等级孔金属—有机骨架配合物的可控合成及性能研究

发布时间：2018-06-23 05:48

本文选题：金属-有机骨架 + 等级孔　；参考：《河南师范大学》2017年硕士论文

【摘要】：金属-有机骨架配合物(Metal-Organic Frameworks,MOFs)是近年来人们非常关注的一类化合物,由于其变化丰富的孔道结构和可调变的组成与性质,在气体吸附、存贮与分离、能量储存/转化、化学传感、非均相催化、药物传输等领域具有重要用途。早期对于金属-有机骨架材料的研究主要集中于新型配位结构和孔道结构配合物的合成与性能,近年来人们的研究重点逐渐转移到了等级孔金属-有机骨架配合物。研究表明,等级孔的形成能够为金属-有机骨架材料带来许多单一孔道MOFs所不具备的特殊性质,不同形状结构和不同大小尺度孔道的共存能够赋予金属-有机骨架材料在催化、分离、吸附等领域的更多的优越性能,所以得到具有等级孔结构的MOFs材料成为人们关注的热点。目前用于合成等级孔MOFs的方法主要有模板法、后合成修饰法、扰动辅助纳米融合法、水解转化法、等离子体刻蚀及配体刻蚀法等,但这些方法往往实验条件比较苛刻且后续处理较为繁琐,且所得等级孔大多孔道结构不规则,分布无序,基本上都属于由微粒无序堆积而形成的孔,而规则有序等级孔结构的MOFs还很少,而孔的结构直接影响到所得MOFs材料的性能,因此合成新型等级孔结构的金属-有机骨架配合物及探索简单可靠的合成等级孔结构的方法具有重要意义。本论文主要进行了以下工作:(1)铜-TATAB等级孔金属-有机骨架的可控合成、表征、合成机理及性能的研究。以硝酸铜为铜盐、H3TATAB(H3TATAB:4,4′,4′′-s-三嗪-1,3,5-三对氨基苯甲酸)为配体、DMF为溶剂,通过简单的原位自组装合成了具有有序等级孔结构的Cu-TATAB金属-有机骨架(记为MM-CuTATAB),利用扫描电镜、透射电镜、X-射线粉末衍射仪、场发射扫描电镜和傅里叶红外等仪器对所得配合物进行了表征,探索了影响孔结构的合成条件,对其在不同溶剂条件下的稳定性进行了研究。同时,以MM-CuTATAB为基础,通过在不同温度和气氛下的碳化处理,得到了金属掺杂的碳基材料,测试了其电催化氧还原反应的性能。结果表明,所得MM-CuTATAB同时具有介孔(37.3nm)和大孔(55.2nm),呈规则分布;合成反应中H2O2加入量的不同和不同的静置时间是影响等级孔结构形成的重要因素。在不同溶剂中的稳定性测试表明其在有机溶剂CH3OH、C2H5OH和CH2Cl2中稳定性较大,在水、HCl及NaOH等介质中稳定性较差。273K和298K下对CO2的吸附实验表明,MM-CuTATAB表现出了273K下对CO21.18mmol/g的吸附量和298K下0.7mmol/g的吸附量。(2)Zn~(2+)、Co~(2+)、Ni~(2+)掺杂的等级孔Cu/M-TATAB配合物的合成、表征及电催化氧还原性能研究。以H3TATAB为配体、DMF为溶剂,分别与硝酸铜、硝酸锌、氯化钴和氯化镍等原位自组装合成了不同比例、不同量的Zn~(2+)、Co~(2+)、Ni~(2+)分别掺杂和Zn~(2+)/Co~(2+)共掺杂的配合物等级孔金属-有机骨架,并进一步进行不同温度的碳化,进行了其电催化氧还原性能研究。结果表明:进行Zn~(2+)、Co~(2+)和Ni~(2+)掺杂后仍然可以保持配合物的等级孔结构;同时铜锌摩尔比3:1及700℃下碳化、铜钴摩尔比4:1及800℃下碳化、铜镍摩尔比5:1及700℃下碳化和铜锌钴摩尔比2:2:2、700℃下碳化所得碳基材料电化学性能较好。(3)三维花状配合物F-Zn-TATAB的合成、表征及染料吸附性能研究。以硝酸锌为锌盐、H3TATAB为配体、DMF为溶剂,通过水热反应合成了具有三维花状结构的Zn-TATAB配合物(记为F-ZnTATAB),利用扫描电镜、透射电镜、X-射线粉末衍射仪、场发射、傅里叶红外等仪器对合成的样品进行表征,研究了三维花状结构形成的机理和其应用于染料吸附的性质。结果表明所得三维花状结构由纳米片状结构组装形成。染料吸附性能测试表明F-ZnTATAB对亚甲基蓝(MB)、孔雀石绿(MG)具有较高的的吸附效率:5min可达到82.57%和83.23%。
[Abstract]:Metal-Organic Frameworks (MOFs) is a kind of compound in recent years. Due to its rich pore structure and its composition and properties, it has important applications in the fields of gas adsorption, storage and separation, energy storage / conversion, chemical sensing, heterogeneous catalysis, drug transmission and so on. The research of metal organic skeleton materials is mainly focused on the synthesis and performance of new coordination structures and pore structure complexes. In recent years, the focus of research has gradually shifted to the hierarchical metal organic framework complexes. The study shows that the formation of grade holes can bring many single channel MOFs for metal organic skeleton materials. The coexistence of different shapes and structures and channels of different sizes can give the metal organic skeleton materials more superior performance in the fields of catalysis, separation and adsorption, so the MOFs material with hierarchical structure becomes the hot point of attention. The main methods used to synthesize the grade hole MOFs at present are mainly The template method, the post synthesis modification method, the perturbation assisted nano fusion method, the hydrolysis transformation method, the plasma etching and the ligands etching method, etc., these methods often have more harsh experimental conditions and the subsequent treatment is more complicated, and most of the pores are irregular in the pore structure and the distribution is unordered, basically all belong to the pores formed by the disordered accumulation of particles. But the MOFs of the regular ordered pore structure is very few, and the structure of the hole directly affects the properties of the obtained MOFs material. Therefore, it is of great significance to