Advances and Application Prospect on Photoresponsive Metal-organic Frameworks Enhanced Publication

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College， Northwestern Polytechnical University， Xi'an 710100， China", "data": [ { "name": "text", "data": "Honors College， Northwestern Polytechnical University， Xi'an 710100， China" } ] } ] }, { "id": "aff3", "intro": [ { "lang": "zh", "label": "3", "text": "中国人民解放军军事科学院 国防工程研究院， 河南 洛阳　471023", "data": [ { "name": "text", "data": "中国人民解放军军事科学院 国防工程研究院， 河南 洛阳　471023" } ] }, { "lang": "en", "label": "3", "text": "Institute of Defense Engineering， AMS， PLA， Luoyang 471023， China", "data": [ { "name": "text", "data": "Institute of Defense Engineering， AMS， PLA， Luoyang 471023， China" } ] } ] }, { "id": "aff4", "intro": [ { "lang": "zh", "label": "4", "text": "河南省特种防护材料重点实验室， 河南 洛阳　471023", "data": [ { "name": "text", "data": "河南省特种防护材料重点实验室， 河南 洛阳　471023" } ] }, { "lang": "en", "label": "4", "text": "Henan Key Laboratory of Special Protective Materials， Luoyang 471023， China", "data": [ { "name": "text", "data": "Henan Key Laboratory of Special Protective Materials， Luoyang 471023， China" } ] } ] } ] }, "abstracts": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "随着智能材料的快速发展，光响应金属有机框架（MOFs）引起了研究者的广泛关注。该类智能材料可在紫外线和可见光的交替照射下，实现MOFs在不同形态之间可逆切换，同时伴随着物理和化学性质的改变，在药物运输、气体分离、光控催化和智能传感等领域具有广阔的发展前景。大部分光响应MOFs由光响应配体和金属离子通过配位作用形成，不同的光响应配体使体系具有独特的性质和应用场景。本文综述了近年来光响应MOFs的研究进展，其中包括光响应MOFs材料的主要类型及其在气体分离、物质运输、动态防伪和光电器件等不同领域中的应用。在此基础上，本文针对光响应MOFs未来发展进行了展望。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "With the rapid development of smart materials， photoresponsive metal-organic frameworks （MOFs） has attracted extensive attention of researchers. Under the alternating irradiation of ultraviolet and visible light， photoresponsive MOFs can be reversibly switched between different morphologies， accompanied by changes in physical and chemical properties， which have broad development prospect in the fields of drug transport， gas separation， photo-controlled catalysis and smart sensing. Most of the photoresponsive MOFs are formed by the coordination of photoresponsive ligands and metal ions. Different photoresponsive ligands make the systems have unique properties and application scenarios. In this article， the recent research progress of photoresponsive MOFs is reviewed， including the main types of photoresponsive MOFs and their applications in different fields such as gas separation， material transport， dynamic anti-counterfeiting， and optoelectronic devices. Finally， the future development of photoresponsive MOFs is prospected." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "金属有机框架" } ], [ { "name": "text", "data": "物质运输" } ], [ { "name": "text", "data": "气体分离" } ], [ { "name": "text", "data": "动态防伪" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "metal-organic frameworks" } ], [ { "name": "text", "data": "material transport" } ], [ { "name": "text", "data": "gas separation" } ], [ { "name": "text", "data": "dynamic anti-counterfeiting" } ] ] } ], "highlights": [], "body": [ { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "1　引　　言" } ], "level": "1", "id": "s1" } }, { "name": "p", "data": [ { "name": "text", "data": "金属有机框架（Metal-organic frameworks， MOFs）是由金属离子或原子簇与多齿有机配体通过配位作用形成一维、二维、三维结构的配位化合物，其具有高孔隙度、大比表面积且多孔以及结构易于修饰调节等特性，成为广受关注的新一代多孔材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "1", "type": "bibr", "rid": "R1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "3", "type": "bibr", "rid": "R3", "data": [ { "name": "text", "data": "3" } ] } } ], "rid": [ "R1", "R2", "R3" ], "text": "1-3", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。早在上世纪九十年代初，就有学者对这种材料进行过探索性的研究，至九十年代末，Yaghi和kitagawa等团队发现和建立了MOFs材料稳定的多孔性" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "4", "type": "bibr", "rid": "R4", "data": [ { "name": "text", "data": "4" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，MOFs材料进入快速发展和应用阶段，一系列高性能的MOFs材料相继问世。例如，Yaghi教授团队在2010年报道的MOF-210，该材料的比表面积已经接近固体材料比表面积的极限" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "5", "type": "bibr", "rid": "R5", "data": [ { "name": "text", "data": "5" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；陈小明院士和张杰鹏教授团队在2017年报道了一种新型的Zn-MOF结构材料，该材料能够在温和条件下，分离纯化结构相似的混合气体中的1,3-丁二烯且选择性可达99.5%" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "6", "type": "bibr", "rid": "R6", "data": [ { "name": "text", "data": "6" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；ZIF系列中的ZIF-8，其热稳定性高达500 ℃" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "7", "type": "bibr", "rid": "R7", "data": [ { "name": "text", "data": "7" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "8", "type": "bibr", "rid": "R8", "data": [ { "name": "text", "data": "8" } ] } } ], "rid": [ "R7", "R8" ], "text": "7-8", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，有效解决了MOFs材料热稳定性差的缺点，而诸如MIL系列、UiO系列" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "9", "type": "bibr", "rid": "R9", "data": [ { "name": "text", "data": "9" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "等MOFs材料也具有独特的物理和化学特性。