【荧光金属有机框架材料发展研究的文献综述6700字】

荧光金属有机框架材料发展研究的文献综述金属有机骨架（MOFs），也称为多孔配位聚合物（PCPs），是一类新兴的晶体多孔材料，由金属中心和有机配体通过配位键结合而来ADDINEN.CITE<EndNote><Cite><Author>Aguilera-Sigalat</Author><Year>2016</Year><RecNum>23</RecNum><DisplayText><styleface="superscript">[54]</style></DisplayText><record><rec-number>23</rec-number><foreign-keys><keyapp="EN"db-id="v9tf25xx5fedfletrem5ttx3pztpvzatxp2a"timestamp="1619487831">23</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Aguilera-Sigalat,Jordi</author><author>Bradshaw,Darren</author></authors></contributors><titles><title>Synthesisandapplicationsofmetal-organicframework–quantumdot(QD@MOF)composites</title><secondary-title>CoordinationChemistryReviews</secondary-title></titles><periodical><full-title>CoordinationChemistryReviews</full-title></periodical><pages>267-291</pages><volume>307</volume><section>267</section><dates><year>2016</year></dates><isbn>00108545</isbn><urls></urls><electronic-resource-num>10.1016/j.ccr.2015.08.004</electronic-resource-num></record></Cite></EndNote>[54]，以及广泛应用于气体储存和分离ADDINEN.CITE<EndNote><Cite><Author>Allendorf</Author><Year>2009</Year><RecNum>4</RecNum><DisplayText><styleface="superscript">[55]</style></DisplayText><record><rec-number>4</rec-number><foreign-keys><keyapp="EN"db-id="v9tf25xx5fedfletrem5ttx3pztpvzatxp2a"timestamp="1619487604">4</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Allendorf,M.D.</author><author>Bauer,C.A.</author><author>Bhakta,R.K.</author><author>Houk,R.J.</author></authors></contributors><auth-address>SandiaNationalLaboratories,Livermore,CA94550-0969,USA.</auth-address><titles><title>Luminescentmetal-organicframeworks</title><secondary-title>ChemSocRev</secondary-title></titles><periodical><full-title>ChemSocRev</full-title></periodical><pages>1330-52</pages><volume>38</volume><number>5</number><edition>2009/04/23</edition><dates><year>2009</year><pub-dates><date>May</date></pub-dates></dates><isbn>0306-0012(Print) 0306-0012(Linking)</isbn><accession-num>19384441</accession-num><urls><related-urls><url>/pubmed/19384441</url></related-urls></urls><electronic-resource-num>10.1039/b802352m</electronic-resource-num></record></Cite></EndNote>[55]、多相催化ADDINEN.CITE<EndNote><Cite><Author>Bosch</Author><Year>2017</Year><RecNum>11</RecNum><DisplayText><styleface="superscript">[56]</style></DisplayText><record><rec-number>11</rec-number><foreign-keys><keyapp="EN"db-id="v9tf25xx5fedfletrem5ttx3pztpvzatxp2a"timestamp="1619487706">11</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Bosch,M.</author><author>Yuan,S.</author><author>Rutledge,W.</author><author>Zhou,H.C.</author></authors></contributors><auth-address>DepartmentofChemistry,TexasA&MUniversity,CollegeStation,Texas77843,UnitedStates.