【多孔有机聚合物修复重金属污染研究的文献综述5500字】

多孔有机聚合物修复重金属污染研究的文献综述目录TOC\o"1-3"\h\u1915多孔有机聚合物修复重金属污染研究的文献综述 1157781.1共价有机骨架概述 1207281.2共价有机骨架材料吸附重金属研究 59031.3共价有机骨架复合材料研究进展 8多孔有机聚合物ADDINEN.CITE<EndNote><Cite><Author>Lv</Author><Year>2019</Year><RecNum>179</RecNum><DisplayText><styleface="superscript">[56]</style></DisplayText><record><rec-number>179</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1583674013">179</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Lv,ShiWen</author><author>Liu,JingMin</author><author>Wang,ZhiHao</author><author>Ma,Hui</author><author>Li,ChunYang</author><author>Zhao,Ning</author><author>Wang,Shuo</author></authors></contributors><titles><title>Recentadvancesonporousorganicframeworksfortheadsorptiveremovalofhazardousmaterials</title><secondary-title>JournalofEnvironmentalSciences</secondary-title></titles><periodical><full-title>JournalofEnvironmentalSciences</full-title><abbr-1>JEnvS</abbr-1></periodical><pages>169-185</pages><volume>80</volume><dates><year>2019</year></dates><urls></urls></record></Cite></EndNote>[56]是通过不同有机单体形成高稳定共价键连接的具有二维或三维网络结构的聚合物。多孔有机聚合物由轻质元素（C、H、O、N和B等）和稳定共价键组成，具有较低的骨架密度及毒性（未涉及重金属元素）和良好的物理化学稳定性，在多个领域前景广阔，特别是重金属吸附领域。多孔有机聚合物主要包括固有微孔聚合物、超交联聚合物、共轭微孔聚合物和共价有机骨架等。和其余几种材料相比，共价有机骨架ADDINEN.CITE<EndNote><CiteExcludeAuth="1"><Year>2005</Year><RecNum>146</RecNum><DisplayText><styleface="superscript">[57]</style></DisplayText><record><rec-number>146</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1575812566">146</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>AdrienPCôté</author><author>AnnabelleIBenin</author><author>NathanWOckwig</author><author>MichaelO'Keeffe</author><author>AdamJMatzger</author><author>OmarMYaghi</author></authors></contributors><titles><title>Porous,Crystalline,CovalentOrganicFrameworks</title><secondary-title>Science</secondary-title></titles><periodical><full-title>Science</full-title><abbr-1>Science</abbr-1><abbr-2>Science</abbr-2></periodical><pages>1166-1170</pages><volume>310</volume><number>5751</number><dates><year>2005</year></dates><urls></urls></record></Cite></EndNote>[57]具有结晶性且相对有序的结构。同时，共价有机骨架可以预先设计，使其对某些重金属具有吸附选择性ADDINEN.CITE<EndNote><CiteExcludeYear="1"><Author>Wei</Author><RecNum>216</RecNum><DisplayText><styleface="superscript">[58,59]</style></DisplayText><record><rec-number>216</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1583689932">216</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Wang,Wei</author><author>Deng,ShuBo</author><author>Ren,Lu</author><author>Li,DanYang</author><author>Wang,WenJing</author><author>VakiliMohammadtaghi</author><author>Wang,Bin</author><author>Huang,Jun</author><author>Wang,Yujue</author><author>Yu,Gang</author></authors></contributors><titles><title>StableCovalentOrganicFrameworksasEfficientAdsorbentsforHighandSelectiveRemovalofAryl-OrganophosphorusFlameRetardantfromWater</title><secondary-title>ACSAppliedMaterials&Interfaces</secondary-title></titles><periodical><full-title>AcsAppliedMaterials&Interfaces</full-title><abbr-1>ACSAppl.Mater.Interfaces</abbr-1></periodical><pages>30265-30272</pages><volume>10