目前，MOFs的发展呈现出多领域、学科交叉共同发展的态势，在物质储存与分离" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "10", "type": "bibr", "rid": "R10", "data": [ { "name": "text", "data": "10" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "11", "type": "bibr", "rid": "R11", "data": [ { "name": "text", "data": "11" } ] } } ], "rid": [ "R10", "R11" ], "text": "10-11", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、光学" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "12", "type": "bibr", "rid": "R12", "data": [ { "name": "text", "data": "12" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、传感器" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、高效催化" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "R14", "data": [ { "name": "text", "data": "14" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "和药物运输" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } } ], "rid": [ "R15", "R16" ], "text": "15-16", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "等领域发挥着重要作用。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "近年来，随着智能材料的蓬勃发展，刺激响应型金属有机框架材料引起了人们的广泛关注。一些MOFs材料在受到温度" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "17", "type": "bibr", "rid": "R17", "data": [ { "name": "text", "data": "17" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、电磁" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "18", "type": "bibr", "rid": "R18", "data": [ { "name": "text", "data": "18" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、pH" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "19", "type": "bibr", "rid": "R19", "data": [ { "name": "text", "data": "19" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、应力" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "20", "type": "bibr", "rid": "R20", "data": [ { "name": "text", "data": "20" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、光" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "等外界刺激时，其孔径、孔隙率等特性会发生改变，同时伴随着物理或化学性质的变化，而这些特性为新一代智能材料的研究及应用提供了新的设计策略。在这些外界刺激中，光刺激具有非接触、易操控以及高精度等优势，因此易于控制刺激强度及作用位点，且能有效降低反应过程中副产物的生成" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "22", "type": "bibr", "rid": "R22", "data": [ { "name": "text", "data": "22" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "24", "type": "bibr", "rid": "R24", "data": [ { "name": "text", "data": "24" } ] } } ], "rid": [ "R22", "R23", "R24" ], "text": "22-24", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。因此，对于光响应MOFs的相关研究成为当前功能材料领域研究的热点。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "近年来，研究人员通过对骨架内的有机配体及不饱和金属位点进行功能化修饰，报道了一系列光响应性能优异的MOFs材料，目前已有许多关于光响应MOFs的综述发表" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "25", "type": "bibr", "rid": "R25", "data": [ { "name": "text", "data": "25" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "26", "type": "bibr", "rid": "R26", "data": [ { "name": "text", "data": "26" } ] } } ], "rid": [ "R25", "R26" ], "text": "25-26", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。最近，吴春飞教授团队发表了一篇关于光响应MOFs在环境保护领域的相关综述，主要报道了通过光开关MOFs粉末或薄膜对CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的可控捕获" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "27", "type": "bibr", "rid": "R27", "data": [ { "name": "text", "data": "27" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。本篇综述首先概述几类光响应MOFs材料，阐明其光响应机理；之后主要介绍最近几年具有代表性的光响应MOFs在不同领域的研究进展，使读者了解目前光响应MOFs在各领域的发展现状及瓶颈问题。最后，对现有技术水平下，光响应MOFs所面临的局限、挑战与未来发展进行分析，探讨MOFs未来的研究及应用方向。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2　光响应MOFs材料介绍" } ], "level": "1", "id": "s2" } }, { "name": "p", "data": [ { "name": "text", "data": "光响应MOFs既具有MOFs材料高比表面积、孔径均一等特点，又可对光刺激作出反应，是一类具有多功能性的先进材料。该类材料一般由光响应基团作为配体，通过和金属离子或团簇形成配位键进而自组装成目标材料。其中光响应配体包括可逆光响应配体和不可逆光响应配体，不可逆光响应配体对光刺激仅存在一次响应，在另一刺激作用下不能恢复至初始状态，可逆光响应配体则与之相反。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "可逆光响应MOFs材料在外界光刺激下，骨架内的分子结构会发生变化，伴随着MOFs孔隙结构的改变，使材料的物理或化学性质发生变化；通常在另一波长光照射或加热条件下，材料会恢复至初始状态，具有可逆性。在前期研究中，可逆光响应MOFs依据其光响应机理不同，通常可分为偶氮苯类" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "28", "type": "bibr", "rid": "R28", "data": [ { "name": "text", "data": "28" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、二芳基乙烯类（Diarylethene，DAE/DTE）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "29", "type": "bibr", "rid": "R29", "data": [ { "name": "text", "data": "29" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、螺吡喃类" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "30", "type": "bibr", "rid": "R30", "data": [ { "name": "text", "data": "30" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "等，其结构如" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "所示。偶氮苯类化合物在受到一种波长光刺激后，稳定的反式结构会转变为亚稳态的顺式结构，使MOFs结构发生改变，进而改变材料孔径及气体吸附性质等，这种特性使该类材料常应用于气体分离、传感及药物运输" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "31", "type": "bibr", "rid": "R31", "data": [ { "name": "text", "data": "31" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "32", "type": "bibr", "rid": "R32", "data": [ { "name": "text", "data": "32" } ] } } ], "rid": [ "R31", "R32" ], "text": "31-32", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "领域。二芳基乙烯类化合物在受到光照之后，会发生可逆的光环化反应，使体系的共轭增大，在可见光区出现吸收峰；而二芳基乙烯类MOFs材料光照前后MOFs的骨架变化较小，但材料的光致发光和颜色会产生明显的改变。因此，该类光响应MOFs材料主要应用于信息存储和信息加密领域" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "R33", "data": [ { "name": "text", "data": "33" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "34", "type": "bibr", "rid": "R34", "data": [ { "name": "text", "data": "34" } ] } } ], "rid": [ "R33", "R34" ], "text": "33-34", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。螺吡喃类化合物具有螺环结构，在受到紫外光（Ultraviolet，UV）照射后，结构中的C—O键会发生断裂开环，使螺吡喃变为共平面的部花菁结构，颜色由无色转变为有色。此外，螺吡喃类化合物不仅具有光响应性，且可对温度、pH等产生响应，因此螺吡喃类MOFs材料常常兼具多刺激响应，螺噁嗪具有和螺吡喃相似的性质。