本文關(guān)鍵詞：卟啉非均相催化劑的設(shè)計、合成及其催化性能研究　出處：《江南大學(xué)》2017年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 烯烴 環(huán)氧化 卟啉 金屬有機(jī)框架 共價有機(jī)框架 共軛微孔聚合物

【摘要】：綠色化學(xué)與技術(shù)處于當(dāng)前國際化學(xué)的前沿領(lǐng)域,它的研究核心是利用化學(xué)原理從根本上消除化學(xué)工業(yè)對環(huán)境的污染。其中,非均相催化為滿足人們對綠色化學(xué)的需求帶來了希望,以其易分離、易回收、能循環(huán)使用、處理效果好等優(yōu)點,成為催化領(lǐng)域中研究開發(fā)和實際應(yīng)用的重點,具有很好的應(yīng)用前景。卟啉及其衍生物,作為重要的仿生催化劑之一,可以有效的模擬細(xì)胞色素酶(P450)的功能,表現(xiàn)出很好的催化效果,但目前卟啉均相催化不穩(wěn)定、易失活和難循環(huán)利用等問題,限制了卟啉仿生催化的進(jìn)一步發(fā)展。近年來,由于框架材料具有可控性好、設(shè)計性強(qiáng)和結(jié)構(gòu)穩(wěn)定等特點,使得它在非均相催化的應(yīng)用中極具競爭力。因此,制備卟啉框架材料,不僅可以通過高活性密度來增強(qiáng)催化活性,還可以利用框架材料的孔道構(gòu)建底物的“限域效應(yīng)”。另外,借助框架材料的表征和分析手段,對卟啉框架催化劑的催化過程進(jìn)行系統(tǒng)的研究,具有重要的理論意義和應(yīng)用價值。本論文設(shè)計合成了一系列基于卟啉為催化活性中心的金屬有機(jī)框架催化劑、共價有機(jī)框架催化劑(其中包括具有周期性排列單元、以共價鍵連接的聚合物催化劑),并對其催化精細(xì)化學(xué)品的合成如不飽和烯烴環(huán)氧化、芐胺偶聯(lián)的催化活性和選擇性進(jìn)行了系統(tǒng)的研究。另外,本工作采用密度泛函理論對卟啉催化劑的制備過程和催化過程進(jìn)行了幾何結(jié)構(gòu)優(yōu)化和單點能計算,以達(dá)到理論與實際相互驗證的目的。本論文的主要內(nèi)容和結(jié)果如下:1)金屬有機(jī)框架(Metal Organic Frameworks,MOFs)材料具有獨特的多孔性,以及高的比表面積和尺寸可調(diào)的孔道,可以人為的在MOFs的空穴中引入功能性的客體分子。本論文選擇類沸石咪唑框架材料(zeolitic imidazolate frameworks,簡稱ZIFs)作為載體,錳卟啉作為模擬血紅蛋白酶的活性中心,構(gòu)建包裹型卟啉MOFs催化劑(Mn-TAPP@ZIF-8,Mn-TAPP四(4-氨基)苯基錳卟啉)。當(dāng)使用催化劑材料Mn-TAPP@ZIF-8進(jìn)行環(huán)己烯環(huán)氧化,Mn-TAPP@ZIF-8的催化活性明顯高于Mn-TAPP的催化活性,說明使用Mn-TAPP@ZIF-8作為烯烴環(huán)氧化催化劑是比較好的非均相催化劑。工作還研究了Mn-TAPP與ZIF-8形成的主-客體關(guān)系,明確了Mn-TAPP與ZIF-8之間協(xié)同效應(yīng)的機(jī)理,發(fā)現(xiàn)了ZIF-8內(nèi)腔上咪唑C-H鍵與氨基卟啉上的N形成了弱氫鍵作用,這樣的鍵能結(jié)合提高了錳卟啉中高價態(tài)錳的含量,進(jìn)而有利于環(huán)氧化的進(jìn)行。Mn-TAPP@ZIF-8在烯烴環(huán)氧化反應(yīng)中具有廣泛的應(yīng)用價值,對不同烯烴都有很好的催化效果。另外,Mn-TAPP@ZIF-8具有典型的非均相催化的特點,循環(huán)利用3次,催化效果幾乎沒有下降的趨勢。2)本章節(jié)內(nèi)容以5,10,15,20-(四羧基苯基)卟啉(H4TCPP)、錳-5,10,15,20-(四羧基苯基)卟啉(Mn-TCPP)為配體,分別與過渡金屬Fe和Ni自組裝得到兩種新型晶態(tài)MMPFs材料(Fe-MMPF和Ni-MMPF),通過單晶衍射分析了它們的結(jié)構(gòu),其中Fe-MMPF包含首次報道的三核鐵氧簇和錳卟啉,Ni-MMPF由一維的帶狀鎳氧鏈與鎳卟啉組裝而成,根據(jù)兩種催化劑結(jié)構(gòu)上的特點,通過兩個催化體系進(jìn)行考察,(1))在Fe-MMPF\H2O2\Na HCO3催化體系中,常溫下環(huán)辛烯的轉(zhuǎn)化率高達(dá)99%,沒有副產(chǎn)物的生成。催化結(jié)果表明,Na HCO3顯示出了高效的催化劑助劑作用。催化機(jī)理的研究結(jié)果明確了氧原子在反應(yīng)中的轉(zhuǎn)移路徑:HCO4-替代H2O2作為新的氧源提供氧原子,氧原子再從HCO4-轉(zhuǎn)移到錳卟啉形成催化活性中間體,活化雙鍵后得到產(chǎn)物。三核鐵氧簇對于錳卟啉有一個吸電子的作用,這樣吸電子的作用是有利于催化反應(yīng)的進(jìn)行,根據(jù)這樣的現(xiàn)象本工作提出了新的概念,稱為“催化有利的電荷移動”。(2))在Ni-MMPF\TBHP催化體系中,根據(jù)催化結(jié)果明確了共軛烯烴周圍電子云密度對環(huán)氧化效果的影響。環(huán)氧化產(chǎn)率與烯烴本身的立體空間結(jié)構(gòu)效應(yīng)有聯(lián)系。另外,苯環(huán)和雙鍵上連接供電子基團(tuán),有利于雙鍵上電子云密度的增加,雙鍵更容易被卟啉的過氧中間體進(jìn)攻活化,因此環(huán)氧化效果會提高。最后對催化劑進(jìn)行了5次循環(huán)利用實驗,發(fā)現(xiàn)經(jīng)過5次循環(huán)利用,轉(zhuǎn)化率90%,選擇性98%。3)采用具有酰肼基團(tuán)的卟啉(Mn-HTCPP)為構(gòu)筑單元,與對苯二甲醛或方酸通過縮合反應(yīng)成功的合成了一類結(jié)構(gòu)新穎且具有優(yōu)良環(huán)氧化效果的固體催化劑Mn-CPFs。兩種框架結(jié)構(gòu)的孔道主要以堆積孔為主,且難溶于常見的極性和非極性有機(jī)溶劑。對這兩種催化劑進(jìn)行烯烴環(huán)氧化實驗測試,結(jié)果表明,催化劑Mn-CPF-1具有更加優(yōu)良的環(huán)氧化效果,說明構(gòu)筑單元Mn-HTCPP與對苯二甲醛的組合有利于提高錳卟啉的催化能力�？疾炝薓n-CPF-1催化劑對環(huán)狀烯烴和鏈狀烯烴的催化能力。催化劑循環(huán)利用的結(jié)果表明Mn-CPF-1穩(wěn)定性良好,具有很好的可循環(huán)利用性。XPS測試表明Mn-CPF-1中錳的電荷分散到共軛有機(jī)骨架程度更高,具有更明顯的氧化還原能力,因此活性中心的催化性能更強(qiáng)。4)設(shè)計合成了具有四個硝基的錳卟啉化合物,在堿性條件下與對苯二胺或聯(lián)苯二胺進(jìn)行偶聯(lián),得到兩種結(jié)構(gòu)不同的微孔有機(jī)聚合物催化劑,命名為azo-CMP-1和azo-CMP-2。報道的合成方法簡便,制備的azo-CMP-1具有更加優(yōu)良的環(huán)氧化效果。