本文選題：亞胺菲羅啉 + 銅鈀雙金屬催化劑��； 參考：《鄭州大學(xué)》2017年碩士論文

【摘要】：雙金屬之間協(xié)同催化作用,使雙金屬催化劑與相應(yīng)的單金屬催化劑相比,往往顯示出優(yōu)異的催化活性、選擇性和穩(wěn)定性。雙金屬催化劑是一類重要的催化劑,它可以通過調(diào)控不同反應(yīng)中關(guān)鍵中間體的穩(wěn)定性來構(gòu)建不同的化學(xué)鍵,進(jìn)而提高其催化活性,因此,雙金屬催化劑的得到了廣泛的關(guān)注。本文合成了L1和L2兩種鄰菲羅啉衍生物配體,并通過了核磁和紅外對其進(jìn)行了結(jié)構(gòu)表征。利用自組裝膜技術(shù),在親水載體表面制備了含有菲羅啉和亞胺結(jié)構(gòu)的新型雙金屬自組裝膜催化劑Si-Cu-Pd,并通過水接觸角法(WCA)、紫外可見光譜(UV-vis)、電化學(xué)阻抗(EIS)、拉曼光譜(Raman)、X-射線光電子能譜(XPS)、X射線衍射(XRD)、掃描電子顯微鏡(SEM)和電感耦合等離子體原子發(fā)射光譜(ICP-AES)等手段對催化劑進(jìn)行了表征,對其催化“Click”反應(yīng)的催化性能、循環(huán)性能以及反應(yīng)機(jī)理進(jìn)行了深入研究,具體研究內(nèi)容如下:1.鄰菲羅啉衍生物配體的合成(L1、L2)(Scheme 1):Scheme 12.亞胺菲羅啉Cu-Pd雙金屬自組裝膜的合成路線(Scheme 2):Scheme 23.以三組分的“Click”反應(yīng)為模板反應(yīng),研究催化劑Si-Cu-Pd的催化性能。結(jié)果顯示:1)雙金屬之間的協(xié)同效應(yīng),使雙金屬催化劑Si-Cu-Pd在催化性質(zhì)上與單金屬催化劑Si-Cu比較,顯示出優(yōu)異的催化活性和循環(huán)穩(wěn)定性;2)催化劑中兩種金屬含量的比例和活性中心的分布對催化活性有著重要的作用;3)自組裝膜催化劑與傳統(tǒng)異相催化劑相比,不需過濾和其他的復(fù)雜操作,容易回收,方便循環(huán)利用。4.通過熱過濾實驗、中毒實驗、水接觸角、X射線衍射、X-射線光電子能譜、掃描電鏡和在線紅外(FTIR)方法對催化過程進(jìn)行研究,提出了異相催化Click反應(yīng)的催化機(jī)理:結(jié)果表明,催化過程中的催化活性物種是Cu(I)和Pd(0),三唑-Cu中間體與Pd進(jìn)行金屬轉(zhuǎn)移是催化過程的關(guān)鍵步驟,而不同活性中心如具有合適間隔與分布將能夠促進(jìn)金屬轉(zhuǎn)移,增加目標(biāo)產(chǎn)物的收率。同時也說明了雙金屬自組裝膜催化劑Si-Cu-Pd催化Click反應(yīng)是在活性物種Cu、Pd協(xié)同催化作用下,在界面上進(jìn)行的一個異相催化過程。
[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.
【學(xué)位授予單位】：鄭州大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TB383.2;O643.36

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