除了常见的上述光开关外，还有一些新兴的光开关在MOFs材料中也具有广阔的应用前景，比如三芳基乙烯类光开关" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "35", "type": "bibr", "rid": "R35", "data": [ { "name": "text", "data": "35" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "39", "type": "bibr", "rid": "R39", "data": [ { "name": "text", "data": "39" } ] } } ], "rid": [ "R35", "R36", "R37", "R38", "R39" ], "text": "35-39", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，和二芳基乙烯衍生物的光响应机理相似，其受到紫外光照射后会进行光环化反应，使化合物的最大吸收波长红移至可见光区。与二芳基乙烯类相比，三芳基乙烯类材料在保持优异的光致变色性能的同时，又有易于合成和修饰的特点，而结构简单且性能优异的有机配体对发展光响应MOFs材料尤为重要。" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "常见可逆光响应分子结构式及光响应机理。 （a）偶氮苯；（b）二芳基乙烯；（c）螺吡喃；（d）螺噁嗪；（e）三芳基乙烯。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.1" } ], "title": [ { "name": "text", "data": "Structural formula and photoresponse mechanism of common photoresponsive molecules. （a）Azobenzene. （b）Diarylethene. （c）Spiropyran. （d）Spirooxazine. （e）Triarylethylene." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031681&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031689&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031686&type=", "width": "65.20776367", "height": "99.97930908", "fontsize": "" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3　光响应MOFs在交叉领域的应用" } ], "level": "1", "id": "s3" } }, { "name": "p", "data": [ { "name": "text", "data": "随着人们对智能材料的不断追求，光响应MOFs材料相关研究迅速发展。将光响应基团引入MOFs结构中，使其发光、颜色、孔径等物理性质具有光响应性。该类材料作为新型智能材料的重要方向之一，近年来的丰富成果为气体分离、可控药物释放、高性能传感、新型存储等前沿领域的发展奠定了材料基础。下面我们将按应用领域介绍近年来光响应MOFs材料具有代表性的成果。" } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.1　气体分离" } ], "level": "2", "id": "s3a" } }, { "name": "p", "data": [ { "name": "text", "data": "MOFs骨架具有大量功能位点，通过对其进行功能化修饰，可使材料在不同气体分子间产生具有差异性的主客体相互作用和/或筛分效应，实现气体分离目的。而光响应MOFs材料可以通过简单地光照，改变MOFs对混合气体的识别、分离能力。这是由于在紫外光照射前后，光响应基团的分子结构会发生变化，伴随着MOFs孔隙结构的改变，进而影响其对气体的分离能力。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2017年，郭国聪教授团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "40", "type": "bibr", "rid": "R40", "data": [ { "name": "text", "data": "40" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "通过以含吡啶的DTE为配体构建MOF，首次实现了通过外部刺激调节MOF对C" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "/C" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "的吸附选择性。由于DTE-MOF对C" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的独特识别，该MOFs对C" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "与C" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "的吸附选择比例在195 K、100 kPa的条件下达到了47.1。而在相同条件下，经紫外光照射后，该比率则下降至3.0，该DTE-MOF可以高效分离C" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "/C" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "中的C" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，其分离过程如" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "（a）所示。之后，在2019年，通过将四乙烯五胺（Tetraethylenepentamine，TEPA）引入偶氮苯功能化的MOFs中，孙林兵教授课题组" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "41", "type": "bibr", "rid": "R41", "data": [ { "name": "text", "data": "41" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "首次报道了一种吸附CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的光响应吸附剂，并命名为T（7.5）/U-azo。TEPA作为CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的一种特殊活性位点，可与CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "产生强相互作用，因此常被用作CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "捕集剂。偶氮苯衍生物配体通过紫外和可见光循环照射，经历可逆的顺反构象，进而影响TEPA与CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "之间的相互作用，这一过程如" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "（b）所示。当偶氮苯基团为顺式异构体时，仲胺周围的表面静电势显著增加，CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "活性位点被有效屏蔽，而反式异构体能有效吸附CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，并且由" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "（c）的紫外-可见吸收光谱可知，该过程伴随着化合物颜色的改变。将T（7.5）/U-azo用于混合气体分离实验，如" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "（d）所示，测得其对CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "/CH" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "和CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "/N" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的选择性分别达到456和334（273 K和10 kPa）。该工作可能通过利用靶向活性位点和刺激基序之间的相互作用，为光响应MOFs的实际应用铺平道路。" } ] }, { "name": "fig", "data": { "id": "F2", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图2" } ], "title": [ { "name": "text", "data": "（a）DTE-MOF作为C" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "/C" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "释放开关示意图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "40", "type": "bibr", "rid": "R40", "data": [ { "name": "text", "data": "40" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "；（b）通过活性位点和光响应分子之间的相互作用，在光响应MOFs上可选择性捕获CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "；（c）T（7.5）/U-azo在顺、反异构化过程中的紫外/可见光谱变化；（d）T（7.5）/U-azo上CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "/CH" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "和CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "/N" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的IAST选择性" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "41", "type": "bibr", "rid": "R41", "data": [ { "name": "text", "data": "41" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "；（e）光照后化合物对CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的吸收能力提高；（f）｛［Cd（bpee）（hfbba）］" }, { "name": "bold", "data": [ { "name": "text", "data": "·" } ] }, { "name": "text", "data": "EtOH｝" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "发生环加成过程前后骨架的结构" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "42", "type": "bibr", "rid": "R42", "data": [ { "name": "text", "data": "42" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.2" } ], "title": [ { "name": "text", "data": "（a）The DTE-MOF serves as the schematic diagram