本文選題：金屬有機(jī)框架 + 離子交換�。� 參考：《山東師范大學(xué)》2017年博士論文

【摘要】：自1995年O.M.Yaghi在《Nature》提出金屬-有機(jī)框架(MOFs)概念以來,MOFs的發(fā)展便以日新月異的速度進(jìn)行著。過去的20年,數(shù)以萬計(jì)的金屬有機(jī)框架材料(MOFs)被化學(xué)家們合成出來。如今,化學(xué)家們不再僅僅追求得到結(jié)構(gòu)新穎的金屬-有機(jī)框架,而是設(shè)計(jì)合成結(jié)構(gòu)明確、性能優(yōu)異的有機(jī)無機(jī)雜化的有用材料。金屬-有機(jī)框架是由金屬中心作為節(jié)點(diǎn)和由有機(jī)配體作為鏈節(jié)組裝而成,可形成從零維到三維的拓?fù)浣Y(jié)構(gòu)。如此的構(gòu)成,也使得金屬-有機(jī)框架材料有了充足的可修飾位點(diǎn),這為人們改變或提高其性能奠定了基礎(chǔ)。更令人振奮的是,金屬-有機(jī)框架材料已經(jīng)在實(shí)驗(yàn)室條件下成功應(yīng)用于氣體儲(chǔ)存、吸附分離、光學(xué)傳感、質(zhì)子傳導(dǎo)、藥物傳輸與緩釋和催化等領(lǐng)域。本文中,我們?cè)O(shè)計(jì)與合成了從一維、二維到三維的有機(jī)無機(jī)配位聚合物,分別對(duì)它們進(jìn)行了陰陽離子同時(shí)交換、后合成修飾、催化氧化、催化還原和上轉(zhuǎn)換光催化等性質(zhì)的研究。I.以5-溴嘧啶為起始原料經(jīng)過Suzuki偶聯(lián)、Click反應(yīng)、親電取代等一系列有機(jī)反應(yīng)合成了嘧啶和吡啶為端基的,四氮唑橋聯(lián)的彎折型有機(jī)配體L1,然后L1與氯化鈷通過溶液法自組裝得到紫紅色一維雙鏈配位聚合物CP-1,CP-1的金屬節(jié)點(diǎn)由Cl-Co-Cl組成,CP-1分別在浸泡在含有氯化銅、溴化銅和硝酸銅的甲醇溶液中能相應(yīng)的發(fā)生肉眼可視的金屬節(jié)點(diǎn)的交換而得到CP-2、CP-3和CP-4,而交換后的鏈狀結(jié)構(gòu)可以保持。這種金屬節(jié)點(diǎn)整體交換首次被報(bào)道,為合成新化合物提供了一種手段;另外,“肉眼”可視的離子交換也許在金屬離子和平衡陰離子的可視化檢測(cè)中有潛在的用途。II.以4,4-二溴苯偶酰為起始原料經(jīng)過成環(huán)、親核取代和Suzuki偶聯(lián)等一系列有機(jī)反應(yīng)合成了吡啶為端基的,咪唑橋聯(lián)的彎折型剛性有機(jī)配體L2,然后L2與對(duì)苯二甲酸和醋酸鈷通過甲醇溶劑熱的方式自組裝得到Co-MOF-1,CoMOF-1含有配位甲醇,配位甲醇在單晶狀態(tài)下很容易丟掉形成具有配位不飽和金屬中心的Co-MOF-2。利用Co-MOF-2作催化劑,實(shí)現(xiàn)了對(duì)環(huán)己烷、苯乙烯、苯甲醇和1-苯乙醇類化合物的氧化,催化反應(yīng)條件溫和,為異相催化,催化劑易于回收與活化,可實(shí)現(xiàn)催化劑的循環(huán)利用。III.以4,4-二溴苯偶酰為起始原料經(jīng)過成環(huán)、親核取代、Suzuki偶聯(lián)和水解等一系列有機(jī)反應(yīng)合成了吡啶為端基的,咪唑橋聯(lián)的彎折型含羧基的有機(jī)配體L3,然后L3與醋酸鎘通過甲醇溶劑熱的方式自組裝得到Cd-MOF-1,CdMOF-1含有未配位的咪唑氮原子,通過后修飾的方式可以在氮原子上修飾上正十二烷的碳鏈合成咪唑鹽,形成咪唑鹽型三相相轉(zhuǎn)移催化劑Cd-MOFIM,利用Cd-MOF-IM作催化劑,首次實(shí)現(xiàn)了MOFs在相轉(zhuǎn)移催化方面的應(yīng)用,成功催化了正溴代丁烷和正溴丙烷的疊氮化與硫醚化。催化反應(yīng)溫度較低,為異相催化,催化劑易于回收與活化,可實(shí)現(xiàn)催化劑的循環(huán)利用。IV.根據(jù)相應(yīng)文獻(xiàn)合成了Ui O-66-NH_2,通過其對(duì)醋酸銅的吸附和還原處理制備了Cu(II)@Ui O-66-NH_2和Cu(0)@Ui O-66-NH_2兩種復(fù)合催化劑。利用Cu(II)@Ui O-66-NH_2作催化劑,實(shí)現(xiàn)了催化環(huán)己烯選擇性氧化;利用Cu(0)@Ui O-66-NH_2作催化劑,實(shí)現(xiàn)了催化苯乙烯的加氫還原反應(yīng)。催化反應(yīng)條件都十分溫和,催化效率極高,為異相催化,催化劑易于回收與活化,可實(shí)現(xiàn)催化劑的循環(huán)利用。V.利用無機(jī)物誘導(dǎo)凝膠轉(zhuǎn)變?yōu)榫w這一基本原理,實(shí)現(xiàn)將無機(jī)上轉(zhuǎn)換材料Na YF_4:Yb,Tm和無機(jī)半導(dǎo)體材料Ti O_2與MOF結(jié)合制備了兩例多元復(fù)合型光催化劑Na YF_4:Yb,Tm@Cd-MOF和Na YF_4:Yb,Tm@Cd-MOF@Ti O_2。主要通過PXRD,IR,TGA,SEM,TEM,ICP,元素分析等手段表征了這兩種催化劑的結(jié)構(gòu)與組成;通過熒光發(fā)射光譜表征了這兩種催化劑的上轉(zhuǎn)化發(fā)光性質(zhì)。初步分別探索了它們近紅外光催化性能,近紅外光催化反應(yīng)合成了“卡洛芬”藥物有機(jī)化合物,首次實(shí)現(xiàn)MOF復(fù)合催化劑的上轉(zhuǎn)換光催化。綜上所述,我們認(rèn)為金屬有機(jī)框架材料在催化等性質(zhì)方面有很大的應(yīng)用價(jià)值,還值得繼續(xù)研究下去。研究發(fā)現(xiàn):離子交換、后合成修飾、金屬離子負(fù)載、材料復(fù)合等手段都可以制備新型MOFs催化劑。