</auth-address><titles><title>StepwiseSynthesisofMetal-OrganicFrameworks</title><secondary-title>AccChemRes</secondary-title></titles><periodical><full-title>AccChemRes</full-title></periodical><pages>857-865</pages><volume>50</volume><number>4</number><edition>2017/03/30</edition><dates><year>2017</year><pub-dates><date>Apr18</date></pub-dates></dates><isbn>1520-4898(Electronic) 0001-4842(Linking)</isbn><accession-num>28350434</accession-num><urls><related-urls><url>/pubmed/28350434</url></related-urls></urls><electronic-resource-num>10.1021/acs.accounts.6b00457</electronic-resource-num></record></Cite></EndNote>[56]、和化学传感ADDINEN.CITE<EndNote><Cite><Author>Calcerrada</Author><Year>2015</Year><RecNum>30</RecNum><DisplayText><styleface="superscript">[57]</style></DisplayText><record><rec-number>30</rec-number><foreign-keys><keyapp="EN"db-id="v9tf25xx5fedfletrem5ttx3pztpvzatxp2a"timestamp="1619487937">30</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Calcerrada,Matías</author><author>García-Ruiz,Carmen</author><author>González-Herráez,Miguel</author></authors></contributors><titles><title>Chemicalandbiochemicalsensingapplicationsofmicrostructuredopticalfiber-basedsystems</title><secondary-title>Laser&PhotonicsReviews</secondary-title></titles><periodical><full-title>Laser&PhotonicsReviews</full-title></periodical><pages>604-627</pages><volume>9</volume><number>6</number><section>604</section><dates><year>2015</year></dates><isbn>18638880</isbn><urls></urls><electronic-resource-num>10.1002/lpor.201500045</electronic-resource-num></record></Cite></EndNote>[57]，以及药物输送ADDINEN.CITE<EndNote><Cite><Author>Chen</Author><Year>2020</Year><RecNum>15</RecNum><DisplayText><styleface="superscript">[58]</style></DisplayText><record><rec-number>15</rec-number><foreign-keys><keyapp="EN"db-id="v9tf25xx5fedfletrem5ttx3pztpvzatxp2a"timestamp="1619487741">15</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Chen,Li</author><author>Liu,Donghao</author><author>Peng,Jun</author><author>Du,Qiuzheng</author><author>He,Hua</author></authors></contributors><titles><title>Ratiometricfluorescencesensingofmetal-organicframeworks:Tacticsandperspectives</title><secondary-title>CoordinationChemistryReviews</secondary-title></titles><periodical><full-title>CoordinationChemistryReviews</full-title></periodical><volume>404</volume><section>213113</section><dates><year>2020</year></dates><isbn>00108545</isbn><urls></urls><electronic-resource-num>10.1016/j.ccr.2019.213113</electronic-resource-num></record></Cite></EndNote>[58]和生物成像ADDINEN.CITE<EndNote><Cite><Author>Cui</Author><Year>2012</Year><RecNum>29</RecNum><DisplayText><styleface="superscript">[59]</style></DisplayText><record><rec-number>29</rec-number><foreign-keys><keyapp="EN"db-id="v9tf25xx5fedfletrem5ttx3pztpvzatxp2a"timestamp="1619487921">29</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Cui,Y.</author><author>Yue,Y.</author><author>Qian,G.</author><author>Chen,B.</author></authors></contributors><auth-address>StateKeyLaboratoryofSiliconMaterials,DepartmentofMaterialsScienceandEngineering,ZhejiangUniversity,Hangzhou310027,China.</auth-address><titles><title>Luminescentfunctionalmetal-organicframeworks</title><secondary-title>ChemRev</secondary-title></titles><periodical><full-title>ChemRev</full-title></periodical><pages>1126-62</pages><volume>112</volume><number>2</number><edition>2011/06/22</edition><keywords><keyword>BiomedicalTechnology</keyword><keyword>DrugCarriers/chemicalsynthesis/*chemistry</keyword><keyword>DrugDeliverySystems</keyword><keyword>*Luminescence</keyword><keyword>LuminescentMeasurements</keyword><keyword>Models,Molecular</keyword><keyword>OrganometallicCompounds/chemicalsynthesis/*chemistry/therapeuticuse</keyword></keywords><dates><year>2012</year><pub-dates><date>Feb8</date></pub-dates></dates><isbn>1520-6890(Electronic) 0009-2665(Linking)</isbn><accession-num>21688849</accession-num><urls><related-urls><url>/pubmed/21688849</url></related-urls></urls><electronic-resource-num>10.1021/cr200101d</electronic-resource-num></record></Cite></EndNote>[59]等众多领域。