of C" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "/C" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": " release switch" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "40", "type": "bibr", "rid": "R40", "data": [ { "name": "text", "data": "40" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （b）Tailorable CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": " capture on the photoresponsive MOFs through an interaction between active sites and photoresponsive molecules. （c）Changes in UV/Vis spectra of T（7.5）/U-azo upon " }, { "name": "italic", "data": [ { "name": "text", "data": "trans" } ] }, { "name": "text", "data": "- and " }, { "name": "italic", "data": [ { "name": "text", "data": "cis" } ] }, { "name": "text", "data": "-isomerization. （d）IAST selectivity of CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "/CH" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": " and CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "/N" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": " on T（7.5）/U-azo" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "41", "type": "bibr", "rid": "R41", "data": [ { "name": "text", "data": "41" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （e）After illumination， the CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": " absorption capacity of compounds is improved. （f）The skeleton structure of MOFs before and after cycloaddition of ｛［Cd（bpee）（hfbba）］" }, { "name": "bold", "data": [ { "name": "text", "data": "·" } ] }, { "name": "text", "data": "EtOH｝" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "42", "type": "bibr", "rid": "R42", "data": [ { "name": "text", "data": "42" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031695&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031705&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031700&type=", "width": "163.00000000", "height": "78.36547852", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "2021年，Hazra教授团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "42", "type": "bibr", "rid": "R42", "data": [ { "name": "text", "data": "42" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "报道了一种MOF‐{[Cd（bpee）（hfbba）]" }, { "name": "bold", "data": [ { "name": "text", "data": "·" } ] }, { "name": "text", "data": "EtOH}" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "，其可以有效分离水蒸气中的二氧化碳（Carbon dioxide，CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "），该MOFs骨架被疏水性三氟甲基（Trifluoromethyl group， —CF" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "）修饰，降低了金属点位对水分子的吸附作用，在CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "与氟原子的相互作用下，材料捕获水蒸气中的CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的能力有所提高。此外，如" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "（e）所示，在紫外光照射后，材料对CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的捕获能力进一步提升，这是因为平行排列的1,2双（4-吡啶基）乙烯在紫外光照射下发生 [2+2] 环加成反应，使MOFs的孔径和表面积发生改变，在CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "和—CF" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "之间产生了额外的弱电子给体-受体相互作用，进而捕获了更多的CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "（f）展示了材料发生环加成反应前后骨架的结构。该研究为从烟气中分离CO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "提供了一种新的可能性。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "光响应MOFs不仅具有高孔隙率、可调孔隙结构及易于功能化等结构特点，且会对光刺激做出响应：在光照条件下MOFs的分离效果可发生显著变化。由于光刺激具有操作条件温和、调控反应精准等特点，光响应MOFs在气体分离领域具有十分广阔的研究前景。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2　物质运输" } ], "level": "2", "id": "s3b" } }, { "name": "p", "data": [ { "name": "text", "data": "物质运输主要涉及物质的负载以及物质的特异性释放，这在靶向治疗等方面具有重要意义。迄今为止，物质运输领域已经开发了许多载体材料，例如用交联组蛋白" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "43", "type": "bibr", "rid": "R43", "data": [ { "name": "text", "data": "43" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "作载体，或用二氧化硅聚合物" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "44", "type": "bibr", "rid": "R44", "data": [ { "name": "text", "data": "44" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "作载体。近年来，研究人员提出用光响应MOFs作为物质运输载体，因为光响应MOFs形成的孔尺寸会受光波长以及照射时间影响，表现为材料的孔径可以通过光照前后结构的变化而改变。这使得光响应MOFs拥有物质负载、运输及释放的能力。2016年，汪成教授课题组" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "45", "type": "bibr", "rid": "R45", "data": [ { "name": "text", "data": "45" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "设计并合成了一种含光敏偶氮苯基团的水稳定锆MOFs（Zr-MOFs），命名为UiO-68-azo，其可以作为一种物质运输的MOFs平台且具有良好的水稳定性。研究人员选择尺寸匹配的罗丹明B（Rhodamine B，RhB）负载于UiO-68-azo，并将其浸泡在β-环糊精（β-Cyclodextrin，β-CD）溶液中，一段时间后，β-CD与UiO-68-azo中的偶氮苯结合，阻塞MOFs的孔隙，实现了客体的储存，" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "（a）展示了该MOFs负载储存RhB的过程。" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "（b）则为UiO-68-azo释放物质的过程，在紫外光下，偶氮苯由反式异构体转变为顺式异构体，破坏了β-CD与偶氮苯之间的相互作用力，进而释放RhB。此外，其他因素也会影响UiO-68-azo释放客体行为，如" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "（c）所示，在20 min时加入金刚烷胺，RhB的释放率显著提升；在120 min时再通过紫外光照射，进一步促进了RhB的释放。总而言之，金刚烷胺可以发出释放物质的指令，紫外光和可见光的交替照射则可以通过改变偶氮苯的顺反式结构来存储和释放物质。实验结果还表明，该光响应MOFs结构在多次循环过程之后仍保持稳定。