基于钛-醇金属有机玻璃和晶态金属有机框架的多孔复合材料  

Porous Composite Materials Based on Titanium Alkoxide Glass and Crystalline Metal–Organic Framework

作　　者：张紫惠 谢志琨 赵英博 ZHANG Zihui;XIE Zhikun;ZHAO Yingbo(School of physical science and technology,ShanghaiTech University,Shanghai 201210,China)

机构地区：[1]上海科技大学物质科学与技术学院,上海201210

出　　处：《硅酸盐学报》2024年第8期2575-2584,共10页Journal of The Chinese Ceramic Society

基　　金：上海科技大学启动经费。

摘　　要：晶态与玻璃态金属有机框架(MOF)的复合材料有望兼具晶态框架的高比表面积和玻璃态材料的高加工性,代表了新型多孔材料研究的重要机遇。本工作设计了一系列基于钛氧簇节点和多元醇配体的玻璃态MOF,其温和的合成条件、模块可设计性和均匀透明的特点令其成为与晶态框架进行复合的理想基质。通过在此类MOF玻璃中引入纳米尺寸、具有良好分散性的Ui O-66和HKUST-1晶体,可制得均匀的复合材料。在合成中此2种MOF都保持了良好的结晶性和气体吸附性能。相比之下,ZIF-8在与玻璃态网络中失去了高结晶性和气体吸附能力。此外,金属有机多面体(MOP),作为MOF在分子尺度的对应体,也可与玻璃态网络形成复合材料并体现出高气体吸附能力。本工作发展了一类新型的自下而上合成的玻璃态MOF,并利用其温和的合成条件和良好的合成兼容性实现了与晶态MOF和MOP的高比表面积复合材料,为发展基于玻璃态MOF的多孔材料提供了可靠途径。Introduction Glassy metal–organic frameworks are emerging types of materials that could combine the modular tunability and high porosity of crystalline metal–organic frameworks(MOF)and the high processability of glassy materials.However,it remains difficult to obtain glassy MOF with high porosity.Thus,an alternative design strategy of embedding crystalline MOF nanocrystals into glassy MOF becomes very attractive to achieve materials with high porosity and liquid-like processability.Glassy materials based on titanium alkoxides are suitable host material for this purpose,which are easy to synthesis at large scale under mild conditions.Also,metal–organic polyhedral(MOP),as the molecular analogue for MOF,are also promising material for synthesizing composite materials.In this report,we developed a series of composite materials made of crystalline MOF and discrete MOP embedded in MOF glasses based on titanium-oxo cluster nodes and alkoxide linkers,and studied their porosity,crystallinity and morphology,which would pave the way for developing composite materials based on MOF glasses.Methods The prototype crystalline MOF,UiO-66,ZIF-8 and HKUST-1 were synthesized through solvothermal condition according to literature reports.The titanium alkoxide glass is made by mixing titanium precursor,titanium isopropoxide and the corresponding alcohol linker in alcohol solvents followed by evaporating the solvent at elevated temperature.To obtain the MOF@MOF glass composite materials,MOF nanocrystals were simply dissolved in the solution mixtures that were used to obtain titanium alkoxide glasses.The MOF@MOF glass composite materials were then washed out with various solvents and activated with super-critical CO_(2) drying,and then tested for N2 uptake at 77 K to obtain porosity data.The crystallinity of MOF after synthesis were measured by XRD,and the composite materials were studied by SEM.For the composite material using MOP,the hydroxyl functionalized MOP were synthesized in a method similar to literature,and then reacted

关 键 词：金属有机框架 比表面积 玻璃材料 孔隙率 复合材料 

分 类 号：TB332[一般工业技术—材料科学与工程]