</volume><number>36</number><dates><year>2018</year></dates><urls></urls></record></Cite><CiteExcludeYear="1"><Author>Merí-Bofí</Author><RecNum>125</RecNum><record><rec-number>125</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1575555165">125</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Merí-Bofí,Laura</author><author>Royuela,Sergio</author><author>Zamora,Felix</author><author>Ruiz-Gonzales,Luisa</author><author>Segura,Jose</author><author>Mu?oz-Olivas,Riansares</author><author>Manche?o,MaríaJosé</author></authors></contributors><titles><title>ThiolGraftedImine-BasedCovalentOrganicFrameworkforWaterRemediationThroughSelectiveRemovalofHg(II)</title><secondary-title>JournalofMaterialsChemistryA</secondary-title></titles><pages>10.1039.C7TA05588A</pages><dates></dates><urls></urls></record></Cite></EndNote>[58,59]，此外，共价有机骨架较大的比表面积和相对均一的孔径分布增加了与重金属离子接触的可能，因此选择将共价有机骨架引入稻壳生物炭制备复合材料。1.1共价有机骨架概述1.1.1共价有机骨架的结构设计COFs材料合成条件较为严苛，在合成设计过程中为了避免合成无定型结构，需要将几个因素列入考虑：构建单元的刚性，有机单体连接的对称性、有机单体间的构型及夹角的匹配与否等ADDINEN.CITE<EndNote><Cite><Author>Kuhn</Author><Year>2008</Year><RecNum>222</RecNum><DisplayText><styleface="superscript">[60]</style></DisplayText><record><rec-number>222</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1584467122">222</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kuhn,Pierre</author><author>MarkusAntonietti</author><author>Thomas,Arne</author></authors></contributors><titles><title>Porous,CovalentTriazine-BasedFrameworksPreparedbyIonothermalSynthesis</title><secondary-title>AngewandteChemieInternationalEdition</secondary-title></titles><periodical><full-title>AngewandteChemieInternationalEdition</full-title><abbr-1>Angew.Chem.Int.Ed.</abbr-1><abbr-2>AngewChemIntEd</abbr-2></periodical><pages>3450-3453</pages><volume>47</volume><number>18</number><keywords><keyword>crystallineorganicnetworks</keyword><keyword>ionothermalpolymerization</keyword><keyword>porouspolymers</keyword><keyword>triazine</keyword><keyword>trimerizations</keyword></keywords><dates><year>2008</year></dates><urls></urls></record></Cite></EndNote>[60]，因此通过对骨架，孔道以及功能化这三部分的合理控制，可以得到结构多样、性能各异的COFs材料。目前所报道COFs材料的拓扑结构主要有六边形、三角形、四边形、菱形以及笼形等，根据构建单元的对称性，可以分为C2、C3、C4和C6对称单元（图1.1）。六边形结构是构建COFs材料中最为常见的，它基本上是通过部分C2对称单元的自身缩合或C3对称单元与C2或C3对称单元的共缩合连接而成的拓扑结构得到的。在构建COFs材料时，孔道结构的设计也是极为重要的。有序孔道的构建方法主要有两种，一种是通过设计刚性构筑单元创建有序的孔道结构ADDINEN.CITE<EndNote><CiteExcludeYear="1"><Author>Budd</Author><RecNum>218</RecNum><DisplayText><styleface="superscript">[61]</style></DisplayText><record><rec-number>218</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1583690889">218</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Budd,P.M.</author><author>E.S.Elabas</author><author>B.S.Ghanem</author><author>S.Makhseed</author><author>N.B.McKeown</author><author>K.J.Msayib</author><author>C.E.Tattershall</author><author>D.Wang</author></authors></contributors><titles><title>Solution-Processed,OrganophilicMembraneDerivedfromaPolymerofIntrinsicMicroporosity</title><secondary-title>AdvancedMaterials</secondary-title></titles><periodical><full-title>AdvancedMaterials</full-title><abbr-1>Adv.Mater.