该工作表明了β-CD封端的Zr-MOFs在药物递送中的可行性及重要性。" } ] }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3" } ], "title": [ { "name": "text", "data": "（a）UiO-68-azo的合成过程，以及负载物质RhB和用β-CD封装得到的结构，其中偶氮苯基团作为茎且其表面被 β-CD覆盖，反式偶氮苯呈绿色；（b）逐步加入金刚烷胺和经过紫外光照射后的物质释放示意图，顺式偶氮苯呈青色；（c）通过添加金刚烷胺然后紫外光照射，RhB负载、β-CD封端的UiO-68-azo的释放曲线" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "45", "type": "bibr", "rid": "R45", "data": [ { "name": "text", "data": "45" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.3" } ], "title": [ { "name": "text", "data": "（a）Schematic illustration of the synthesis of UiO-68-azo and further construction of RhB-loaded， β-CD-capped UiO-68-azo， azobenzene units as stalks encircled by β-CD on the surface. The " }, { "name": "italic", "data": [ { "name": "text", "data": "trans" } ] }, { "name": "text", "data": "-azobenzene is colored in green. （b）Step-by-step on-command release. Schematic illustration of the step-by-step release. The " }, { "name": "italic", "data": [ { "name": "text", "data": "cis" } ] }, { "name": "text", "data": "-azobenzene is colored in cyan. （c）Release profiles of RhB-loaded， β-CD-capped UiO-68-azo by addition of amantadine and then UV irradiation" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "45", "type": "bibr", "rid": "R45", "data": [ { "name": "text", "data": "45" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031709&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031718&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031714&type=", "width": "154.11010742", "height": "65.48104095", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "然而，大多数光响应MOFs的光开关对外界温度非常敏感，导致MOFs的封装效果难以达到预期效果。因此，迫切需要开发具有高光响应效率和热稳定性的光响应MOFs。为解决上述问题，王焕庭教授团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "46", "type": "bibr", "rid": "R46", "data": [ { "name": "text", "data": "46" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "在2020年提出将螺吡喃聚合物引入MOFs结构中，他们设计并合成了苯乙烯基芘MOFs化合物（SP-MIL），通过表面改性，SP-MIL结构在持续升温至50 ℃时保持稳定。之后，研究人员检测了SP-MIL的孔容量，并证明SP-MIL可以通过可逆[2+2]光环加成反应储存和释放客体。此外，他们还通过负载催化水凝胶形成的胺，利用光响应基团的特殊性能，制备出多种形状的水凝胶，这些水凝胶均具有良好的稳定性，表明该系统在物质运输领域具有实际应用性。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "除此之外，光响应MOFs在药物运输方面也有所突破。2020年，刘笔锋教授及合作者" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "47", "type": "bibr", "rid": "R47", "data": [ { "name": "text", "data": "47" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "设计了一种简单的一步生物矿化策略，将ZIF-8前驱体、光敏剂（Ce6）、化疗药物（DOX）及具有肿瘤靶向性的大肠杆菌（E.coli, MG1655）混合搅拌，直接制成了负载两种药物的生物矿化大肠杆菌（E. coli@ZIF-8/C" }, { "name": "text", "data": "&" }, { "name": "text", "data": "D）。E.coli表面的ZIF-8纳米层对药物分子的负载效率接近100%，并且该材料保持了很高的活性，适于长期保存。与初始的E.coli相比，E.coli@ZIF-8/C" }, { "name": "text", "data": "&" }, { "name": "text", "data": "D仍然具有很高的肿瘤富集效率，经近红外激光照射后，负载药物的生物矿化大肠杆菌成功实现了联合治疗，有效地抑制了小鼠肿瘤的生长。该研究为肿瘤治疗提供了一种新的策略。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "光响应MOFs在物质运输尤其是药物运输领域具有巨大的应用前景，但是其目前也存在一定局限性，例如如何修饰MOFs结构以使其具有高效靶向性、如何用可见光激发等还有待更深入研究。此外，关于MOFs自身毒性的研究都还比较匮乏。这些都限制着光响应MOFs材料的实际应用。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.3　防伪与传感" } ], "level": "2", "id": "s3c" } }, { "name": "p", "data": [ { "name": "text", "data": "在光刺激下，一些MOFs材料表现出光致变色及光致发光现象。材料产生光致变色现象是因为其结构中存在光致变色基团，光致变色基团在紫外光照射后结构发生改变，在可见光区域出现吸收带，使MOFs材料颜色发生改变，并且这一过程可重复多次。而光响应MOFs的光致发光机理是由于基态的光响应MOFs吸收了特定波长的光能后跃迁到激发态，电子在激发态回到基态的过程中伴随着辐射跃迁和非辐射跃迁，其中辐射跃迁有荧光和磷光两种形式" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "48", "type": "bibr", "rid": "R48", "data": [ { "name": "text", "data": "48" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。随着人们对信息安全的重视，光致变色及发光MOFs在多重防伪、信息加密和存储以及传感领域具有研究潜力。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "在2019年的一项研究中，李焕荣和陈邦林教授合作的团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "49", "type": "bibr", "rid": "R49", "data": [ { "name": "text", "data": "49" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "通过将光致变色二噻吩乙烯发色团封装到含有稀土离子Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "的多孔MOFs中，实现了具有动态发光的可逆光开关，" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "（a）展示了封装在ZJU-88中的光致变色DAE生色团的结构式及在交替紫外光和可见光照射下ZJU-88⊃OF-DAE的光异构化过程。值得一提的是，该研究创新性地将光致变色单元封装到多孔MOFs中，而不是使其作为连接分子的一部分直接集成到MOFs结构的主链中，这样的改动有效地提高了光开关的光异构化速率。在紫外光照射下，闭环DTE在450~700 nm波长范围内产生新的吸收带，该吸收带与峰值为623 nm的Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "发射光谱高度重叠，通过福斯特共振能量转移（Förster resonance energy transfer，FRET）过程，Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "的发光逐渐猝灭。最后，该课题组设计了一种新的信息编码和防伪策略，将该主客体复合物用作隐形安全墨水。如" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "（b）所示，使用该墨水在蓝色滤纸上绘制二维码，可以实现编码信息在阳光下不可见、在紫外光下可见的效果。此外，在365 nm紫外光照射下，从OF-DAE状态到CF-DAE状态的转换过程非常缓慢，为读取编码信息提供了便利。" } ] }, { "name": "fig", "data": { "id": "F4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图4" } ], "title": [ { "name": "text", "data": "（a）并入ZJU-88的光致变色DAE生色团示意图，以及在紫外和可见光交替照射下，ZJU-88⊃OF-DAE的光开关异构化行为；（b）光触发主客体复合物的可逆信息防伪行为" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "49", "type": "bibr", "rid": "R49", "data": [ { "name": "text", "data": "49" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.4" } ], "title": [ { "name": "text", "data": "（a）Schematic of photochromic DAE chromophores incorporated into ZJU-88， and photoswitchable isomerization behavior of ZJU-88⊃OF-DAE under alternating UV and visible light irradiation. （b）Light-triggered reversible information anti- counterfeiting behaviors of the host-guest complex" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "49", "type": "bibr", "rid": "R49", "data": [ { "name": "text", "data": "49" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031726&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031736&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031731&type=", "width": "145.79598999", "height": "49.10665894", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "在2021年的一项研究中，白凤英教授课题组" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "50", "type": "bibr", "rid": "R50", "data": [ { "name": "text", "data": "50" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "以甘氨酸修饰的萘二酰亚胺（Naphthalene diimide，NDI）基团为配体，分别与碱土金属Ca" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "、Mg" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "和Sr" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "连接，制备并命名了如" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "（a）所示的化合物Mg-CMNDI、Ca-CMNDI和Sr-CMNDI。