MOFs: New Useful Materials – A Special Issue in Honor of Prof. Susumu Kitagawa
MOFs: New Useful Materials – A Special Issue in Honor of Prof. Susumu Kitagawa
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MOFs：新的有用材料-荣誉北川进教授的特刊
DOI：
10.1002/adma.201803613
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发表时间：
2018-09
影响因子：
29.4
通讯作者：
Qiang Xu;H. Kitagawa
中科院分区：
文献类型：
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作者：
Qiang Xu;H. Kitagawa
DOI：10.1002/adma.201803613涉及使用MOFs的安全储存系统是C2 H2和其他爆炸性气体储存和运输技术的重大成就。这两项研究很早就证明了MOFs的实用性和多功能性。除了这些坚固的多孔框架外，Kitagawa还开发了框架的概念，具有多孔性和结构灵活性。他预言了这类材料的存在和重要性，并将其统称为软多孔晶体。一类重要的软质多孔晶体是柔性MOFs，它们被认为是“柔软性”和“结晶性”的协同集成。金属离子和有机配体的精确结合创造了各种柔性MOF，他还展示了用于分离的超临界气体识别（2003年）。柔性框架通过结构变化在一定压力下吸附目标气体，然后通过变压法释放被吸附气体。他优化了结构的灵活性，并在低再生能量材料中实现了对CH 4的高CO2分离能力（2012年）。已经表明，他的一些灵活的MOFs提供低能量的二氧化碳从沼气分离。他创造了MOF材料，其气体吸附性能可以通过施加外部刺激（如光或电场）来控制。合成了可转换的孔表面，其可以通过光照射程序活化（2010）。分子解码系统的按需捕获使用结构缠结来检测具有相应发光读数的蒸汽形式的苯衍生物的单个目标分子（2011）。通过使用氧化还原活性的MOF，证明了对O2和NO的高选择性超过各种气体。MOFs含有一种给电子有机连接体，当特定气体被吸附时，配体发生氧化（2010年）。除了这种对宿主框架的功能化之外，他还通过使用客人住宿来制作响应性MOF。他在多孔结构中引入了荧光信号分子，通过吸附CO2气体（2011）来打开/关闭混合材料的荧光，从而实现低浓度气体传感。他通过客体吸附证明了MOF中磁性状态的可逆切换（2009年）。在室温下，具有氰基-配体桥连的Fe 2+基MOF表现出高自旋（HS）态和低自旋（LS）态之间的双稳态。取决于吸附的气体，MOF可以采用HS和LS状态。这些磁性状态在室温下通过气体吸附/脱附来切换。将这种响应性基团并入MOF中表明了它们在制造先进多孔材料方面的巨大潜力。Kitagawa注意到，在分子/离子传输技术中重要的受限有机聚合物的热转变可以在纳米空间内控制。他指出，可以定制MOFs的孔径和表面功能来研究受限聚合物的转变行为，提供金属有机框架（MOFs），也称为多孔配位聚合物（PCP），是一类新兴的多孔材料。由于其结构和功能的可调性，MOFs领域已成为化学和材料科学中发展最快的领域之一。随着合成方法、结构表征和功能修饰的成熟，MOFs作为一种有用材料的新时代已经开始，在过去的几年中出现了大量的出版物，涉及它们在各种方向甚至器件中的应用。在此，我们非常荣幸地汇集了一个概要的最新工作，对他们的应用从材料的角度，在这个特殊的问题，荣誉教授，在京都大学北川进，一个先驱的MOF领域。早在1997年，Kitagawa就通过气体吸附实验成功地证明了固体配位网络的多孔性。他合成了各种各样的MOFs，并开发了一种全面的结构化学。在MOF化学的早期阶段，他专注于足够小和均匀的孔，这些孔具有与氧分子相当的尺寸，并意识到气态氧可以形成规则的一维链。这使人们对受限气体的性质有了前所未有的了解，由此产生的O2的高度压缩包装可与2 GPa（2002）下的固体氧相媲美。乙炔是一种具有许多工业应用的气体;然而，由于其爆炸性，它很难处理。一种将其与其密切关系二氧化碳（CO2）分离的高效方法，是净化和储存“战略”气体的一种有前途的途径。他成功地在环境条件下对乙炔（C2 H2）气体进行高选择性捕获和储存，以对抗CO2（2005年）。的
DOI: 10.1002/adma.201803613 safe storage system involving the use of MOFs is a significant achievement for technologies for the storage and transport of C2H2 and other explosive gas. These two studies demonstrated early on the usefulness and versatility of MOFs. Beyond these robust porous frameworks, Kitagawa also developed the concept of the framework, possessing both porosity and structural flexibility. He predicted the existence and importance of this class of materials, and gave it the generic name of soft porous crystals. An important class of soft porous crystals is the flexible MOFs, which are regarded as cooperatively integrating “softness” and “crystallinity”. The precise combination of metal ions and organic ligands created a variety of flexible MOFs, and he demonstrated the supercritical gas recognition for separation (2003). A flexible framework can adsorb the target gas at a certain pressure via structural changes, and then release the adsorbed gas by the pressure-swing method. He optimized the flexibility in the structures, and achieved high CO2-separation ability over CH4 in low-regeneration-energy materials (2012). It has been shown that some of his flexible MOFs offer lowenergy CO2 separation from biogas. He created MOF materials whose gas-adsorption properties are controllable by applying external stimuli such as light or electric fields. Switchable pore surfaces were synthesized that can be activated by the photoirradiation procedure (2010). On-demand trapping of a molecular