在众多已报道的荧光材料中，荧光金属有机框架（LMOFs）由于其易于诱导发光、结构和功能成分多样以及检测机制多样等优点，近年来逐渐成为一种潜在的化学传感器其荧光来源主要有以下四种：1.基于配体的荧光发射。MOF中的有机配体大多是基于多羧酸基团和杂环基团的刚性骨架，当有机配体受到光刺激后，就会发生从基态到激发态的跃迁，即π→π*或n→π*ADDINEN.CITEADDINEN.CITE.DATA[60]。MOF结构中有机配体的荧光常常会受到金属中心的影响，比如一些顺磁性金属会对有机配体的荧光产生猝灭作用。因此控制这些因素对调节MOF的有机配体的发光特性十分关键。2.基于镧系金属的荧光发射。常见镧系金属离子包括Eu、Tb、Sm、Tm等分别对应于红色、绿色、橙色和蓝色的荧光ADDINEN.CITE<EndNote><Cite><Author>Islamoglu</Author><Year>2017</Year><RecNum>10</RecNum><DisplayText><styleface="superscript">[61]</style></DisplayText><record><rec-number>10</rec-number><foreign-keys><keyapp="EN"db-id="v9tf25xx5fedfletrem5ttx3pztpvzatxp2a"timestamp="1619487696">10</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Islamoglu,T.</author><author>Goswami,S.</author><author>Li,Z.</author><author>Howarth,A.J.</author><author>Farha,O.K.</author><author>Hupp,J.T.</author></authors></contributors><auth-address>DepartmentofChemistry,NorthwesternUniversity,2145SheridanRoad,Evanston,Illinois60208,UnitedStates. DepartmentofChemistry,FacultyofScience,KingAbdulazizUniversity,Jeddah21589,SaudiArabia.</auth-address><titles><title>PostsyntheticTuningofMetal-OrganicFrameworksforTargetedApplications</title><secondary-title>AccChemRes</secondary-title></titles><periodical><full-title>AccChemRes</full-title></periodical><pages>805-813</pages><volume>50</volume><number>4</number><edition>2017/02/09</edition><dates><year>2017</year><pub-dates><date>Apr18</date></pub-dates></dates><isbn>1520-4898(Electronic) 0001-4842(Linking)</isbn><accession-num>28177217</accession-num><urls><related-urls><url>/pubmed/28177217</url></related-urls></urls><electronic-resource-num>10.1021/acs.accounts.6b00577</electronic-resource-num></record></Cite></EndNote>[61]。由于f-f跃迁被禁止，镧系金属的光吸收很弱，除非使用大功率的激光直接激发，否则其荧光发射效率非常低ADDINEN.CITE<EndNote><Cite><Author>Kaur</Author><Year>2019</Year><RecNum>16</RecNum><DisplayText><styleface="superscript">[62]</style></DisplayText><record><rec-number>16</rec-number><foreign-keys><keyapp="EN"db-id="v9tf25xx5fedfletrem5ttx3pztpvzatxp2a"timestamp="1619487750">16</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kaur,Harmeet</author><author>Sundriyal,Shashank</author><author>Pachauri,Vivek</author><author>Ingebrandt,Sven</author><author>Kim,Ki-Hyun</author><author>Sharma,AmitL.