这三种MOFs材料均具有光致变色特性，其光致变色机理与自由基NDI" }, { "name": "sup", "data": [ { "name": "text", "data": "*" } ] }, { "name": "text", "data": "的产生与消失有关，光诱导产生的自由基在n-π 相互作用和 π-π 相互作用的协同下进行电子转移。在此基础上，研究人员还利用Mg-CMNDI的光致变色特性，如" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "（b）所示，制成可擦除加密墨水，用于写入、读取和擦除纸张上的信息。此外，三种化合物还可作为检测药物巴柳氮和秋水仙碱浓度的荧光传感器，因为药物分子能有效地猝灭三种化合物的荧光，如" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "（c）所示，二者的检测限分别为0.16 μmol/L和0.70 μmol/L。该研究提供了一种变色发光双响应MOFs材料的设计策略。" } ] }, { "name": "fig", "data": { "id": "F5", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图5" } ], "title": [ { "name": "text", "data": "（a）Mg-CMNDI、Ca-CMNDI和Sr-CMNDI的分子结构和拓扑网络；（b）Mg-CMNDI在紫外照射下随时间的颜色变化（顶部），以及相应的紫外-可见吸收光谱；（c）Sr-CMNDI在含有不同浓度秋水仙碱的DMF中的荧光光谱" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "50", "type": "bibr", "rid": "R50", "data": [ { "name": "text", "data": "50" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.5" } ], "title": [ { "name": "text", "data": "（a）Molecular structure and topological network of Mg-CMNDI， Ca-CMNDI and Sr-CMNDI. （b）Color change of Mg-CMNDI under UV irradiation over time（top）， and corresponding UV-Vis absorption spectra. （c）Fluorescence spectra of Sr-CMNDI in DMF containing various concentrations of colchicine" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "50", "type": "bibr", "rid": "R50", "data": [ { "name": "text", "data": "50" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031741&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031751&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031746&type=", "width": "137.29571533", "height": "115.21849060", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "上述光响应MOFs材料在光刺激下表现出光致变色和荧光猝灭现象，还有一些材料在光刺激下表现出多种光响应特性。2018年，孙燕琼教授研究团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "51", "type": "bibr", "rid": "R51", "data": [ { "name": "text", "data": "51" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "报道了一种由Cd" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "和羧酸官能化紫精衍生物配体组成的Cd-紫精化合物1，{[Cd" }, { "name": "sub", "data": [ { "name": "text", "data": "1.5" } ] }, { "name": "text", "data": "（Cebpy）（Hbtc）Cl]" }, { "name": "bold", "data": [ { "name": "text", "data": "·" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O}" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "，" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "（a）展示了1中两个配体1-羧乙基-4,4'-联吡啶（1-carboxyethyl-4,4'-bipyridine，Cebpy）和脱去两个氢的1,3,5-苯三甲酸（1,3,5-benzenetricarboxylic acid，H" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "Hbtc）离子的配位模式，该化合物兼具光致变色、光调制荧光及发光传感特性。如" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "（b）所示，在氙灯照射后，化合物的颜色从浅棕色变为深蓝灰色，其紫外-可见漫反射光谱在波长为409 nm和621 nm处有两个特征带。通过电子自旋共振（Electron spin resonance，ESR）光谱可知，光照后化合物在" }, { "name": "italic", "data": [ { "name": "text", "data": "g" } ] }, { "name": "text", "data": "值为2.004处显示出较强的单线自由基信号，与文献报道的Cebpy" }, { "name": "bold", "data": [ { "name": "text", "data": "·" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "-" } ] }, { "name": "text", "data": "自由基信号相似，这表明化合物的光致变色机理与自由基的产生与消失有关。化合物1也表现出光调制荧光特性，在氙灯照射1 min后，604 nm处的最大发射峰从2.0×10" }, { "name": "sup", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "迅速下降至1.1×10" }, { "name": "sup", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "。随着辐照时间的增加，化合物1在604 nm处的发光峰变弱，晶体颜色变深。此外，" }, { "name": "xref", "data": { "text": "图 6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图 6" } ] } }, { "name": "text", "data": "（c）表明该材料具有离子检测能力，化合物1对有色过渡金属离子Co" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "、Ni" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "、Cu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "和Fe" }, { "name": "sup", "data": [ { "name": "text", "data": "3+" } ] }, { "name": "text", "data": "具有良好的选择性，这使得它在发光传感方面显示出良好的发展潜力。" } ] }, { "name": "fig", "data": { "id": "F6", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图6" } ], "title": [ { "name": "text", "data": "（a）化合物1的结构式；（b）化合物1在紫外光照前后的照片、紫外-可见漫反射光谱和ESR光谱；（c）将1引入各种0.1 mol/L阳离子水溶液中的光致发光光谱" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "51", "type": "bibr", "rid": "R51", "data": [ { "name": "text", "data": "51" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "；（d）MOF-" }, { "name": "italic", "data": [ { "name": "text", "data": "M" } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "M" } ] }, { "name": "text", "data": "=Zn，Cd，Co，Mn）的分子结构和拓扑网络；（e）使用MOF-Zn的持续发光和光致变色的多重信息加密模型；（f）外延生长过程和基于MOFs的异质结图" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "52", "type": "bibr", "rid": "R52", "data": [ { "name": "text", "data": "52" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.6" } ], "title": [ { "name": "text", "data": "（a）Structural formula of compound 1. （b）The photographic images， UV-visible diffuse reflectance spectra and ESR spectra of compound 1 before and after UV irradiation. （c）Photoluminescence spectra of 1 introduced into various 0.1 mol/L aqueous cation solutions" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "51", "type": "bibr", "rid": "R51", "data": [ { "name": "text", "data": "51" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": ". （d）Molecular configuration and topology of