【作者】 王文静；

【导师】 董彬；

【作者基本信息】 中国矿业大学 ， 物理化学， 2020， 硕士

【摘要】 作为一种具有晶型的多孔材料,共价有机骨架（Covalent Organic Frameworks,COFs）是由构筑单元通过共价键连接而成,其分子结构可以通过拓扑学原理进行调整。共价键的可逆形成是构成COFs的关键,允许进行误差校正来生成高度有序的结构。由于COFs具有密度小、比表面积大、均一的孔道、高的热稳定性以及容易功能化的特点,其在染料吸附、催化、质子传导和气体吸附分离等方面有很大的应用前景。COFs最常使用的合成方法是溶剂热法,通常使用易挥发和有毒性的混合有机溶剂。为了减小环境污染问题,研究COFs的绿色合成是有必要的。本论文致力于绿色溶剂中COFs的合成、性质及应用研究,主要研究内容包括以下两个部分:1.使用离子液体1-丁基磺酸-3-甲基咪唑硫酸氢盐（[BSMIm]HSO₄）作为绿色反应介质,以1,3,5-三甲酰基间苯三酚（TFP）和不同的胺基单体在敞开体系中基于席夫碱反应成功合成了四种二维COFs,其中包括首次合成的一种新COF（TFP-AHAn-COF）。基于二维COFs的开放通道,离子液体可以被完全去除,COFs表现出与溶剂热法类似的晶型和多孔性质。离子液体不仅作为溶剂和催化剂,还可以重复使用而无活性损失,展示出作为绿色溶剂合成COFs的广阔前景。2.使用四丁基溴化铵/咪唑（Bu₄NBr/Im）低共熔溶剂作为绿色反应介质,以TFP和2,5-二氨基苯甲酸（PaCOOH）为单体基于席夫碱反应制备羧基功能化COF（TFP-PaCOOH-COF）。因为低共熔溶剂具有低的蒸气压,合成过程仍在开放体系中进行。TFP-PaCOOH-COF具有较好的晶型、多孔性和高的热稳定性。另外,TFP-PaCOOH-COF对阴离子染料曙红吸附能力差,而对藏红和亚甲基蓝两种阳离子染料具有很好的选择性吸附能力。更多还原

【Abstract】 As a type of porous materials that own crystalline structures,covalent organic frameworks（COFs）are built from building blocks linked by covalent bonds,whose molecular structures can be modulated by using the principle of topology.The reversible formation of covalent bonds is the key to the construction of COFs,which allows for error correction to generate highly ordered frameworks.COFs have great application prospects in dye adsorption,catalysis,proton conduction,gas storage and separation as a result of low density,high surface area,uniform pores,high thermal stability and easy functionality.Solvothermal method is commonly used to synthesize COFs,which is usually carried out in closed systems using a mixture of volatile and toxic organic solvents.In order to reduce environmental pollution,it is necessary to study the green synthesis of COFs.This paper was focused on the synthesis of COFs in green solvents as well as their properties and appplications.The main research contents include the following two parts:1.Four kinds of two-dimensional（2D）COFs were successfully synthesized by using an ionic liquid 1-butylsulfonic-3-methylimidazolium hydrogensulfate（[BSMIm]HSO₄）as the green reaction medium with the condensation of1,3,5-triformylresorcinol（TFP）and amine monomers through Schiff-base reactions in an open system,including a new COF（TFP-AHAn-COF）synthesized for the first time.Based on the open channels of 2D COFs,the ionic liquid can be removed completely,and COFs exhibited crystallinity and porous properties similar to those prepared by solvothermal synthesis.Not only the ionic liquid acted as both solvent and catalyst,it was also recycled for further use without activity loss,showing broad prospects for the synthesis of COFs as green solvents.2.Using a deep eutectic solvent（DES）tetrabutylammonium bromide and glyoxaline（Bu₄NBr/Im）as the green reaction medium,a carboxyl-functionalized COF（TFP-PaCOOH-COF）was prepared by the reaction of TFP and2,5-diaminobenzoic（PaCOOH）as monomers through Schiff-base reaction.The synthetic process was carried out in an open system because of the low vapor pressure of the Bu₄NBr/Im DES.TFP-PaCOOH-COF had good crystallinity,porosity,and high thermal stability.In addition,TFP-PaCOOH-COF exhibited poor adsorption capacity for anion dye（Eosin B）,while it showed excellent adsorption capacity for two cationic dyes（Safranine T and Methylene blue）.更多还原