</author><author>Deep,Akash</author></authors></contributors><titles><title>Luminescentmetal-organicframeworksandtheircomposites:Potentialfuturematerialsfororganiclightemittingdisplays</title><secondary-title>CoordinationChemistryReviews</secondary-title></titles><periodical><full-title>CoordinationChemistryReviews</full-title></periodical><volume>401</volume><section>213077</section><dates><year>2019</year></dates><isbn>00108545</isbn><urls></urls><electronic-resource-num>10.1016/j.ccr.2019.213077</electronic-resource-num></record></Cite></EndNote>[62]，而镧系金属离子与有机配体合成MOF后，有机配体能够有效的将激发光的能量转移至镧系金属，使镧系金属离子产生电子能级的跃迁，这种能量的转移被称为“天线效应”或者“敏化”ADDINEN.CITE<EndNote><Cite><Author>Knebel</Author><Year>2018</Year><RecNum>38</RecNum><DisplayText><styleface="superscript">[63]</style></DisplayText><record><rec-number>38</rec-number><foreign-keys><keyapp="EN"db-id="v9tf25xx5fedfletrem5ttx3pztpvzatxp2a"timestamp="1619488071">38</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Knebel,Alexander</author><author>Zhou,Chen</author><author>Huang,Aisheng</author><author>Zhang,Jian</author><author>Kustov,Leonid</author><author>Caro,Juergen</author></authors></contributors><titles><title>SmartMetal-OrganicFrameworks(MOFs):SwitchingGasPermeationthroughMOFMembranesbyExternalStimuli</title><secondary-title>ChemicalEngineering&Technology</secondary-title></titles><periodical><full-title>ChemicalEngineering&Technology</full-title></periodical><pages>224-234</pages><volume>41</volume><number>2</number><section>224</section><dates><year>2018</year></dates><isbn>09307516</isbn><urls></urls><electronic-resource-num>10.1002/ceat.201700635</electronic-resource-num></record></Cite></EndNote>[63]。镧系金属离子可以被作为金属中心，与有机配体通过一锅水热法直接合成为MOF，或者通过合成后功能化的方式，具体是将镧系金属离子与有机配体中游离的羧基配位，负载到MOF上后，镧系金属离子仍与MOF中的有机配体实现能量的转移，该方法常常被应用于MOF的荧光检测中。3.客体导致的荧光发射。由于MOF材料规整的孔隙结构，常常作为荧光传感平台，与其他的荧光发光客体结合，形成复合荧光探针。常见的荧光客体分子有稀土元素、碳点、有机染料、荧光酶等物质ADDINEN.CITE<EndNote><Cite><Author>Li</Author><Year>2020</Year><RecNum>33</RecNum><DisplayText><styleface="superscript">[64]</style></DisplayText><record><rec-number>33</rec-number><foreign-keys><keyapp="EN"db-id="v9tf25xx5fedfletrem5ttx3pztpvzatxp2a"timestamp="1619487991">33</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Li,H.Y.</author><author>Zhao,S.N.</author><author>Zang,S.Q.</author><author>Li,J.</author></authors></contributors><auth-address>GreenCatalysisCenter,andCollegeofChemistry,ZhengzhouUniversity,Zhengzhou450001,China.zangsqzg@.</auth-address><titles><title>Functionalmetal-organicframeworksaseffectivesensorsofgasesandvolatilecompounds</title><secondary-title>ChemSocRev</secondary-title></titles><periodical><full-title>ChemSocRev</full-title></periodical><pages>6364-6401</pages><volume>49</volume><number>17</number><edition>2020/08/05</edition><dates><year>2020</year><pub-dates><date>Sep7</date></pub-dates></dates><isbn>1460-4744(Electronic) 0306-0012(Linking)</isbn><accession-num>32749390</accession-num><urls><related-urls><url>/pubmed/32749390</url></related-urls></urls><electronic-resource-num>10.1039/c9cs00778d</electronic-resource-num></record></Cite></EndNote>[64]。需要注意的是，当客体荧光封装到负载到MOF内后，其在MOF孔道内的分布聚集、有机配体之间的电荷转移、以及金属中心的种类与作用，都会影响到荧光分子的荧光性质，以及有些MOF的合成条件需要在酸性及高温环境中，故在选择封装客体分子时要格外注意。对于单一的荧光猝灭“Turn-Off”有其弊端：单一荧光颜色的猝灭，会限制荧光探针的灵敏度，且当待测物浓度较小时，引起的荧光变化可能太小而无法监测。而且具有相似结构或电子性质的其他物质会对荧光的检测产生干扰。为了提高基于MOF的传感器的灵敏度和选择性，需要采取“荧光开启”的检测策略，当荧光探针检测到待测物时开启荧光发射，或者发射荧光发射峰的偏移甚至开启新的荧光发射。暗背景可以通过使用具有自由旋转部分的荧光基团作为有机配体或结合顺磁性金属离子来实现，这两者都可以有效抑制LMOF的荧光。