本文選題：金屬卟啉 + 環(huán)鈀雙亞胺�。� 參考：《鄭州大學(xué)》2015年碩士論文

【摘要】：高效、可持續(xù)、經(jīng)濟(jì)的綠色化學(xué)是當(dāng)今工業(yè)催化所面臨的重大挑戰(zhàn)。過渡金屬有機(jī)超分子能模擬生物酶在溫和條件下高效催化很多反應(yīng),但是有些缺點,比如循環(huán)利用差、TON值較低。將其固定到載體上,制備可回收、高活性、原子經(jīng)濟(jì)的異相催化劑,是實現(xiàn)綠色化學(xué)的有效途徑,同時為反應(yīng)機(jī)理的研究提供了理想模板。本文主要包含以下的內(nèi)容:1.用多步自組裝法將環(huán)鈀雙亞胺通過化學(xué)鍵固載在硅基表面上,成功制備了環(huán)鈀雙亞胺席夫堿自組裝薄膜(1DIS、2DIS、3DIS)。研究表明:1)鏈的長短,配位方式對固載鈀的量影響很大,固載鈀量從高到低依次是3DIS、2DIS、1DIS;2)雙亞胺席夫堿配體通過配位鍵固載Pd(Ⅱ);3)亞胺的結(jié)構(gòu)對基片表面的分子排列具有調(diào)控作用。2.1DIS、2DIS、3DIS分子薄膜異相催化Suzuki偶聯(lián)反應(yīng)研究表明:1)1DIS固載的鈀含量低,催化活性較低;2)2DIS對溴代芳烴,碘代芳烴有很高的催化活性,而對氯代芳烴不催化,烷基鏈上的亞胺的α-碳上活性氫使得亞胺容易水解,導(dǎo)致其循環(huán)使用效果不佳;3)3DIS對催化溴代芳烴,碘代芳烴有很高的活性,同時對氯代芳烴也有一定的催化活性,循環(huán)8次后仍有較高的催化活性。3.自組裝膜異相催化Suzuki反應(yīng)機(jī)理的探討。利用XPS、AFM、CV、靜態(tài)水接觸角對催化反應(yīng)中膜的接觸角、形貌、元素相對含量和價態(tài)的變化進(jìn)行了詳細(xì)研究,并推測可能的催化機(jī)理:1)首先是催化表面先吸附反應(yīng)底物(鹵代芳烴),然后與零價鈀作用生成氧化加成中間體,芳基硼酸與中間體通過協(xié)同作用生成偶聯(lián)產(chǎn)物并脫離催化表面,實現(xiàn)催化循環(huán);2)反應(yīng)是在表面進(jìn)行的吸附與解吸附動態(tài)過程,前期主要是吸附反應(yīng),后期是解吸附,催化過程中催化活性中心逐漸被包埋,催化活性降低,反應(yīng)結(jié)束后,產(chǎn)物脫離薄膜,其中解吸附占主導(dǎo)地位,偶聯(lián)產(chǎn)物脫離薄膜;3)催化過程膜表面的形貌研究表明,膜的變化是一個有序到無序最后恢復(fù)有序的過程,證明催化反應(yīng)發(fā)生在表面,是典型的異相催化過程;4.以銅基石墨片來固載Mn-TPP,在高壓反應(yīng)釜中催化氧化環(huán)己烷,初步研究了溫度和壓力對產(chǎn)率及選擇性影響并選擇最優(yōu)反應(yīng)條件(150℃、1.2MPa)。
[Abstract]:Green chemistry, which is efficient, sustainable and economical, is a major challenge for industrial catalysis today. Transition metal organic supramolecular can mimic many reactions of biological enzymes under mild conditions, but there are some disadvantages, such as low recycling of ton. Immobilized on the carrier to prepare heterogeneous catalysts with recoverable high activity and atomic economy is an effective way to realize green chemistry and provides an ideal template for the study of reaction mechanism. This article mainly includes the following contents: 1. The cyclic palladium biimide was chemically bonded onto the silicon substrate by multistep self-assembly method, and the cyclopalladium biimide Schiff base self-assembled thin film was successfully prepared. The results show that the length and coordination mode of the chain have great influence on the amount of palladium supported. The order of supported palladium content from high to low is 3DIS-2DIS-1DIS-2DIS-2DIS-2DIS-2DIS-2DIS-2DIS-2DIS-2DIS-2DIS-2DIS-2DIS-2DIS-2DIS-2DIS-2DIS-2DIS-2DIS-3DIS. The results show that the structure of the biimide Schiff base ligands can regulate the molecular arrangement on the substrate surface by the coordination bond. The fixed palladium content is low, The catalytic activity of iodide aromatics and bromoaromatics is very high, but it is not catalyzed by chlorinated aromatics. The 偽 -carbon active hydrogen of imines on alkyl chain makes imines hydrolyze easily. The results showed that the catalytic activity of iodide aromatics and bromoaromatics was very high, and the catalytic activity of iodide aromatics was also higher than that of chlorinated aromatics. After 8 cycles, the catalytic activity of DIS was still high. Mechanism of heterogeneous Suzuki reaction catalyzed by self-assembled membrane. The changes of contact angle, morphology, relative content and valence state of the film in the catalytic reaction were studied in detail by using the static water contact angle and the XPSN AFM CVV, and the changes of the contact angle, morphology, relative content and valence state of the film in the catalytic reaction were studied. It is suggested that the possible catalytic mechanism is to first adsorb the substrate (halogenated aromatics) on the surface of the catalyst, and then interact with palladium to form an oxidized addition intermediate. Aryl boric acid and the intermediate form a coupling product by synergistic action and leave off the catalytic surface. The catalytic cycle 2) reaction is the dynamic process of adsorption and desorption on the surface, which is mainly the adsorption reaction in the early stage, and the desorption reaction in the later stage. The catalytic active center is gradually embedded in the catalytic process, and the catalytic activity decreases after the reaction is finished. The surface morphology of the membrane was studied in the catalytic process of coupling product dissociation. The results showed that the change of the membrane was a process from order to disorder, which proved that the catalytic reaction took place on the surface. It is a typical heterogeneous catalytic process. The catalytic oxidation of cyclohexane was carried out in a autoclave with copper based graphite sheet. The effects of temperature and pressure on the yield and selectivity were studied and the optimum reaction conditions were selected.
【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】：2015
【分類號】：TB383.2;O621.25

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本文編號：1879473