1、L2)(Scheme 1):Scheme 12.亚胺菲罗啉Cu-Pd双金属自组装膜的合成路线(Scheme 2):Scheme 23.以三组分的“Click”反应为模板反应,研究催化剂Si-Cu-Pd的催化性能。结果显示:1)双金属之间的协同效应,使双金属催化剂Si-Cu-Pd在催化性质上与单金属催化剂Si-Cu比较,显示出优异的催化活性和循环稳定性;2)催化剂中两种金属含量的比例和活性中心的分布对催化活性有着重要的作用;3)自组装膜催化剂与传统异相催化剂相比,不需过滤和其他的复杂操作,容易回收,方便循环利用。4.通过热过滤实验、中毒实验、水接触角、X射线衍射、X-射线光电子能谱、扫描电镜和在线红外(FTIR)方法对催化过程进行研究,提出了异相催化Click反应的催化机理:结果表明,催化过程中的催化活性物种是Cu(I)和Pd(0),三唑-Cu中间体与Pd进行金属转移是催化过程的关键步骤,而不同活性中心如具有合适间隔与分布将能够促进金属转移,增加目标产物的收率。同时也说明了双金属自组装膜催化剂Si-Cu-Pd催化Click反应是在活性物种Cu、Pd协同催化作用下,在界面上进行的一个异相催化过程。
[Abstract]:The synergistic catalysis between bimetallic catalysts makes the bimetallic catalysts exhibit excellent catalytic activity, selectivity and stability compared with the corresponding monometallic catalysts. Bimetallic catalysts are a kind of important catalysts, which can construct different chemical bonds by regulating the stability of key intermediates in different reactions, and thus improve their catalytic activity. Therefore, bimetallic catalysts have received extensive attention. Two kinds of ligands of L _ 1 and L _ 2 derivatives were synthesized and characterized by NMR and IR. Using self-assembled film technology, Si-Cu-Pd, a novel bimetallic self-assembled film catalyst with phenanthroline and imine structure, was prepared on the surface of hydrophilic carrier. The catalyst Si-Cu-Pd was prepared by water contact angle method (WCA), UV-vis spectroscopy (UV-Vis), electrochemical impedance spectroscopy (EIS), Raman spectroscopy (Ram), and X-ray photoelectron spectroscopy (XPS). The catalysts were characterized by linear diffraction, scanning electron microscopy (SEM) and inductively coupled plasma atomic emission spectrometry (ICP-AESe). The catalytic performance, cycling performance and reaction mechanism of the Click reaction were studied in detail. The specific research contents are as follows: 1. Synthesis of Ligand of o-Phenanthroline Derivatives 1):Scheme 1):Scheme 12. Synthesis of Imiphenanthroline Cu-Pd bimetallic Self-Assembly Film Scheme 2):Scheme 23. The catalytic performance of the catalyst Si-Cu-Pd was studied by using the three-component "Click" reaction as a template reaction. The results show that the synergistic effect between the bimetallic catalyst Si-Cu-Pd and monometallic catalyst Si-Cu is better than that of the monometallic catalyst Si-Cu. It is shown that the ratio of two kinds of metal content and the distribution of active sites play an important role in the catalytic activity of the catalyst with excellent catalytic activity and cyclic stability. 3) the self-assembled film catalyst is compared with the traditional heterogeneous catalyst. No need for filtering and other complex operations, easy to recycle, easy to recycle. 4. The catalytic process was studied by means of thermal filtration experiment, poisoning experiment, X-ray diffraction of water contact angle, X-ray photoelectron spectroscopy, scanning electron microscope and on-line infrared FTIR. The catalytic mechanism of heterogeneous catalytic Click reaction was proposed. The active species in the catalytic process are Cui) and PD. The metal transfer between triazol-Cu intermediates and PD is the key step in the catalytic process, and different active sites with suitable spacing and distribution can promote the metal transfer. Increase the yield of the target product. It is also shown that the bimetallic self-assembled membrane catalyst Si-Cu-Pd catalyzes the Click reaction in a heterogeneous process at the interface under the co-catalysis of the active species CuPd.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.2;O643.36

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