MOF材料在荧光传感领域有其特殊的优势：一是MOF的孔久孔隙提供了大的比表面积和大量的活性位点，可以大大加速表面的主客体之间的反应，同时孔隙结构可以将待检测物质进行有效的富集，从而提高检测的灵敏度ADDINEN.CITE<EndNote><Cite><Author>Liu</Author><Year>2019</Year><RecNum>18</RecNum><DisplayText><styleface="superscript">[65]</style></DisplayText><record><rec-number>18</rec-number><foreign-keys><keyapp="EN"db-id="v9tf25xx5fedfletrem5ttx3pztpvzatxp2a"timestamp="1619487781">18</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Liu,Yang</author><author>Liu,Zhifeng</author><author>Huang,Danlian</author><author>Cheng,Min</author><author>Zeng,Guangming</author><author>Lai,Cui</author><author>Zhang,Chen</author><author>Zhou,Chengyun</author><author>Wang,Wenjun</author><author>Jiang,Danni</author><author>Wang,Han</author><author>Shao,Binbin</author></authors></contributors><titles><title>Metalormetal-containingnanoparticle@MOFnanocompositesasapromisingtypeofphotocatalyst</title><secondary-title>CoordinationChemistryReviews</secondary-title></titles><periodical><full-title>CoordinationChemistryReviews</full-title></periodical><pages>63-78</pages><volume>388</volume><section>63</section><dates><year>2019</year></dates><isbn>00108545</isbn><urls></urls><electronic-resource-num>10.1016/j.ccr.2019.02.031</electronic-resource-num></record></Cite></EndNote>[65]。二是MOF对检测物质的吸附和解吸附拥有良好的可逆性，这一性质对于荧光传感探针十分重要，可以提高荧光探针的可回收性ADDINEN.CITE<EndNote><Cite><Author>Lustig</Author><Year>2017</Year><RecNum>3</RecNum><DisplayText><styleface="superscript">[66]</style></DisplayText><record><rec-number>3</rec-number><foreign-keys><keyapp="EN"db-id="v9tf25xx5fedfletrem5ttx3pztpvzatxp2a"timestamp="1619487594">3</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Lustig,W.P.</author><author>Mukherjee,S.</author><author>Rudd,N.D.</author><author>Desai,A.V.</author><author>Li,J.</author><author>Ghosh,S.K.</author></authors></contributors><auth-address>DepartmentofChemistryandChemicalBiology,RutgersUniversity,Piscataway,NJ08854,USA.jingli@.</auth-address><titles><title>Metal-organicframeworks:functionalluminescentandphotonicmaterialsforsensingapplications</title><secondary-title>ChemSocRev</secondary-title></titles><periodical><full-title>ChemSocRev</full-title></periodical><pages>3242-3285</pages><volume>46</volume><number>11</number><edition>2017/05/04</edition><keywords><keyword>ChemistryTechniques,Analytical/*methods</keyword><keyword>Cyanides/analysis</keyword><keyword>DiaminopimelicAcid/analysis</keyword><keyword>HydrogenSulfide/analysis</keyword><keyword>*Luminescence</keyword><keyword>LuminescentAgents/*chemistry</keyword><keyword>Metal-OrganicFrameworks/*chemistry</keyword><keyword>Mycotoxins/analysis</keyword><keyword>NitricOxide/analysis</keyword><keyword>*Photons</keyword></keywords><dates><year>2017</year><pub-dates><date>Jun6</date></pub-dates></dates><isbn>1460-4744(Electronic) 0306-0012(Linking)</isbn><accession-num>28462954</accession-num><urls><related-urls><url>/pubmed/28462954</url></related-urls></urls><electronic-resource-num>10.1039/c6cs00930a</electronic-resource-num></record></Cite></EndNote>[66]。三是MOF的孔径大小、结构和表面官能团是可设计调控的，这意味着可以通过合理的设计从而达到预想的结构、孔径，从来改变MOF的荧光传感的选择性好灵敏度ADDINEN.CITE<EndNote><Cite><Author>Mahata</Author><Year>2017</Year><RecNum>2</RecNum><DisplayText><styleface="superscript">[67]</style></DisplayText><record><rec-number>2</rec-number><foreign-keys><keyapp="EN"db-id="v9tf25xx5fedfletrem5ttx3pztpvzatxp2a"timestamp="1619487572">2</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Mahata,P.