通過SEM分析,發(fā)現(xiàn)azo-CMP-1具有對催化有利的片層結(jié)構(gòu),這與催化劑骨架的構(gòu)成有關(guān),片層結(jié)構(gòu)不僅能夠增強(qiáng)催化劑的疏水性,還有利于產(chǎn)物的釋放和降低叔丁醇與活性中心的接觸;對催化劑的環(huán)氧化機(jī)理進(jìn)行探討,XPS的結(jié)果進(jìn)一步證實了有機(jī)骨架對活性中心的影響:電荷分散到共軛有機(jī)骨架中的程度更高,從而使azo-CMP-1中的錳具有更明顯的氧化還原能力。對催化劑進(jìn)行循環(huán)利用實驗,結(jié)果表明azo-CMP-1穩(wěn)定性良好,具有很好的可循環(huán)利用性。5)成功將卟啉和蜜勒胺通過偶氮鍵連接成為一種具有良好孔道結(jié)構(gòu)的框架催化劑(PMP),基于電子供-受的光催化體系,建立起了空穴氧化、電子轉(zhuǎn)移和能量轉(zhuǎn)移的“三位一體”光催化過程。PMP的高比表面積可以有效地提高底物的傳質(zhì)過程。計算化學(xué)和穩(wěn)態(tài)、動態(tài)熒光測試的結(jié)果表明,PMP可以吸收可見光,能夠有效的抑制電子和空穴的復(fù)合行為,以此增強(qiáng)電子轉(zhuǎn)移的過程。另外,通過ESR和UV-Vis分析,PMP相對于TNPP能夠產(chǎn)生更多單線態(tài)氧,說明能量轉(zhuǎn)移過程被增強(qiáng)。上述的雙重增強(qiáng)作用說明,PMP是一種在可見光下具有高效光催化活性的非金屬催化材料,而且具有很好的可循環(huán)利用性。
[Abstract]:Green chemistry and technology in the current international frontiers of chemistry, the essence of the research is to eliminate the environmental pollution of chemical industry fundamentally by chemical principle. The heterogeneous catalytic brings hope to meet the demand for green chemistry, with its easy separation, easy recovery, energy recycling, treatment effect and the like well, become the focus in the field of catalysis and practical application of research and development, has good application prospects. The porphyrin and its derivatives, as one of the most important bionic catalyst, can simulate cytochrome enzyme effective (P450) function, showed good catalytic effect, but the porphyrin homogeneous catalysis is not stable, easy to deactivation and recycling difficult problems, limiting the further development of porphyrin biomimetic catalysis. In recent years, because the frame material has good controllability and stability characteristics of strong in design and structure, making it in the heterogeneous. Very competitive of application. Therefore, the preparation of porphyrin framework material, not only can enhance the catalytic activity by high activity density, "confinement" can also build the substrate utilization frame material channels. In addition, by means of material characterization and analysis framework, the systematic research on the catalytic process of porphyrin catalyst framework that has important theoretical significance and application value. Based on a series of porphyrins in the catalytic center of the metal organic framework catalysts were designed and synthesized in this paper, covalent organic frameworks (including catalyst with periodic unit polymer catalyst covalently bound), and its catalytic synthesis of fine chemicals such as unsaturated olefin the coupling of epoxidation, catalytic activity and selectivity were studied. In addition, by using the density functional theory of porphyrin catalyst preparation The process and catalytic process of geometry optimization and single point calculations, in order to achieve the theory and practice of mutual authentication. The main contents and results of this thesis are as follows: 1) metal organic frameworks (Metal Organic Frameworks, MOFs) has unique porous materials, and the specific surface area and pore size adjustable high the artificially introduced functional guest molecules in the MOFs cavity. This paper selected materials (zeolitic imidazolate zeolitic imidazolate framework frameworks, referred to as ZIFs) as the carrier, as