</abbr-1><abbr-2>AdvMater</abbr-2></periodical><pages>456-459</pages><volume>16</volume><number>5</number><dates><year>2004</year></dates><urls></urls></record></Cite></EndNote>[61]；另一种是使用模板剂ADDINEN.CITE<EndNote><Cite><Author>Davis</Author><Year>2002</Year><RecNum>217</RecNum><DisplayText><styleface="superscript">[62]</style></DisplayText><record><rec-number>217</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1583689932">217</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Davis,M.E.</author></authors></contributors><titles><title>OrderedPorousMaterialsforEmergingApplications</title><secondary-title>Nature</secondary-title></titles><periodical><full-title>Nature</full-title><abbr-1>Nature</abbr-1><abbr-2>Nature</abbr-2></periodical><pages>813-821</pages><volume>417</volume><number>40</number><dates><year>2002</year></dates><urls></urls></record></Cite></EndNote>[62]的方法。迄今为止，大多数COFs材料的孔道形成均是通过刚性构筑单元来构建有序的孔结构，而孔径的大小受构筑单元间所形成的拓扑结构以及构筑直链长短控制ADDINEN.CITE<EndNote><Cite><Author>Fang</Author><Year>2015</Year><RecNum>188</RecNum><DisplayText><styleface="superscript">[63]</style></DisplayText><record><rec-number>188</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1583674013">188</key></foreign-keys><ref-typename="ConferenceProceedings">10</ref-type><contributors><authors><author>Fang,QianRong</author><author>Qiu,ShiLun</author><author>Yan,YuShan</author></authors></contributors><titles><title>DesignedSynthesisofLarge-PoreCrystallinePolyimideCovalentOrganicFrameworks</title><secondary-title>中国化学会第九届全国无机化学学术会议</secondary-title></titles><dates><year>2015</year></dates><urls></urls></record></Cite></EndNote>[63]。图1.12DCOFs的部分拓扑学结构类型Figure1.1Topologydiagramsfordesigning2DCOFs.骨架和孔道的设计在实现多孔结晶COFs的合成十分重要，但为了构建应用于某些领域的功能性COFs时，需要着重考虑如何将功能基团引入COFs材料上。从合成方法的角度看，COFs材料的功能化修饰大体上可以分为两类（图1.2）：一类是后修饰法ADDINEN.CITE<EndNote><CiteExcludeYear="1"><Author>Sun</Author><RecNum>159</RecNum><DisplayText><styleface="superscript">[64]</style></DisplayText><record><rec-number>159</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1576171050">159</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Sun,Qi</author><author>Aguila,Briana</author><author>Perman,JasonA.</author><author>Nguyen,NicholasThien-Khoa</author><author>Ma,Shengqian</author></authors></contributors><titles><title>FlexibilityMatters:CooperativeActiveSitesinCovalentOrganicFrameworkandThreadedIonicPolymer</title><secondary-title>JournaloftheAmericanChemicalSociety</secondary-title></titles><periodical><full-title>JournaloftheAmericanChemicalSociety</full-title><abbr-1>J.Am.Chem.Soc.</abbr-1><abbr-2>JAmChemSoc</abbr-2></periodical><pages><styleface="normal"font="default"size="100%">15790</style><styleface="normal"font="default"charset="134"size="100%">–</style><styleface="normal"font="default"size="100%">15796</style></pages><volume>138</volume><number>48</number><dates><year>2016</year></dates><urls></urls></record></Cite></EndNote>[64]，利用不同的反应单体通过缩合反应生成具有一定晶体结构的COF骨架，然后再用适当的基团去修饰孔壁，使COFs材料上嵌入功能化的基团。