金属有机框架有机配体官能团吸/给电子效应及熔点调控  

Electron-Absorbing Functional Groups Modulate Melting Point of Metal-Organic Frameworks

作　　者：李续 高成伟 周添跃 谭林玲 康世亮 焦清 林常规 LI Xu;GAO Chengwei;ZHOU Tianyue;TAN Linling;KANG Shiliang;JIAO Qing;LIN Changgui(Laboratory of Infrared Materials and Devices,Institute of Advanced Technology,Ningbo University,Ningbo 315211,Zhejiang,China;Zhejiang Key Laboratory of Optoelectronic Detection Materials and Devices,Ningbo 315211,Zhejiang,China;State Key Laboratory of Silicate Building Materials,Wuhan University of Science and Technology,Wuhan 430070,China)

机构地区：[1]宁波大学高等技术研究院,红外材料及器件实验室,浙江宁波315211 [2]浙江省光电探测材料及器件重点实验室,浙江宁波315211 [3]硅酸盐建筑材料国家重点实验室,武汉理工大学,武汉430070

出　　处：《硅酸盐学报》2024年第8期2559-2565,共7页Journal of The Chinese Ceramic Society

基　　金：国家自然科学基金青年基金(52202005);浙江省自然科学基金(LQ23E020005);硅酸盐材料工程教育部重点实验室(武汉理工大学)开放课题基金(SYSJJ2023-11)。

摘　　要：金属有机框架(MOF)玻璃,作为第4种熔融淬冷玻璃,在能源、气体分离等领域都具有潜在的应用价值。但目前只有部分MOF可制备成为玻璃,且其熔点与分解温度相近,导致玻璃成品中分解杂质多,制备能耗高。基于有机配体上官能团的吸/给电子效应,通过调控咪唑基配体的种类和含量,调节配体与金属中心的配位键强弱,可将TIF-4的熔点从375℃降至295℃。证明了有机配体上官能团吸/给电子效应对MOF熔点调控的有效性和通用性,为指导开发更多MOF玻璃提供了理论基础,有利于促进MOF玻璃的实际应用。Introduction MOF-based electrolytes exhibit excellent chemical and thermal stability,which can improve the service life and safety of the whole battery.The research of MOF electrolytes is expected to promote the progress and development of solid-state battery technology with high energy density and high safety.The MOF electrolytes has more grain boundaries,which tend to cause interfacial problems such as dendrite growth.In order to eliminate the grain boundaries of MOF,vitrification is a more effective strategy.However,the strong coordination bonds between the metal and organic ligands in MOF lead to high melting points and higher energy consumption required for the MOF glass preparation.In addition,the melting point and decomposition temperature of MOF are very close,and only several MOF can melt when heated,and most of MOF will decompose before melting,accompanied by carbonization of organic ligands,and oxidation of metal ions.Therefore,for most MOF crystals,it is challenging to transform them into glass state by the conventional melt-quenching method.To expand the variety of MOF glasses,researchers have increased the entropy of melting by introducing functional groups with electron-absorbing ability and modified MOFs by strategies such as ion exchange and surface engineering,thereby lowering the melting temperature of MOFs.However,there is no clear mechanistic guidance for the melting point regulation of MOF crystals,and the relationship between its coordination bonds and its melting process is still unclear.Methods By introducing different functional groups with different electron-withdrawing/donating effects on organic ligands,the strength of coordination bonds between metal ions and organic ligands can be adjusted,through which the mechanism and influence law of MOF melting point regulation is investigated.The ligand and metal ions were dissolved in 15 mL of DMF,and then the above solutions were heated and held at 130℃for 48 h.After cooling,the products were collected by centrifugation,washed out with DMF

关 键 词：金属有机框架 玻璃 熔点调控 玻璃化 熔融淬冷 分解温度 

分 类 号：TQ171.1[化学工程—玻璃工业]