decoding system used a structural entanglement to detect a single target molecule of benzene derivatives in a vapor form with a corresponding luminescent readout (2011). By the use of a redox-active MOF, the high selectivity for O2 and NO over various gases was demonstrated. MOFs contain an electrondonating organic linker and oxidation of the ligand occurs as specific gases are adsorbed (2010). Beyond this functionalization of the host framework, he also made a responsive MOF by using guest accommodation. He incorporated fluorescence signaling molecules in the porous structure, with the fluorescence of the hybrid material being switched ON/OFF via adsorption of CO2 gas (2011), allowing low-concentration gas sensing. He demonstrated reversible switching of magnetic states in MOFs by guest adsorption (2009). An Fe2+-based MOF with cyano-ligand bridging exhibits bistability between the high spin (HS) state and the low spin (LS) state at room temperature. The MOF can adopt both the HS and LS states depending on the adsorbed gases. These magnetic states are switched by gas adsorption/desorption at room temperature. The incorporation of such responsive groups in MOFs demonstrates their large potential to create advanced porous materials. Kitagawa noticed that the thermal transitions of confined organic polymers, important in molecule-/ion-transport technology, can be controlled within nanospaces. He showed that the pore size and surface functionality of MOFs can be tailored to study the transition behavior of confined polymers, providing Metal–organic framewrks (MOFs), also known as porous coordination polymers (PCPs), are an emerging class of porous materials. Due to their structural and functional tunability, the field of MOFs has become one of the fastest growing fields in not only chemistry but also material science. With the maturation of the synthesis methodology, structure characterization, and functionality modification, a new era of MOFs as a useful material has begun, with a huge number publications appearing in the last few years, dealing with their applications in a variety of directions, even devices. Here, we are greatly honored to assemble a compendium of the latest work on MOFs toward their applications from the materials angle, in this special issue in honor of Professor Susumu Kitagawa at Kyoto University, one of the pioneers of the MOF field. As early as in 1997, Kitagawa successfully demonstrated porosity in solid coordination networks with gas-sorption experiments. He synthesized a wide variety of MOFs and developed a comprehensive structural chemistry. In the early stage of MOF chemistry, he focused on sufficiently small and uniform pores, which possess comparable size to the oxygen molecule, and realized that gaseous oxygen can be made to form regular one-dimensional chains. This gave unprecedented insight into the properties of confined gases, with the resulting highly compressed packing of O2 comparable to that in solid oxygen at 2 GPa (2002). Acetylene is a gas with many industrial applications; however, it is hard to handle because of its explosive nature. A highly efficient method to separate it from its close relation, carbon dioxide (CO2), is a promising route for purifying and storing “strategic” gases in general. He succeeded in the highly selective capture and storage of acetylene (C2H2) gas against CO2 under ambient conditions (2005). The