the manganese porphyrin active center simulation hemoglobin enzyme, construction of encapsulated porphyrin MOFs catalyst (Mn-TAPP@ZIF-8, Mn-TAPP four (4- amino phenyl) porphyrin manganese). When using the catalyst material Mn-TAPP@ZIF-8 for the epoxidation of cyclohexene, the catalytic activity of Mn-TAPP@ZIF-8 was significantly higher than that of the catalytic activity of Mn-TAPP, use Mn-TAPP@ZIF-8 as olefin ring Is a good catalyst for oxidation of heterogeneous catalyst was also studied. Mn-TAPP and ZIF-8 formed the main object relation, the mechanism between Mn-TAPP and ZIF-8 synergistic effect, ZIF-8 was found on the inner imidazole C-H bond with amino porphyrin formation of N weak hydrogen bonds, such bonds can high valence manganese content manganese porphyrin increased the binding and.Mn-TAPP@ZIF-8 in olefin epoxidation has wide application value for the epoxidation, have good catalytic effect to different olefins. In addition, Mn-TAPP@ZIF-8 has the typical characteristics of heterogeneous catalysis, 3 recycling, the catalytic effect of almost no downward trend.2) this chapter by 5,10,15,20- (four carboxyl phenyl) porphyrin manganese (H4TCPP), -5,10,15,20- (four carboxy phenyl) porphyrin (Mn-TCPP) as the ligand, respectively with transition metal Fe and Ni self-assembly get two new crystalline MMPFs materials (Fe-MMPF and Ni-MMPF), their structures were analyzed by X-ray diffraction, which contains Fe-MMPF first reported three nuclear iron oxide clusters and manganese porphyrin Ni-MMPF by nickel oxide and nickel porphyrin ribbon chain assembly into one-dimensional, according to the two kinds of catalysts on the structure characteristics, were evaluated by two catalyst system. (1) Fe-MMPFH2O2Na) in the HCO3 catalytic system, room temperature cyclooctene conversion rate as high as 99% generation of by-products. The catalytic results show that Na HCO3 shows the catalyst effect and efficiency. Research results confirm the catalytic mechanism of the transfer path of oxygen atoms in the reaction: HCO4- instead of H2O2 as the source of oxygen the new oxygen atoms, oxygen atoms and then transferred from the HCO4- to the formation of the catalytic activity of manganese porphyrin intermediates, activated double bond product is obtained after three. Nuclear ferrite clusters have a electron withdrawing role for manganese porphyrin, so the electron withdrawing effect is Favorable to the catalytic reaction, according to this phenomenon put forward the new concept of this work, called "charge mobile" favorable catalytic. (2)) in the Ni-MMPFTBHP catalytic system, based on the catalytic results clarified the electron cloud density around the shadow on the epoxidation effect of conjugated olefin ring. With three-dimensional space structure effect epoxidation of olefin yield and itself. In addition, the benzene ring and double bond connected with electron donating group, is conducive to the double bond electron cloud density increases, the double bond is more likely to be peroxy intermediate porphyrin attack activation, so the epoxidation effect will be improved. Finally, the catalyst was 5 cycles using the experiment, found that after 5 times recycling 90%, the conversion