后修饰法可以将具有不同功能的基团引入到COFs材料骨架中，从而扩大功能化COFs材料的应用范围，但会导致COFs材料的比表面积下降、孔径减小，而且该方法存在一定的不可控性，其引入的功能团基团的分布不均匀；另一类则是自下而上合成法ADDINEN.CITE<EndNote><Cite><Author>Ding</Author><Year>2016</Year><RecNum>182</RecNum><DisplayText><styleface="superscript">[65]</style></DisplayText><record><rec-number>182</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1583674013">182</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ding,SanYuan</author><author>Dong,Ming</author><author>Wang,YaWen</author><author>Chen,YanTao</author><author>Wang,Hz</author><author>Su,Cy</author><author>Wang,W</author></authors></contributors><titles><title>Thioether-BasedFluorescentCovalentOrganicFrameworkforSelectiveDetectionandFacileRemovalofMercury(II)</title><secondary-title>JournaloftheAmericanChemicalSociety</secondary-title></titles><periodical><full-title>JournaloftheAmericanChemicalSociety</full-title><abbr-1>J.Am.Chem.Soc.</abbr-1><abbr-2>JAmChemSoc</abbr-2></periodical><pages>3031-3037</pages><volume>138</volume><number>9</number><dates><year>2016</year></dates><urls></urls></record></Cite></EndNote>[65]，主要是将携带特定功能化基团的单体直接用于合成COFs材料。这种合成方法可以将功能化基团均匀地引入到COFs材料的骨架中，然而功能化单体的合成通常比较困难，在合成COFs的过程中有可能因为功能化单体的刚性或者对称性的改变而更加困难。图1.2共价有机框架功能化方法Figure1.2SynthesismethodsoffunctionalizedCOFs:post-syntheticmethod(a)andbottom-upmethod(b).1.1.2共价有机骨架的反应类型共价有机骨架最重要的特征是基于可逆有机反应形成的以动态共价键连接的具有周期性的二维或三维多孔聚合物网络ADDINEN.CITE<EndNote><Cite><Author>唐俊杰</Author><Year>2018</Year><RecNum>628</RecNum><DisplayText><styleface="superscript">[66]</style></DisplayText><record><rec-number>628</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1618766388">628</key></foreign-keys><ref-typename="Thesis">32</ref-type><contributors><authors><author>唐俊杰</author></authors><tertiary-authors><author>陈奇丹,</author><author>方千荣,</author></tertiary-authors></contributors><titles><title>新型二维多级孔共价有机框架及其复合材料的设计合成和结构表征</title></titles><keywords><keyword>共价有机框架材料</keyword><keyword>多级孔</keyword><keyword>硅藻土基复合材料</keyword></keywords><dates><year>2018</year></dates><publisher>吉林大学</publisher><work-type>硕士</work-type><urls></urls><remote-database-provider>Cnki</remote-database-provider></record></Cite></EndNote>[66]。目前为止，已经形成了几种比较典型的构筑COFs材料的连接类型：B-O键、C=N键、C-C键、B-N及其它。其中C=N是构建COFs最具代表性的连接类型（图1.3）。通过含胺和含醛的单体之间的醛亚胺缩合反应可以形成C=N连接的COFs，其中包括具有芳香性的单体如芳香胺和芳香醛。此外，由酰肼和醛可逆缩合形成的腙连接的COFs也被认为是另一种基于亚胺的COFsADDINEN.CITE<EndNote><CiteExcludeYear="1"><Author>Uribe-Romo</Author><RecNum>186</RecNum><DisplayText><styleface="superscript">[67]</style></DisplayText><record><rec-number>186</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1583674013">186</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>FernandoJ.Uribe-Romo</author><author>Doonan,ChristianJ.</author><author>Furukawa,Hiroyasu</author><author>KounosukeOisaki</author><author>Yaghi,</author><author>OmarM.</author></authors></contributors><titles><title>CrystallineCovalentOrganicFrameworkswithHydrazoneLinkages</title><secondary-title>JournaloftheAmericanChemicalSociety</secondary-title></titles><periodical><full-title>JournaloftheAmericanChemicalSociety</full-title><abbr-1>J.Am.Chem.Soc.