MOF-" }, { "name": "italic", "data": [ { "name": "text", "data": "M" } ] }, { "name": "text", "data": "（" }, { "name": "italic", "data": [ { "name": "text", "data": "M" } ] }, { "name": "text", "data": " = Zn， Cd， Co， Mn）. （e）The multiple information encryption model using persistent luminescence and photochromism of MOF-Zn. （f）Diagram of epitaxial growth process and MOFs based heterojunctions" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "52", "type": "bibr", "rid": "R52", "data": [ { "name": "text", "data": "52" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031757&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031765&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031762&type=", "width": "160.45254517", "height": "73.21063232", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "2021年，闫东鹏教授研究团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "52", "type": "bibr", "rid": "R52", "data": [ { "name": "text", "data": "52" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "通过选择4,4’-联吡啶作为配体合成了一系列光致变色/长寿命室温磷光MOFs——MOF-Zn/Cd/Co/Mn，" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "（d）展示了这些化合物的分子结构和拓扑网络。在波长为310 nm的紫外光激发下，MOF-Zn样品呈白色且在波长360 nm处具有荧光发射峰、在波长490 nm处有磷光发射峰；而用氙灯照射时，由于吡啶自由基的形成，该系列化合物在波长550~700 nm范围内出现新的吸收带，样品由白色变为蓝色，又由于配体之间的电荷转移，两个发射峰均减小，发光减弱，实现了可逆光致变色调控长寿命室温磷光的特性。基于这种动态切换，研究人员设计了一个多重加密模型，如" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "（e）所示。此外，通过外延生长过程，利用同质结构MOFs制备了多块核壳异质结——MOF-Co@Zn和MOF-Mn@Zn，如" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "（f）所示，其中壳显示出明亮的黄色余辉发射，在进一步辐照后逐渐消失，但核没有显示出该特性。这些基于MOFs的光学异质结具有潜在的空间/时间分辨信息加密能力和防伪应用前景，更进一步提高了信息加密的安全程度。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "总之，具有光致变色与光致发光特性的MOFs可以应用在多重防伪和信息安全、信息存储等领域。但是，如何提高材料的稳定性、抗疲劳性以及降低生产成本，还有待进一步研究。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.4　新能源" } ], "level": "2", "id": "s3d" } }, { "name": "p", "data": [ { "name": "text", "data": "目前环境污染问题和能源枯竭问题日益显著，开发利用新能源已经成为相关领域内大多数研究者的共识。新能源是除去以化石燃料为主体的传统能源的新式清洁能源，主要包括太阳能、风能、生物质能、氢能、核能等。随着对MOFs的深入研究，研究者开始探索MOFs材料在太阳能电池" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "53", "type": "bibr", "rid": "R53", "data": [ { "name": "text", "data": "53" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、氢能存储等新能源领域的应用。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "由于MOFs具有高比表面积、空位配位点以及强表面偶极矩的特点，因此具备优异的储氢性能。增强MOFs储氢性能的关键是增强其结构稳定性和提高孔面积。目前，许多储氢MOFs的研究是将储氢材料（MgH" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "54", "type": "bibr", "rid": "R54", "data": [ { "name": "text", "data": "54" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "等）或是H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "负载到MOFs的孔隙中，释放H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "时，MOFs材料需要受到高温加热或者其他接触性刺激，极大损耗MOFs材料的耐受性。而应用于储氢领域的光响应MOFs通过将光作为刺激条件，具有易操控、无接触的特点，且大多数光响应MOFs均具有优良的耐受性。近期，Butova课题组" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "55", "type": "bibr", "rid": "R55", "data": [ { "name": "text", "data": "55" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "报道了一种光驱动储氢的Zr-MOF，该材料通过用DAE修饰UiO-66-NH" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "从而得到一种高结晶性多孔化合物。经过测试表征，在紫外光照射下，“开放式”DAE分子转变为“封闭式”DAE分子，进而形成两种结构不同的化合物，如" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": "（a）所示。这种结构的改变会使MOFs的孔隙发生变化，“开放式”DAE分子会增大氢气的容量，而“封闭式”DAE分子储氢能力降低。如" }, { "name": "xref", "data": { "text": "图 7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图 7" } ] } }, { "name": "text", "data": "（b）所示，在波长520 nm的可见光照射下，样品在77 K时吸附的H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "为0.58%。这个值略高于合成样品的H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "容量。" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": "（c）展示了在可见光、紫外光连续多次照射下，化合物的储氢量柱形图，分析可知，可见光照射下化合物储氢量远高于紫外光照射下化合物的储氢量，并且该过程可重复多次。这项研究为开发吸附-释放H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的智能储氢设备提供了新思路。" } ] }, { "name": "fig", "data": { "id": "F7", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图7" } ], "title": [ { "name": "text", "data": "（a）紫外光（" }, { "name": "italic", "data": [ { "name": "text", "data": "hν" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "）和可见光（" }, { "name": "italic", "data": [ { "name": "text", "data": "hν" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）作用下，DAE-UiO-66孔内的DAE转换示意图；（b）DAE-UiO-66在波长为520 nm的可见光（绿色图）和波长为450 nm的紫外光（紫图）照射下氢吸附等温线（77 K）；（c）波长520 nm可见光（绿色柱）和450 nm紫外光（紫柱）连续照射时H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "容量的变化" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "55", "type": "bibr", "rid": "R55", "data": [ { "name": "text", "data": "55" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.7" } ], "title": [ { "name": "text", "data": "（a）Scheme of DAE transformations inside DAE-UiO-66 pores under UV-light（" }, { "name": "italic", "data": [ { "name": "text", "data": "hν" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "） and visible light（" }, { "name": "italic", "data": [ { "name": "text", "data": "hν" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）. （b）Isotherms of hydrogen adsorption（77 K） for DAE-UiO-66 sample irradiated with visible light with a wavelength of 520 nm（green plot） and UV-light with a wavelength of 450 nm（violet plot）. （c）Diagram of changing in H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": " capacity during sequential irradiation with visible light with a wavelength of 520 nm（green columns） and UV-light with a wavelength of 450 nm（violet columns）" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "55", "type": "bibr", "rid": "R55", "data": [ { "name": "text", "data": "55" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031769&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031778&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031773&type=", "width": "144.40179443", "height": "112.51977539", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "除在储氢领域的应用，光响应导电MOFs材料的发展打破了以往MOFs的桎梏。