rate, selectivity of 98%.3) with hydrazide group porphyrin (Mn-HTCPP) as the construction units, and two of benzene formaldehyde or acid successfully through condensation reaction of synthesis of a novel structure and has the advantages of Solid catalyst Mn-CPFs. Lianghuan oxidation effect of two kinds of frame structure mainly by the accumulation of pore pore, and insoluble in common polar and non-polar organic solvents. For olefin epoxidation test of the two kinds of catalysts showed that Mn-CPF-1 catalyst has excellent epoxidation effect more, that building unit Mn-HTCPP in combination with two of benzene formaldehyde can improve the catalytic ability of manganese porphyrin was studied. The catalytic performance of Mn-CPF-1 catalyst on cyclic olefin and chain olefin catalyst recycling. The results show that Mn-CPF-1 has good stability, good recyclability of.XPS test indicated that the charge of Mn in Mn-CPF-1 dispersed into the conjugated organic skeleton degree higher, with more obvious oxidation reduction ability, so the active center of the catalytic performance of manganese porphyrin compounds with stronger.4) four nitro groups were designed and synthesized in alkali Under the condition of two of benzene and biphenyl amine or two amine coupling by microporous organic polymers catalyst with two different structure, named the synthesis method of azo-CMP-1 and azo-CMP-2. report is prepared by epoxidation of azo-CMP-1 has better results. Through SEM analysis, the azo-CMP-1 has favorable on the catalytic layer structure this, and the catalyst skeleton on the composition, the lamellar structure can not only enhance the hydrophobic catalyst, but also conducive to the product and reduce the release of tert butyl alcohol and active center contact; epoxidation mechanism of catalyst was discussed, the results of XPS further confirmed the effect of organic skeleton on the active center: charge dispersion to conjugated organic in the framework of higher degree, so that the azo-CMP-1 of Mn has more obvious oxidation reduction ability. The catalyst recycling experiment results show that the stability of azo-CMP-1 Good use of.5, has good circulation) successfully porphyrin and melem connected into a framework of the catalyst has good pore structure by azo bond (PMP), the photocatalytic system based on electron donor acceptor, up hole oxidation, electron transfer and energy transfer of "three-in-one" photocatalytic the process of specific surface area of.PMP can effectively improve the mass transfer process of substrate. Computational chemistry and steady-state fluorescence, dynamic test results show that PMP can absorb visible light, the composite can inhibit the behavior of electrons and holes effectively, in order to enhance the electron transfer process. In addition, through the analysis of ESR and UV-Vis, PMP to TNPP can produce more singlet oxygen, energy transfer process is enhanced. The double enhancement shows that PMP is a kind of high efficient photocatalytic activity under visible light non metal catalytic materials, but also has Good recyclability.

【學(xué)位授予單位】：江南大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O643.36

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