[Abstract]:Since O.M.Yaghi proposed the metal organic framework (MOFs) concept in in 1995, the development of MOFs was at a rapid pace. In the past 20 years, tens of thousands of metal organic frame materials (MOFs) have been synthesized by chemists. Now chemists are no longer only pursuing a new structure of metal organic framework, but rather the creation of a new metal organic framework. An organic and inorganic hybrid material with clear structure and excellent performance. The metal organic frame is composed of a metal center as a node and an organic ligand as a chain. It can form a topological structure from zero to three dimensions. This makes the metal organic frame material having sufficient modifiable sites, and this is one of the people. It is more exciting that metal organic frame materials have been successfully applied to the fields of gas storage, adsorption separation, optical sensing, proton conduction, drug transmission and slow release and catalysis in the laboratory conditions. In this paper, we designed and synthesized organic and inorganic compounds from one dimension, two to three dimensions. A study on the properties of the simultaneous exchange of anion and Yang ion, post synthesis modification, catalytic oxidation, catalytic reduction and upconversion photocatalytic catalysis, respectively,.I. using 5- bromo pyrimidine as the starting material through Suzuki coupling, Click reaction, electrophilic substitution and other organic reactions to synthesize pyrimidine and pyridine as the end group, and the bending of tetrazolium bridge. The folded organic ligand L1, then L1 and cobaltous chloride are self-assembled by solution method to obtain the one dimensional double chain coordination polymer CP-1 of the purple red. The metal nodes of CP-1 are composed of Cl-Co-Cl, and CP-1 can obtain CP-2, CP-3, respectively, in the exchange of visible metal nodes in the memeo eye in the methanol solution containing copper chloride, copper bromide and copper nitrate respectively. And CP-4, and the exchange of chain structure can be maintained. The overall exchange of this metal node is reported for the first time, providing a means for the synthesis of new compounds; in addition, the "naked eye" visual ion exchange may have a potential use in the visual detection of metal ions and balanced anions by.II. with 4,4- two bromo benzoyl as the starting material. A series of organic reactions such as nucleophilic and nucleophilic substitution and Suzuki coupling have been used to synthesize the end group of pyridine, a flexural rigid organic ligand L2 with imidazole bridge, and then L2 and terephthalic acid and cobalt acetate are self assembled by the methanol solvent heat, and CoMOF-1 contains coordination methanol, and coordination methanol is easily lost in the state of single crystal. The formation of Co-MOF-2. with a coordination unsaturated metal center using Co-MOF-2 as the catalyst for the oxidation of cyclohexane, styrene, benzyl alcohol and 1- benzyl alcohol compounds, the catalytic reaction conditions are mild, the catalyst is heterogeneous catalysis, the catalyst is easy to recover and activate, and the catalytic agent can