【作者】 张帅；

【导师】 贲腾；

【作者基本信息】 吉林大学 ， 高分子化学与物理， 2021， 博士

【摘要】 有机多孔材料是一类只由有机物组成的多孔材料,由于其较低的骨架密度,高的比表面积、大的孔隙率和孔体积以及优异的溶剂稳定性和热稳定性被广泛地应用于多种领域,如气体储存、质子导电、催化、大气水收集和气体分离等。此外,有机多孔材料的单体复杂多样,合成手段种类繁多,所以又包含:固有微孔聚合物（PIMs）、共价有机骨架材料（COFs）、超交联聚合物（HCPs）、共价三嗪骨架材料（CTFs）、共轭微孔聚合物（CMPs）、多孔芳香骨架材料（PAFs）、多孔有机笼和多孔有机盐等。多孔有机盐作为有机多孔材料的一种,是一种由有机酸和有机碱之间通过离子键连接而成的具有多孔性的有机盐类材料。其作为一种新兴的有机多孔材料,目前的发展仍处在初级阶段,面临着一些问题。例如大部分的多孔有机盐在移除客体分子后无法保持骨架结构,不具备永久多孔性。因此继续开发新型的具有永久多孔性的多孔有机盐对其发展至关重要,这不仅可以丰富多孔有机盐的种类,还可以促进其合成策略的进步。此外,合成新型的具有不同应用价值的多孔有机盐还可以扩展其应用范围提高与其它材料的竞争力。本论文合成了一系列新型的多孔有机盐,丰富了多孔有机盐种类的同时,把其应用到大气水收集领域。此外,通过制备大单晶和不同结构的多孔有机盐研究了其结构和性能之间的关系,对研究多孔有机盐的合成策略具有帮助,主要内容如下:（1）第一章综述了有机多孔材料的发展及一般应用,并介绍了新兴的有机多孔材料——多孔有机盐的发展历程和基本性质。（2）第二章通过选用具有T_d对称性的四（4-脒基苯基）甲烷和四（4-磺酸苯基）甲烷两种单体,在水和甲醇的混合溶剂中于室温下制备了四方晶系的多孔有机盐CPOS-9。由于多孔有机盐的极性孔道和高的亲水性,随后测试了一系列CPOSs的水蒸气吸附曲线,通过对比可以发现,新合成的CPOS-9具有S型的水吸附曲线,是一种理想的大气水收集技术的吸附剂材料。此外,通过研究S型曲线的阶梯区间发现其与我国新疆地区的气候环境完美吻合,可以用于新疆地区进行大气水收集应用,对于缓解当地的水资源短缺问题具有潜在的应用价值。通过Masterials studio模拟、不同湿度下的原位红外测试,水蒸汽吸附计算的等容吸附热和水吸附动力学计算的表观活化能证实了CPOS-9的水吸附过程机理。（3）第三章通过控制合成条件,用C₃对称性的cis,cis-1,3,5-三氨基环己烷·3HBr和C₂对称性的均苯四甲酸在水和甲醇的条件下合成了具有毫米级尺寸的大单晶,且其外观为规整的平行六面体形状,这为研究其不同面的质子导电提供了可能。随后通过电化学交流阻抗谱对CPOS-10不同面间的质子导电性进行了研究,通过与CPOS-10不同面间的晶体结构一一对应,发现了各向异性质子导电与晶面结构之间的关联。（4）第四章使用T_d对称性的单体四（4-磺酸苯基）甲烷和C₂对称性的哌嗪,在仅改变生长溶剂的条件下制备了三种不同的CPOSs。通过XRD、¹H NMR、FTIR、TGA研究了其结构组成和热稳定性,CO₂气体吸附表明三种CPOSs均具有永久的多孔性,其微孔表面积分别为97.6 m²/g、73.0 m²/g和21.4 m²/g。之后通过电化学交流阻抗谱研究了三种CPOSs的质子电导率,发现其质子电导率并不相同,其中在水和DMF中合成的CPOS-11-DMF在40℃、98%相对湿度下具有高达1.36×10^-2 S/cm的质子电导率。本章成功地在宏观上实现了从结构到性质的调控,得到了一种具有高质子导电性的多孔有机盐。更多还原