</abbr-1><abbr-2>JAmChemSoc</abbr-2></periodical><pages>p.11478-11481</pages><volume>133</volume><number>30</number><dates><year>2011</year></dates><urls></urls></record></Cite></EndNote>[67]。基于亚胺的COF不仅具有更高的结晶度和结构规则性，而且在水和大多数有机溶剂中（在酸性环境中不稳定）更稳定ADDINEN.CITE<EndNote><Cite><Author>Fang</Author><Year>2015</Year><RecNum>188</RecNum><DisplayText><styleface="superscript">[63]</style></DisplayText><record><rec-number>188</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1583674013">188</key></foreign-keys><ref-typename="ConferenceProceedings">10</ref-type><contributors><authors><author>Fang,QianRong</author><author>Qiu,ShiLun</author><author>Yan,YuShan</author></authors></contributors><titles><title>DesignedSynthesisofLarge-PoreCrystallinePolyimideCovalentOrganicFrameworks</title><secondary-title>中国化学会第九届全国无机化学学术会议</secondary-title></titles><dates><year>2015</year></dates><urls></urls></record></Cite></EndNote>[63]。同时，骨架中丰富的氮原子可以与各种金属配位实现对重金属离子的吸附，因此选择C=N作为共价有机骨架的连接类型。图1.3共价有机框架连接方式Figure1.3VariouslinkagesforCOFformation.1.1.3共价有机骨架的合成方法COFs要在实际中应用，需要找到合适的合成条件。目前科研工作者们已经发展了多种合成COFs的方法：溶剂热法将合成COFs的单体和溶剂在特定温度和压力下于密封系统中进行。研究发现，溶剂热合成COFs材料受多种因素影响，主要有：混合溶剂的搭配、催化剂的选择、温度的控制、反应原料的摩尔比、反应时间的控制等。不同的反应类型对溶剂热合成条件的要求也不尽相同，如硼酸类和亚胺类反应，温度大多都在85~120℃之间，使用的混合溶剂大多数为均三甲苯/1，4-二氧六环并以醋酸作催化剂；而酰胺类反应需要将温度控制在170~250℃之间，使用的混合溶剂大多数为均三甲苯/N-甲基吡咯烷酮并用异喹啉作为催化剂。溶剂热法需要高温高压，反应时间长，不利于大规模生产，但是它在多数情况下可以得到结晶性较好和比表面积较高的COFs材料。微波加热法微波加热法可以使反应系统更均匀加热，是一种加快化学反应的有效手段，Cooper等ADDINEN.CITE<EndNote><CiteExcludeYear="1"><Author>Ritchie</Author><RecNum>194</RecNum><DisplayText><styleface="superscript">[68]</style></DisplayText><record><rec-number>194</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1583674013">194</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ritchie,LyndseyK.</author><author>AbbieTrewin</author><author>AidaReguera-Galan</author><author>TomHasell</author><author>AndrewI.Cooper</author></authors></contributors><titles><title>SynthesisofCOF-5usingmicrowaveirradiationandconventionalsolvothermalroutes</title><secondary-title>MicroporousandMesoporousMaterials</secondary-title></titles><periodical><full-title>MicroporousandMesoporousMaterials</full-title><abbr-1>MicroporousMesoporousMater.</abbr-1><abbr-2>MicroporousMesoporousMater</abbr-2></periodical><pages>132-136</pages><volume>132</volume><number>1-2</number><dates><year>2010</year></dates><urls></urls></record></Cite></EndNote>[68]通过微波加热法，在20分钟内就合成了2DCOF-5和3DCOF-102，极大提高合成速率，并且使大规模制备COFs材料成为可能。微波加热合成COFs实验操作较为简易，可以在没有冷冻泵解冻和火焰密封过程的开放系统中进行，并且能够捕集和去除在COFs孔中的杂质，提供获得更大比表面积的机会。离子热合成法离子热法中，将熔融盐或离子液体同时用作溶剂和催化剂，在高温（约400℃）和压力下形成COFs。离子热法常用于制备基于三嗪的共价有机骨架材料。Kuhn等ADDINEN.CITE<EndNote><Cite><Author>Kuhn</Author><Year>2008</Year><RecNum>195</RecNum><DisplayText><styleface="superscript">[60]</style></DisplayText><record><rec-number>195</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1583674013">195</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kuhn,Pierre</author><author>MarkusAntonietti</author><author>Thomas,Arne</author></authors></contributors><titles><title>Porous,CovalentTriazine-BasedFrameworksPreparedbyIonothermalSynthesis</title><secondary-title>AngewandteChemieInternationalEdition</secondary-title></titles><periodical><full-title>AngewandteChemieInternationalEdition</full-title><abbr-1>Angew.Chem.Int.Ed.