摘要
金属有机框架(metal-organic framework,MOF)材料是由金属离子(簇)与有机配体通过配位键自组装而成,具有丰富多样的结构以及可调控的孔隙等特性,在诸多领域展现出重要应用前景.MOF材料的性能受其结构因素、客体分子性质以及外部环境因素的影响,因此MOF材料的结构表征对于理解其功能和性能优化至关重要.大科学装置,如先进光源、先进中子源、核磁共振仪和电子显微镜等,提供了先进实验技术和方法.利用先进的表征技术探究MOF材料在实际应用中的结构-性能关系,将为实现功能导向MOF材料的合理设计和可控制备提供重要理论基础.本文综述了MOF材料的绿色合成及结构,先进的原位表征技术及其在气体吸附与分离、荧光传感、质子传导、催化及工业领域中的应用及其前景分析,最后对MOF材料的未来发展进行了展望.尽管目前已经取得了诸多进展,但仍需要解决诸如精确调控结构与相互作用、改善实际应用稳定性等问题.未来的研究将着眼于开发功能导向MOF基材料、深入探究作用机制以及加强跨领域研究,以此推动MOF材料的进一步发展,为解决实际应用中重要的科学问题创造更多的可能性.
Over the past three decades,porous materials have attracted great attention in many research fields,including physics,chemistry and materials science.Metal-organic frameworks(MOFs),as a class of crystalline porous materials,constructed by metal ions/clusters and organic ligands via coordination self-assembly,featuring atomically precise and highly tailorable structures,which have broad applications in various fields of natural science.MOFs demonstrate compatibility with a diverse range of materials,including metal nanoparticles,polymers,metal oxides,metal complexes,organic molecules and even biological macromolecules such as enzymes and DNA.This versatility facilitates the construction of composites using MOFs and various vip species.By employing approaches such as direct or post-synthetic modification of ligands and metal secondary building units within the MOF framework,as well as introducing vip species,researchers can achieve meticulous modulation of the structural and functional properties of MOFs.From a fundamental science perspective,the interactions between MOFs and vip species are varied,encompassing van der Waals forces,hydrogen bonds,electrostatic interactions,π-πinteractions,coordination interactions and more.These interactions are influenced by multiple factors,including the structural characteristics of MOFs,such as pore size,properties of metal nodes and organic ligands and framework flexibility;the properties of vip molecules,including size,shape,functional groups and chemical properties,as well as external environmental factors like temperature,pressure and solvent effects.In consideration of the large number of MOF-related reviews reported in recent years,this article provides a comprehensive overview of the green synthesis and structures of MOFs,advanced in-situ characterization techniques and their applications and prospects in various fields,including gas adsorption and separation,fluorescence sensing,proton conduction,catalysis and industry.Traditional synthesis methods have significantly limited the large-scale production and industrialization of MOFs.In this review,we first introduced the green synthesis of MOFs and their distinctive structural advantages,such as stability and pore characteristics,in detail.Subsequently,we systematically summarise advanced characterization techniques employed to investigate the relationship between the microstructure and properties of MOFs.The properties of MOFs are intricately influenced by their intrinsic structural characteristics,the physico-chemical properties of vip molecules,and various external environmental conditions.Given this complex interplay,the structural characterization of MOFs is of paramount importance.Hence,it is essential to characterize the structures of MOFs to understand their functions and enhance their properties Utilising advanced characterization techniques to analyze MOF structures and properties is critical for comprehending their functions and optimizing their performance.The scientific facilities,such as advanced light sources,spallation neutron sources,nuclear magnetic resonance spectrometers and electron microscopes,provide sophisticated experimental techniques and methodologies.Via the employment of advanced characterization methodologies to investigate the structure-activity correlation toward important applications of MOFs,theoretical foundations can be established for the rational design and controllable fabrication of functionoriented MOFs.Furthermore,we systematically introduce the exploration of MOFs in various functional applications,such as gas adsorption and separation,fluorescence sensing,proton conduction,catalysis and industry,with particular emphasis on the structure-performance relationship.Finally,the future development prospects of MOFs are discussed.Although significant progress has been achieved,challenges such as precisely modulating structures and interactions,as well as enhancing stability for practical applications remain unaddressed.Future research endeavors will be centered on the development of novel MOFs,indepth exploration of interaction mechanisms,expansion of application fields and enhancement of transdisciplinary research.This will promote the further advancement of MOFs,thereby creating more opportunities to address scientific and practical challenges.
作者
高明亮
薛天威
李江南
郭利霞
郑和奇
卢江封
彭丽
杨四海
崔元靖
钱国栋
徐刚
江海龙
Ming-Liang Gao;Tianwei Xue;Jiangnan Li;Lixia Guo;He-Qi Zheng;Jiangfeng Lu;Li Peng;Sihai Yang;Yuanjing Cui;Guodong Qian;Gang Xu;Hai-Long Jiang(Hefei National Research Center for Physical Sciences at the Microscale,Department of Chemistry,University of Science and Technology of China,Hefei 230026,China;College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China;College of Chemistry and Molecular Engineering,Beijing National Laboratory for Molecular Sciences,Peking University,Beijing 100871,China;State Key Laboratory of Silicon Materials,School of Materials Science&Engineering,Zhejiang University,Hangzhou 310027,China;State Key Laboratory of Structural Chemistry,Fujian Provincial Key Laboratory of Materials and Techniques toward Hydrogen Energy,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China)
出处
《科学通报》
北大核心
2026年第2期370-399,共30页
Chinese Science Bulletin
基金
国家重点研发计划(2021YFA1500400)
国家自然科学基金(22101269,22373080,22078274,22405274,22325109,52025131)
中国科学院战略性先导科技专项(XDB0450302,XDB0540000)
北京市科技新星计划
中国博士后科学基金(2024M750053)
浙江省科学技术厅(2024C01191)资助。
关键词
金属有机框架材料
合成与先进表征
气体吸附与分离
荧光传感
质子传导
催化
metal-organic framework
synthesis and characterization
gas sorption and separation
fluorescent sensor
proton conduction
catalysis