【Abstract】 Porous organic materials are a kind of porous materials only composed of organic compounds.Due to their low skeleton density,high specific surface area,large porosity and pore volume,excellent solvent and thermal stability,they are widely used in many fields,such as gas storage,gas separation,catalysis,atmospheric water collector and proton conduction.In addition,the monomers of organic porous materials are complex and diverse,and the synthesis methods are various,so they include:Hyper-cross-linked polymers（HCPs）,Polymers of intrinsic microporosity（PIMs）,Conjugated microporous polymers（CMPs）,Covalent organic frameworks（COFs）,Covalent triazine frameworks（CTFs）,Porous aromatic frameworks（PAFs）,Porous organic cages（POCs）and Crystalline porous organic salts（CPOSs）.As a kind of organic porous materials,Crystalline porous organic salts are a kind of organic salt materials with permanent pores,which is connected by ionic bonds between organic acids and organic bases.As a new type of organic porous material,it is still in its infancy and faces some problems.For example,most of the porous organic salts cannot maintain the skeleton structure after removing the guest molecules,and do not have permanent porosity.Therefore,it is very important to continue to develop new types of porous organic salts with permanent porosity,which can not only enrich the types of porous organic salts,but also promote the progress of their synthesis strategies.In addition,the synthesis of new porous organic salts with different application values can not only expand their application scope and improve their competitiveness with other materials,but also promote the research and development enthusiasm of scientific researchers and accelerate the development of porous organic salt materials.In this paper,a series of new porous organic salts were synthesized,which not only enriched the types of porous organic salts,but also applied to new technical fields and expanded their application scope.In addition,we prepared large single crystals and porous organic salts with different structures to study the relationship between their structures and properties,which is of great significance to the regulation of the synthesis strategy of porous organic salts,the main contents are as follows:（1）In the first chapter,the development and general application of porous organic materials are reviewed,and the development process and basic properties of porous organic salts are introduced.（2）In chapter 2,we prepared the Crystalline porous organic salts CPOS-9 by using tetra（4-amidophenyl）methane and tetra（4-sulfophenyl）methane as monomers in the mixed solvent of water and methanol at room temperature.Due to the polar channels and high hydrophilicity of porous organic salts,we measured a series of water vapor adsorption curves of CPOSs.By comparison,we found that the newly synthesized CPOS-9 has S-type water adsorption curve,which is an ideal adsorbent material for atmospheric water collector technology.The water adsorption mechanism of CPOS-9was confirmed by the simulation of Materials Studio,the FTIR measurement under different humidity,the adsorption heat calculated by steam adsorption and the apparent activation energy calculated by water adsorption kinetics.CPOSs has been applied in atmospheric water collector for the first time and its application scope has been expanded.（3）In chapter 3,by controlling the synthesis conditions,large single crystals with millimeter size were synthesized with cis,cis-1,3,5-triaminocyclohexane·3HBr and pyromellitic acid in the presence of water and methanol,and their appearance was regular parallelepiped shape.It is possible for us to study the proton conduction in different faces.Subsequently,we studied the proton conductivity between different faces of CPOS-10 by electrochemical impedance spectroscopy,and found the correlation between the anisotropic proton conductivity and the crystal structure through one-to-one correspondence with the crystal structure between different faces of CPOS-10.The mechanism of anisotropic proton conduction in CPOSs is explained to deepen our understanding of proton conduction in CPOSs.（4）In chapter 4,we prepared three different CPOSs using the same monomer tetra（4-sulfophenyl）methane and piperazine in different growth solvents.The structure and thermal stability of CPOSs were studied by XRD,¹H NMR,FTIR and TGA.CO₂adsorption showed that the three CPOSs had permanent porosity,and the microporous surface areas were 97.6 m² g^-1,73.0 m² g^-1 and 21.4 m² g^-1,respectively.After that,we studied the proton conductivities of three CPOSs by electrochemical impedance spectroscopy,and found that their proton conductivities were different.Among them,the proton conductivity of CPOS-11-DMF synthesized in water and DMF was as high as 1.36×10^-2 S cm^-1 at 40℃and 98%RH.The experimental results show that we successfully control the structure of porous organic salt by changing the type of solvent,which affects the proton conductivity of porous organic salt and realizes the macro-control from structure to property and obtain a porous organic salt with high proton conductivity.更多还原