synthesize the metal organic framework complex of the new class pore structure and to explore the simple and reliable synthetic grade hole structure. The main work of this paper is as follows: (1) copper -TATAB grade hole The controllable synthesis, characterization, synthesis mechanism and properties of the metal organic framework, with copper nitrate as copper salt, H3TATAB (H3TATAB:4,4 ', 4' '-s- three azine -1,3,5- three p-aminophenic acid) as ligands and DMF as the solvent, have synthesized a Cu-TATAB metal organic skeleton with an ordered hierarchical structure by simple in situ self-assembly (recorded as MM-CuTATAB). By means of scanning electron microscopy, transmission electron microscopy, X- ray powder diffractometer, field emission scanning electron microscope and Fourier infrared instrument, the synthetic conditions of the pore structure are explored, and the stability of the structure under different solvent conditions is studied. At the same time, MM-CuTATAB is based on different temperatures and atmospheres. The carbon based material doped with metal was obtained. The performance of the electrocatalytic oxygen reduction reaction was tested. The results showed that the MM-CuTATAB had a regular distribution of mesoporous (37.3nm) and large pores (55.2nm), and the difference in the amount of H2O2 added and the different stationary time in the synthesis reaction were important factors affecting the formation of the structure of the grade hole. The stability test in different solvents showed that the stability of the organic solvent CH3OH, C2H5OH and CH2Cl2 was larger. The adsorption experiments on CO2 under the low stability.273K and 298K in water, HCl and NaOH showed that MM-CuTATAB showed the adsorption amount of CO21.18mmol/g under 273K and the amount of adsorption under 298K. (2) 2+) synthesis, characterization and electrocatalytic oxygen reduction properties of doped grade hole Cu/M-TATAB complexes, with H3TATAB as the ligand and DMF as solvent, respectively, with copper nitrate, zinc nitrate, cobalt chloride and nickel chloride in different proportions, different amounts of Zn~ (2+), Co ~ (2+), Ni~ (2+) and Zn~ (2+) Co doped complexes Zn~ (2+), Co~ (2+) and Ni~ (2+) can still maintain the grade pore structure of the complex; at the same time, the molar ratio of copper and zinc mole to 3:1 and 700 C, copper and cobalt molar ratio 4:1 and 800 C, copper and nickel at the same time The carbon based carbon based materials obtained by carbonization at mole ratio 5:1 and 700 C and Cu ZnCo molar ratio 2:2:2700 C are better. (3) synthesis, characterization and dye adsorption properties of three dimensional flower like complex F-Zn-TATAB, with zinc nitrate as zinc salt, H3TATAB as ligand and DMF as solvent, by hydrothermal reaction to synthesize a three-dimensional flower like structure of Zn- TATAB complex (F-ZnTATAB) was used to characterize the synthesized samples by scanning electron microscopy, transmission electron microscopy, X- ray powder diffractometer, field emission, Fourier infrared and other instruments. The mechanism of the formation of three-dimensional flower structure and the properties of its application to dye adsorption were studied. The results showed that the three-dimensional flower structure was assembled by nano sheet structure. Dye adsorption tests showed that F-ZnTATAB had high adsorption efficiency for methylene blue (MB) and malachite green (MG): 5min could reach 82.57% and 83.23%..
【学位授予单位】：河南师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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