后合成法构筑钛基金属有机框架及其应用  

A Post-Synthetic Method for the Construction of Titanium-Based Metal Organic Frameworks and Their Applications

作　　者：齐学平 王飞[1] 张健[1] Qi Xueping;Wang Fei;Zhang Jian(State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002)

机构地区：[1]中国科学院福建物质结构研究所结构化学国家重点实验室,福州350002

出　　处：《化学学报》2023年第5期548-558,共11页Acta Chimica Sinica

基　　金：国家自然科学基金(No.21971241)资助。

摘　　要：钛基金属有机框架(Ti-MOFs)因其优异的光催化活性成为当前材料研究领域的热点.但由于Ti离子极高的反应活性和亲氧属性,在反应过程中极易形成氧化物和其它竞争性的副产物,使得Ti-MOFs的合成极具挑战性.在MOFs发展的初期,关于Ti-MOFs的研究便同步开展,然而经过二十多年的发展,已报道的Ti-MOFs只有数十种,在上万种的MOFs中占比极其有限.为了避免或减少钛离子副反应的发生,通常在已知MOFs框架中引入金属Ti离子,来定向合成Ti-MOFs,该方法被称为后合成法(PSM),也是构筑Ti-MOF框架的一种有效方法.对PSM构筑Ti-MOFs的实例进行了系统的调研和总结.首先,依据钛离子引入方式和位置的不同,分为离子交换、离子插入(金属节点或簇单元位置引入钛离子)和配体修饰(有机配体位置引入钛离子)三种途径,并通过实例介绍了每种途径构筑的Ti-MOFs.随后,对PSM构筑的Ti-MOFs及其复合材料的设计与应用进行讨论.最后,对PSM构筑Ti-MOFs的现状进行总结并展望了未来的发展方向.Titanium-based metal organic frameworks(Ti-MOFs)have become a hot topic in current materials research due to their excellent photocatalytic activity.However,due to the extremely high reactivity and oxygenophilic properties of Ti ions,oxides and other competing by-products are easily formed during the reaction process,making the synthesis of Ti-MOFs extremely challenging.The research on Ti-MOFs was carried out simultaneously at the early stage of MOFs development,however,after more than two decades of development,only tens of Ti-MOFs have been reported,accounting for an extremely limited proportion of the tens of thousands of MOFs.In order to avoid or reduce the occurrence of titanium ion side reactions,Ti-MOFs are usually synthesized by introducing metal Ti ions into the framework of known MOFs to orientate the synthesis of Ti-MOFs,which is called post-synthetic method(PSM)and is also an effective method to construct Ti-MOF framework.The examples of PSM for constructing Ti-MOFs are systematically investigated and summarized in a timely manner.Firstly,based on the different ways and positions of titanium ion introduction,three routes are classified as ion exchange,ion insertion(introduction of titanium ion at the position of metal nodes or cluster units)and ligand modification(introduction of titanium ion at the position of organic ligands),and the Ti-MOFs constructed by each route are introduced by examples.Subsequently,the design and application of Ti-MOFs constructed by PSM and their composites are discussed.Finally,the current status of PSM-constructed Ti-MOFs is summarized and the future development direction is foreseen.

关 键 词：金属有机框架 后合成法 钛 光催化 

分 类 号：O641.4[理学—物理化学]