</abbr-1><abbr-2>AngewChemIntEd</abbr-2></periodical><pages>3450-3453</pages><volume>47</volume><number>18</number><dates><year>2008</year></dates><urls></urls></record></Cite></EndNote>[60]使用离子热法以熔融的ZnCl2盐同时作为溶剂和反应的催化剂，在400℃下通过腈结构单元的环化和三聚反应得到了多孔晶态共价三嗪框架材料。但在合成COFs的过程中也存在一些问题，如需要长时间高温反应的条件，以及在该条件下材料的部分碳化和熔融盐的残留等，导致这类多孔材料比溶剂热合成法的COFs材料结晶度差，限制了离子热合成方法的应用。离子液体是具有低熔点的熔融有机盐，对环境无害，可以重复使用而不会失去活性，近年来作为反应介质来合成亚胺基的2DCOF和3DCOF。这种方法合成COFs材料快速简单且具有成本效益。已经有研究将室温下为液体的1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐同时作为\o"从ScienceDirect的AI生成的主题页面中了解有关Schiff基地的更多信息"席夫碱反应合成COFs的溶剂和催化剂，开发了一种在环境温度和压力下高反应速度合成3DCOF（3D-IL-COF）的技术ADDINEN.CITE<EndNote><Cite><Author>Guan</Author><Year>2018</Year><RecNum>527</RecNum><DisplayText><styleface="superscript">[69]</style></DisplayText><record><rec-number>527</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1615115011">527</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Guan,XinYu</author><author>Ma,YunChao</author><author>Li,Hui</author><author>Yusran,Yusran</author><author>Xue,Ming</author><author>Fang,QianRong</author><author>Yan,YuShan</author><author>Valtchev,Valentin</author><author>Qiu,ShiLun</author></authors></contributors><titles><title>Fast,AmbientTemperatureandPressureIonothermalSynthesisofThree-DimensionalCovalentOrganicFrameworks</title><secondary-title>JournaloftheAmericanChemicalSociety</secondary-title></titles><periodical><full-title>JournaloftheAmericanChemicalSociety</full-title><abbr-1>J.Am.Chem.Soc.</abbr-1><abbr-2>JAmChemSoc</abbr-2></periodical><pages>4494-4498</pages><volume>140</volume><number>13</number><dates><year>2018</year><pub-dates><date>03/19</date></pub-dates></dates><urls></urls><electronic-resource-num>10.1021/jacs.8b01320</electronic-resource-num></record></Cite></EndNote>[69]。机械研磨法机械研磨法是利用研钵和研杵等简单实验装置将单体磨碎即可合成COF材料。Banerjee教授等ADDINEN.CITE<EndNote><CiteExcludeYear="1"><Author>Biswal</Author><RecNum>196</RecNum><DisplayText><styleface="superscript">[70]</style></DisplayText><record><rec-number>196</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1583674013">196</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Biswal,BishnuP.</author><author>Chandra,Suman</author><author>Kandambeth,Sharath</author><author>Lukose,Binit</author><author>Heine,Thomas</author><author>Banerjee,Rahul</author></authors></contributors><titles><title>MechanochemicalSynthesisofChemicallyStableIsoreticularCovalentOrganicFrameworks</title><secondary-title>JournaloftheAmericanChemicalSociety</secondary-title></titles><periodical><full-title>JournaloftheAmericanChemicalSociety</full-title><abbr-1>J.Am.Chem.Soc.</abbr-1><abbr-2>JAmChemSoc</abbr-2></periodical><pages>5328-5331</pages><volume>135</volume><number>14</number><dates><year>2013</year></dates><urls></urls></record></Cite></EndNote>[70]通过室温无溶剂的机械研磨法成功制备了化学稳定的COFs材料（TpPa-1，TpPa-2和TpBD）。机械研磨法合成的COFs化学稳定性与溶剂热法较为一致，合成过程操作快速，只需要简单的实验装置，但合成的COFs材料结晶度较低，比表面积小，产物通常为无定形或结晶不良的结构。1.2共价有机骨架材料吸附重金属研究COFs优异的理化性质在去除重金属离子中发挥重要作用。