</author><author>Mondal,S.K.</author><author>Singha,D.K.</author><author>Majee,P.</author></authors></contributors><auth-address>DepartmentofChemistry,SuriVidyasagarCollege,Suri,Birbhum,PIN-731101,WestBengal,India.parthachem@. DepartmentofChemistry,Siksha-Bhavana,Visva-BharatiUniversity,Santiniketan-731235,WestBengal,India.sudip.mondal@visva-bharati.ac.in.</auth-address><titles><title>Luminescentrare-earth-basedMOFsasopticalsensors</title><secondary-title>DaltonTrans</secondary-title></titles><periodical><full-title>DaltonTrans</full-title></periodical><pages>301-328</pages><volume>46</volume><number>2</number><edition>2016/12/06</edition><dates><year>2017</year><pub-dates><date>Jan3</date></pub-dates></dates><isbn>1477-9234(Electronic) 1477-9226(Linking)</isbn><accession-num>27918044</accession-num><urls><related-urls><url>/pubmed/27918044</url></related-urls></urls><electronic-resource-num>10.1039/c6dt03419e</electronic-resource-num></record></Cite></EndNote>[67]。四是MOF晶格十分规整，可以通过判断反应前后MOF结构是否完整，从而更好的推断MOF与检测物质的反应原理。五是MOF尝尝具有良好的温湿度稳定性，其荧光发射在实际检测中，不易受到外界环境的干扰，适合实际检测中复杂多变的环境。1.1荧光金属有机框架材料的研究进展1.对气体的检测利用金属有机框架的孔隙结构和多活性位点，金属有机框架可以有效的吸附气体ADDINEN.CITE<EndNote><Cite><Author>Mehta</Author><Year>2016</Year><RecNum>21</RecNum><DisplayText><styleface="superscript">[68]</style></DisplayText><record><rec-number>21</rec-number><foreign-keys><keyapp="EN"db-id="v9tf25xx5fedfletrem5ttx3pztpvzatxp2a"timestamp="1619487814">21</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Mehta,Jyotsana</author><author>Bhardwaj,Neha</author><author>Bhardwaj,SanjeevK.</author><author>Kim,Ki-Hyun</author><author>Deep,Akash</author></authors></contributors><titles><title>Recentadvancesinenzymeimmobilizationtechniques:Metal-organicframeworksasnovelsubstrates</title><secondary-title>CoordinationChemistryReviews</secondary-title></titles><periodical><full-title>CoordinationChemistryReviews</full-title></periodical><pages>30-40</pages><volume>322</volume><section>30</section><dates><year>2016</year></dates><isbn>00108545</isbn><urls></urls><electronic-resource-num>10.1016/j.ccr.2016.05.007</electronic-resource-num></record></Cite></EndNote>[68]，从而实现气体的荧光传感，拥有其他荧光传感材料不可比拟的优势。比如对气体H2S的检测，常见的对H2S检测的荧光开启机制有以下三种：一是H2S与金属离子的沉淀反应，从而实现荧光的开启，如图1.12(a)，所示Yuan-YuanCaoADDINEN.CITE<EndNote><Cite><Author>Cao</Author><Year>2017</Year><RecNum>27</RecNum><DisplayText><styleface="superscript">[69]</style></DisplayText><record><rec-number>27</rec-number><foreign-keys><keyapp="EN"db-id="2ev0teddmsxaxoevzfhv9fanpdxz5afs9aaz"timestamp="1619440662">27</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Cao,Yuan-Yuan</author><author>Guo,Xiao-Feng</author><author>Wang,Hong</author></authors></contributors><titles><title>Highsensitiveluminescencemetal-organicframeworksensorforhydrogensulfideinaqueoussolution:Atrialofnovelturn-onmechanism</title><secondary-title>SensorsandActuatorsB:Chemical</secondary-title></titles><periodical><full-title>SensorsandActuatorsB:Chemical</full-title></periodical><pages>8-13</pages><volume>243</volume><section>8</section><dates><year>2017</year></dates><isbn>09254005</isbn><urls></urls><electronic-resource-num>10.1016/j.snb.2016.11.085</electronic-resource-num></record></Cite></EndNote>[69]等人以铁离子为金属中心、二氨基对苯二甲酸（NH2-H2BDC）为有机荧光配体，合成了一种顺磁性的MOF，在结构上，铁离子位于结构的顶点，荧光有机配体被封装在MOF体系内，由于顶点上铁离子的顺磁性，使得MOF整体失去荧光性能，但该MOF与被检测物质H2S接触后，由于S2-和Fe3+之间超强的亲和力，会破坏MOF的整体结构，从而使得封装在内的有机荧光配体重新产生荧光，从而实现对H2S气体的荧光响应。