recycle.III. with 4,4- two bromo benzoyl as the starting source. Through a series of organic reactions, such as nucleophilic substitution, nucleophilic substitution, Suzuki coupling and hydrolysis, a series of organic reactions such as coupling and hydrolysis of pyridine have been synthesized. The carboxyl carboxyl containing organic ligand L3 of imidazole bridged, and then L3 and cadmium acetate are self assembled by methanol solvent heat, and CdMOF-1 contains uncoordinated imidazole nitrogen atoms, which can be modified by post modification. The imidazole salt was synthesized on the nitrogen atom with a carbon chain of positive twelve alkane to form an imidazolate three phase phase transfer catalyst Cd-MOFIM and Cd-MOF-IM as a catalyst. The application of MOFs in phase transfer catalysis was realized for the first time. The azide and thio etherification of n-brominated butane and n-brominated propane were successfully catalyzed. The catalytic reaction temperature was lower and the phase was different. Catalyze, the catalyst is easy to recover and activate, and the catalyst can be recycled by.IV.. Ui O-66-NH_2 is synthesized according to the corresponding literature. By its adsorption and reduction of copper acetate, the Cu (II) @Ui O-66-NH_2 and Cu (0) @Ui O-66-NH_2 are prepared. The catalytic cyclohexene selection is realized by using Cu (II) as a catalyst. With Cu (0) @Ui O-66-NH_2 as a catalyst, the hydrogenation reduction reaction of catalytic styrene is realized. The catalytic reaction conditions are very mild, the catalytic efficiency is very high, the catalyst is heterogeneous catalysis, the catalyst is easy to recover and activate, and the basic principle that the catalyst is recycled by.V. by using the non machine induced gel into crystal can be realized. Inorganic upconversion materials Na YF_4:Yb, Tm and inorganic semiconductor material Ti O_2 and MOF are combined to prepare two multiple composite photocatalysts, Na YF_4:Yb, Tm@Cd-MOF and Na YF_4:Yb. The properties of the upper conversion luminescence of these two catalysts were observed. Their near infrared photocatalytic properties were preliminarily explored. The organic compounds of "calenin" were synthesized by near infrared light catalytic reaction. The first realization of the upconversion photocatalytic catalysis of MOF composite catalysts. In summary, we think that the metal organic frame materials have the properties of catalysis and other aspects. A new MOFs catalyst can be prepared by means of ion exchange, post synthesis, metal ion load, and material recombination.
【學(xué)位授予單位】：山東師范大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4

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1 王建成;幾例功能化的金屬—有機(jī)框架（MOFs）的合成制備及在催化和傳感方面的研究[D];山東師范大學(xué);2017年

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本文編號(hào)：2014344

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