2019年，Heinke教授课题组" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "56", "type": "bibr", "rid": "R56", "data": [ { "name": "text", "data": "56" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "通过在衬底上逐层制备的方法，报道了一种含螺吡喃基团的质子传导纳米多孔材料SURMOF。经测试表征，SURMOF表现出良好的稳定性以及在光照下具有可逆光开关能力。并且，当不同的普通质子传导分子被负载到SURMOF中时，它们表现出优异的质子传导性能。在这些质子传导客体分子中，水质子传导的通断比最高。在紫外光照射下，水质子传导的SURMOF的电阻由（3.45 ± 0.5） MΩ变为（279.5 ± 19） MΩ，异构化前后的电导率降低了近82倍。研究人员推测，如果开关的偶极矩增加，该比率将进一步提升。这种具有光调离子传导的材料可能在新能源电池方向有所应用。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "MOFs的光电理论作为能源技术开发的基础，近期也有了新的进展。2021年，Shustova课题组" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "57", "type": "bibr", "rid": "R57", "data": [ { "name": "text", "data": "57" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "首次建立了金属有机光化胺框架（An-MOFs）的光物理-电子相关理论。他们在An-MOFs中应用了动态调制的电子特性。研究人员设计了异金属An-MOFs、" }, { "name": "italic", "data": [ { "name": "text", "data": "M" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "IV" } ] }, { "name": "text", "data": "-MOFs（" }, { "name": "italic", "data": [ { "name": "text", "data": "M" } ] }, { "name": "text", "data": "=U和Th），并引入碘和7,7,8,8-四氰基二甲烷作为两种类型的客体来调节MOFs电子结构，该过程如" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "（a）所示。此外，研究人员首次利用光致变色MOFs构建了一个场效应晶体管，为了反映电流的变化，他们使用了一个带有两个发光二极管（Light emitting diode，LED）的故障安全指示器电路。" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "（b）~（c）展示了场效应晶体管示意图以及LED故障电路示意图。通过测试，他们将电路暴露在紫外光和可见光中，并测量绿色LED的光强度。试验表明，光和栅极电压会影响电路中的电流，说明An-MOFs具有良好的光电特性。这项研究可能成为探索利用核废料和核能的新方法。" } ] }, { "name": "fig", "data": { "id": "F8", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图8" } ], "title": [ { "name": "text", "data": "（a）MOFs电子性质的可调性示意图，其作为刺激响应性封端连接体整合（蓝色和红色螺旋）、f-块元素（蓝绿色和/或橙色球体）和客体分子（紫色椭圆形）的函数；（b）基于MOFs的场效应晶体管示意图，插图显示了电极之间的滴铸晶体的光学图像；（c）设计用于电子性能控制可视化的双LED故障保护电路" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "57", "type": "bibr", "rid": "R57", "data": [ { "name": "text", "data": "57" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.8" } ], "title": [ { "name": "text", "data": "（a）A schematic representation of the tunability of MOFs electronic properties as a function of stimuli-responsive capping linker integration（blue and red spirals）， f-block elements（teal and/or orange spheres）， and guest molecules（purple ovals）. （b）A schematic representation of the MOFs-based field-effect transistor. The inset shows an optical image of drop-cast crystals between the electrodes. （c）Two-LED fail-safe circuit designed for visualization of electronic property control" }, { "name": "sup", "data": [ { "name": "text", "data": "［" }, { "name": "xref", "data": { "text": "57", "type": "bibr", "rid": "R57", "data": [ { "name": "text", "data": "57" } ] } }, { "name": "text", "data": "］" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031783&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031793&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=41031788&type=", "width": "144.52600098", "height": "49.03709412", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "目前新能源领域的研究热点之一是开发具有体积小、重量轻、效率高、寿命长等特性的新型电池。理论上，导电MOFs材料结合了有机材料绿色环保、可循环、易于改性和无机材料稳定性好、导电率高的优势" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "58", "type": "bibr", "rid": "R58", "data": [ { "name": "text", "data": "58" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，其在新型电池领域具有广阔的发展前景；然而受有机材料生长无法长程有序、电荷迁移率等限制，真正产业化的MOFs材料还有待进一步研究。" } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4　总结和展望" } ], "level": "1", "id": "s4" } }, { "name": "p", "data": [ { "name": "text", "data": "随着人们对新材料智能化要求逐渐提高，光响应MOFs的需求也愈发迫切。本文总结了近年来光响应MOFs材料的研究进展及应用，为该领域后续的研究提供一定的指导帮助。本综述主要包括光响应MOFs材料的分类，包括偶氮苯类、二芳基乙烯类、螺吡喃类等；详述了光响应MOFs材料在气体分离、物质运输、防伪、传感和光电器件等不同领域中的最新应用进展。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "该领域近年来虽然已经取得了长足进展，但光响应MOFs仍有许多问题亟待进一步深入研究。 （1）光响应配体是光响应MOFs的重要构成部分，目前已经报道的多类光响应基团存在着合成路线复杂、对可见光不敏感、响应效率低等缺陷。这极大地限制了该类材料在药物递送（需可见光及红外光激发）、光电器件等领域的发展。因此，开发对可见光或长波敏感的光控材料十分必要。 （2）大多数光响应基团均存在于金属有机框架的主链，这在一定程度上限制了材料的光响应速率和光异构化程度，而将光响应发色团封装在MOFs的孔隙中是一种行之有效的方法，未来可以着重这方面的研究。 （3）目前一些光响应MOFs存在材料抗疲劳性能差、环境稳定性差、光照前后性能差异小、生产成本高等劣势，这些均阻碍了其在实际中的应用。光响应MOFs作为智能材料特别具有吸引力，如果将材料的光响应行为与另一种刺激（如热响应、pH响应和电响应）相结合，预计可以发掘材料更多性能以扩大应用范围。对于一些用作信息存储材料的光控MOFs，可以加大其信息存储量，提高其存储精度。此外，MOFs还可以与纳米颗粒等非均质材料结合形成复合材料，实现协同功能。随着研究人员的不断探索研究，相信光响应MOFs材料的各方面性能将进一步提升、光响应机理不断深入及完善、应用领域不断拓展。届时，MOFs将走进我们的生产与生活中，为我们创造无限的未来。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "本文专家审稿意见及作者回复内容的下载地址：" }, { "name": "extlink", "data": { "text": [ { "name": "text", "data": "http://cjl.lightpublishing.cn/thesisDetails#10.37188/" } ], "href": "http://cjl.lightpublishing.cn/thesisDetails#10.37188/" } } ] }, { "name": "p", "data": [ { "name": "text", "data": "CJL.20220289." } ] } ] } ], "footnote": [], "reflist": { "title": [ { "name": "text", "data": "参考文献" } ], "data": [ { "id": "R1", "label": "1", "citation": [ { "lang": "en", "text": [ { "name": "text", "data": "ZHOU H C" }, { "name": "text", "data": "， " }, { "name": "text", "data": "LONG J R" }, { "name": "text", "data": "， " }, { "name": "text", "data": "YAGHI O M" }, { "name": "text", "data": ". 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