且该MOF对H2S气体具有良好的选择性响应，检测限低至10μM。YuMaADDINEN.CITE<EndNote><Cite><Author>Ma</Author><Year>2014</Year><RecNum>32</RecNum><DisplayText><styleface="superscript">[70]</style></DisplayText><record><rec-number>32</rec-number><foreign-keys><keyapp="EN"db-id="2ev0teddmsxaxoevzfhv9fanpdxz5afs9aaz"timestamp="1619440722">32</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ma,Y.</author><author>Su,H.</author><author>Kuang,X.</author><author>Li,X.</author><author>Zhang,T.</author><author>Tang,B.</author></authors></contributors><auth-address>CollegeofChemistry,ChemicalEngineeringandMaterialsScience,CollaborativeInnovationCenterofFunctionalizedProbesforChemicalImaging,KeyLaboratoryofMolecularandNanoProbes,MinistryofEducation,ShangdongProvincialKeyLaboratoryofCleanProductionofFineChemicals,ShandongNormalUniversity,Jinan250014,People'sRepublicofChina.</auth-address><titles><title>Heterogeneousnanometal-organicframeworkfluorescenceprobeforhighlyselectiveandsensitivedetectionofhydrogensulfideinlivingcells</title><secondary-title>AnalChem</secondary-title></titles><periodical><full-title>AnalChem</full-title></periodical><pages>11459-63</pages><volume>86</volume><number>22</number><edition>2014/10/25</edition><keywords><keyword>CellSurvival</keyword><keyword>FluorescentDyes/*chemistry</keyword><keyword>HepG2Cells</keyword><keyword>Humans</keyword><keyword>HydrogenSulfide/*analysis</keyword><keyword>Nanostructures/*chemistry</keyword><keyword>OrganometallicCompounds/chemicalsynthesis/*chemistry</keyword><keyword>TumorCells,Cultured</keyword></keywords><dates><year>2014</year><pub-dates><date>Nov18</date></pub-dates></dates><isbn>1520-6882(Electronic) 0003-2700(Linking)</isbn><accession-num>25342497</accession-num><urls><related-urls><url>/pubmed/25342497</url></related-urls></urls><electronic-resource-num>10.1021/ac503622n</electronic-resource-num></record></Cite></EndNote>[70]等人利用类似的原理，如图1.12(b)所示：利用顺磁性金属铜与荧光有机配体4-羧基苯基卟啉合成了一种卟啉MOF，铜离子位于卟啉中心，当该MOF与H2S接触后，铜离子会和H2S生成CuS沉淀，从而实现荧光的开启。二是利用H2S的强还原性降低电子受体对电子供体的作用。如图1.12(c)所示，SanjogS.NagarkarADDINEN.CITEADDINEN.CITE.DATA[71]等人利用氯化锆为金属中心，2硝基对苯二甲酸为有机配体合成出了一种硝基功能化的金属有机框架，该MOF上-NO2作吸电子基团，使MOF处于荧光关闭的状态，当与H2S接触后，吸电子的-NO2变为给电子-NH2，使得苯环上的电子密度增加，从而实现荧光的开启。RanaDalapatiADDINEN.CITE<EndNote><Cite><Author>Dalapati</Author><Year>2017</Year><RecNum>33</RecNum><DisplayText><styleface="superscript">[72]</style></DisplayText><record><rec-number>33</rec-number><foreign-keys><keyapp="EN"db-id="2ev0teddmsxaxoevzfhv9fanpdxz5afs9aaz"timestamp="1619440728">33</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Dalapati,Rana</author><author>Balaji,S.N.