几例功能化的金属—有机框架（MOFs）的合成制备及在催化和传感方面的研究

发布时间：2018-06-13 14:33

本文选题：金属有机框架 + 离子交换　；参考：《山东师范大学》2017年博士论文

【摘要】：自1995年O.M.Yaghi在《Nature》提出金属-有机框架(MOFs)概念以来,MOFs的发展便以日新月异的速度进行着。过去的20年,数以万计的金属有机框架材料(MOFs)被化学家们合成出来。如今,化学家们不再仅仅追求得到结构新颖的金属-有机框架,而是设计合成结构明确、性能优异的有机无机杂化的有用材料。金属-有机框架是由金属中心作为节点和由有机配体作为链节组装而成,可形成从零维到三维的拓扑结构。如此的构成,也使得金属-有机框架材料有了充足的可修饰位点,这为人们改变或提高其性能奠定了基础。更令人振奋的是,金属-有机框架材料已经在实验室条件下成功应用于气体储存、吸附分离、光学传感、质子传导、药物传输与缓释和催化等领域。本文中,我们设计与合成了从一维、二维到三维的有机无机配位聚合物,分别对它们进行了阴阳离子同时交换、后合成修饰、催化氧化、催化还原和上转换光催化等性质的研究。I.以5-溴嘧啶为起始原料经过Suzuki偶联、Click反应、亲电取代等一系列有机反应合成了嘧啶和吡啶为端基的,四氮唑桥联的弯折型有机配体L1,然后L1与氯化钴通过溶液法自组装得到紫红色一维双链配位聚合物CP-1,CP-1的金属节点由Cl-Co-Cl组成,CP-1分别在浸泡在含有氯化铜、溴化铜和硝酸铜的甲醇溶液中能相应的发生肉眼可视的金属节点的交换而得到CP-2、CP-3和CP-4,而交换后的链状结构可以保持。这种金属节点整体交换首次被报道,为合成新化合物提供了一种手段;另外,“肉眼”可视的离子交换也许在金属离子和平衡阴离子的可视化检测中有潜在的用途。II.以4,4-二溴苯偶酰为起始原料经过成环、亲核取代和Suzuki偶联等一系列有机反应合成了吡啶为端基的,咪唑桥联的弯折型刚性有机配体L2,然后L2与对苯二甲酸和醋酸钴通过甲醇溶剂热的方式自组装得到Co-MOF-1,CoMOF-1含有配位甲醇,配位甲醇在单晶状态下很容易丢掉形成具有配位不饱和金属中心的Co-MOF-2。利用Co-MOF-2作催化剂,实现了对环己烷、苯乙烯、苯甲醇和1-苯乙醇类化合物的氧化,催化反应条件温和,为异相催化,催化剂易于回收与活化,可实现催化剂的循环利用。III.以4,4-二溴苯偶酰为起始原料经过成环、亲核取代、Suzuki偶联和水解等一系列有机反应合成了吡啶为端基的,咪唑桥联的弯折型含羧基的有机配体L3,然后L3与醋酸镉通过甲醇溶剂热的方式自组装得到Cd-MOF-1,CdMOF-1含有未配位的咪唑氮原子,通过后修饰的方式可以在氮原子上修饰上正十二烷的碳链合成咪唑盐,形成咪唑盐型三相相转移催化剂Cd-MOFIM,利用Cd-MOF-IM作催化剂,首次实现了MOFs在相转移催化方面的应用,成功催化了正溴代丁烷和正溴丙烷的叠氮化与硫醚化。催化反应温度较低,为异相催化,催化剂易于回收与活化,可实现催化剂的循环利用。IV.根据相应文献合成了Ui O-66-NH_2,通过其对醋酸铜的吸附和还原处理制备了Cu(II)@Ui O-66-NH_2和Cu(0)@Ui O-66-NH_2两种复合催化剂。利用Cu(II)@Ui O-66-NH_2作催化剂,实现了催化环己烯选择性氧化;利用Cu(0)@Ui O-66-NH_2作催化剂,实现了催化苯乙烯的加氢还原反应。催化反应条件都十分温和,催化效率极高,为异相催化,催化剂易于回收与活化,可实现催化剂的循环利用。V.利用无机物诱导凝胶转变为晶体这一基本原理,实现将无机上转换材料Na YF_4:Yb,Tm和无机半导体材料Ti O_2与MOF结合制备了两例多元复合型光催化剂Na YF_4:Yb,Tm@Cd-MOF和Na YF_4:Yb,Tm@Cd-MOF@Ti O_2。主要通过PXRD,IR,TGA,SEM,TEM,ICP,元素分析等手段表征了这两种催化剂的结构与组成;通过荧光发射光谱表征了这两种催化剂的上转化发光性质。初步分别探索了它们近红外光催化性能,近红外光催化反应合成了“卡洛芬”药物有机化合物,首次实现MOF复合催化剂的上转换光催化。综上所述,我们认为金属有机框架材料在催化等性质方面有很大的应用价值,还值得继续研究下去。研究发现:离子交换、后合成修饰、金属离子负载、材料复合等手段都可以制备新型MOFs催化剂。
[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.
【学位授予单位】：山东师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.4

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