</author><author>Trivedi,Vishal</author><author>Khamari,Laxmikanta</author><author>Biswas,Shyam</author></authors></contributors><titles><title>Adinitro-functionalizedZr(IV)-basedmetal-organicframeworkascolorimetricandfluorogenicprobeforhighlyselectivedetectionofhydrogensulphide</title><secondary-title>SensorsandActuatorsB:Chemical</secondary-title></titles><periodical><full-title>SensorsandActuatorsB:Chemical</full-title></periodical><pages>1039-1049</pages><volume>245</volume><section>1039</section><dates><year>2017</year></dates><isbn>09254005</isbn><urls></urls><electronic-resource-num>10.1016/j.snb.2017.02.005</electronic-resource-num></record></Cite></EndNote>[72]等人与SanjogSNagarkar的做法类似，在单硝基功能化MOF上，采用二硝基MOF作为荧光探针在生理条件下实现了对H2S的荧光检测。以4,8-二硝基萘-2,6-二羧酸为配体，金属离子为锆，合成的MOF具有更好的H2S荧光检测性能，检测限为20μM。(a)(b)(c)另外，对于的H2S气体的实际检测，(a)(b)(c)图1.12（a）Fe-MIL-88-NH2对H2S的荧光开启检测；(b)nano-MOFPAC对H2S的荧光开启检测；（c）硝基功能化MOF对H2S的荧光开启检测。如图1.13所示，JunZhangADDINEN.CITE<EndNote><Cite><Author>Zhang</Author><Year>2019</Year><RecNum>30</RecNum><DisplayText><styleface="superscript">[73]</style></DisplayText><record><rec-number>30</rec-number><foreign-keys><keyapp="EN"db-id="2ev0teddmsxaxoevzfhv9fanpdxz5afs9aaz"timestamp="1619440683">30</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhang,Jun</author><author>Liu,Fang</author><author>Gan,Jiulin</author><author>Cui,Yuanjing</author><author>Li,Bin</author><author>Yang,Yu</author><author>Qian,Guodong</author></authors></contributors><titles><title>Metal-organicframeworkfilmforfluorescenceturn-onH2Sgassensingandanti-counterfeitingpatterns</title><secondary-title>ScienceChinaMaterials</secondary-title></titles><periodical><full-title>ScienceChinaMaterials</full-title></periodical><pages>1445-1453</pages><volume>62</volume><number>10</number><section>1445</section><dates><year>2019</year></dates><isbn>2095-8226 2199-4501</isbn><urls></urls><electronic-resource-num>10.1007/s40843-019-9457-5</electronic-resource-num></record></Cite></EndNote>[73]等人在在ITO板上，以氯化铟为金属中心、1,3,5-均苯三甲酸为有机配体，一步水热在ITO基材上合成了MIL-100（In）薄膜，随后采用合成后功能化的方式，利用MIL-100上未配位的-COOH负载上上稀土元素Eu以及铜离子，由于铜离子会阻碍稀土元素Eu与有机配体之间的能量转移，从而猝灭Eu3+的红色荧光，当该MOF与H2S接触后，H2S和Cu之间的亲和力会生成CuS沉淀，把Cu离子从该MOF体系中抽离而不会破坏MOF原有的结构，从而恢复Eu和有机配体之间的能量转移，实现荧光的开启，最后得到的对H2S的检测限为0.535ppm，低于大多数被报道过的荧光探针。更具有启发性的是，JunZhang等人将MIL-100（In）作为承印物，镧系金属离子作为油墨，在MIL-100衬底上利用喷墨打印的方式实现了荧光防伪图案的制备。打印到MIL-100衬底上的镧系金属能够与有机配体之间实现良好的能量转移，这为荧光防伪图案的制备提供了一种新的思路。图1.13MIL-100@Eu3+/Cu2+对H2S的荧光开启响应部分金属有机框架对氨气（NH3）有很好的气体吸附能力。一般含有大量游离-COOH和活性金属位点的金属有机框架对NH3的吸附能力较强。游离的-COOH可以与NH3结合生成-COONH4，从而大量的吸附氨气，而活性金属位点有如Cu2+，则是可以和NH3生成一种络合物，作为锚点吸附氨气。比如MichaelJ.Katz等人介绍了一种Cu-MOF-74比较了该MOF与HKUST-1对NH3的吸收能力，Cu-MOF-74对NH3的吸收会受到水分的影响，在潮湿环境下，该MOF对NH3的吸收明显增加，但是会破坏MOF的结晶度，这可能是由于Cu-COOH键的断裂，允许更多的NH3与铜离子配位，并推测生成了一种羧酸铵盐和Cu(OH)2等物质。在干燥情况下，Cu-MOF-74的吸能能力为为2.6NH3/nm3而HKUST-1为2.9；在80％相对湿度时，Cu-MOF-74为5.9NH3/nm3而HKUST-1为3.9。利用这种特性，研究出了许多对氨气敏感的荧光探针材料。图1.14Eu3+@MIL-124对氨气的灵敏度响应如图1.14所示JunZhangADDINEN.CITE<EndNote><Cite><Author>Zhang</Author><Year>2017</Year><RecNum>26</RecNum><DisplayText><styleface="superscript">[74]</style></DisplayText><record><rec-number>26</rec-number><foreign-keys><keyapp="EN"db-id="2ev0teddmsxaxoevzfhv9fanpdxz5afs9aaz"timestamp="1619440656">26</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhang,Jun</author><author>Yue,Dan</author><author>Xia,Tifeng</author><author>Cui,Yuanjing</author><author>Yang,Yu</author><auth