目前已开展一些COFs吸附重金属离子的研究，包括Hg2+、Pb2+、Cd2+和变价金属离子等。COFs作为性能稳定的吸附剂材料，主要通过表面络合配位和离子交换等机制实现对重金属的吸附。1.2.1Hg2+在众多重金属离子中，利用COFs从水溶液中去除Hg2+已经被广泛探究。研究表明Hg2+倾向于与含N和S官能团形成稳定的络合物，例如-NH2，-NH-、-N=、-CN、-SR、-SH等ADDINEN.CITE<EndNote><CiteExcludeYear="1"><Author>Zhu</Author><RecNum>226</RecNum><DisplayText><styleface="superscript">[71]</style></DisplayText><record><rec-number>226</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1584467122">226</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhu,JianZhong</author><author>Deng,BaoLin</author><author>JohnYang</author><author>GangDianChen</author></authors></contributors><titles><title>Modifyingactivatedcarbonwithhybridligandsforenhancingaqueousmercuryremoval</title><secondary-title>Carbon</secondary-title></titles><pages>2014-2025</pages><volume>47</volume><number>8</number><dates><year>2009</year></dates><urls></urls></record></Cite></EndNote>[71]，因此一些含N和S基团的共价有机骨架对重金属离子表现出优异的吸附性能。Huang等ADDINEN.CITE<EndNote><CiteExcludeYear="1"><Author>Huang</Author><RecNum>117</RecNum><DisplayText><styleface="superscript">[72]</style></DisplayText><record><rec-number>117</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1575554118">117</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Huang,Ning</author><author>Zhai,LiPeng</author><author>Xu,Hong</author><author>Jiang,DongLin</author></authors></contributors><titles><title>StableCovalentOrganicFrameworksforExceptionalMercuryRemovalfromAqueousSolutions</title><secondary-title>JournaloftheAmericanChemicalSociety</secondary-title></titles><periodical><full-title>JournaloftheAmericanChemicalSociety</full-title><abbr-1>J.Am.Chem.Soc.</abbr-1><abbr-2>JAmChemSoc</abbr-2></periodical><pages>2428-2434</pages><volume>139</volume><number>6</number><dates><year>2017</year></dates><urls></urls></record></Cite></EndNote>[72]以自下而上法直接合成的共价有机骨架（TAPB-BMTTPA-COF）对Hg2+饱和吸附量可达734mg/g，并且发现TAPB-BMTTPA-COF捕获Hg2+的主要机制为甲硫基与Hg（II）的配位作用。和直接合成法一样，后修饰法合成含硫官能团的COFs也能实现对Hg2+的吸附。He等ADDINEN.CITE<EndNote><Cite><Author>He</Author><Year>2020</Year><RecNum>632</RecNum><DisplayText><styleface="superscript">[73]</style></DisplayText><record><rec-number>632</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1618766642">632</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>He,YuLong</author><author>Wang,XiaoMin</author><author>Wang,Kang</author><author>Wang,LiMin</author></authors></contributors><titles><title>Atriarylamine-basedfluorescentcovalentorganicframeworkforefficientdetectionandremovalofMercury(II)ion</title><secondary-title>DyesandPigments</secondary-title></titles><pages>107880</pages><volume>173</volume><keywords><keyword>Suzukipolymerization</keyword><keyword>Fluorescentsensor</keyword><keyword>Hgdetection</keyword><keyword>Hgremoval</keyword></keywords><dates><year>2020</year><pub-dates><date>2020/02/01/</date></pub-dates></dates><isbn>0143-7208</isbn><urls><related-urls><url><styleface="underline"font="default"size="100%">/science/article/pii/S0143720819315682</style></url></related-urls></urls><electronic-resource-num><styleface="underline"font="default"size="100%">/10.1016/j.dyepig.2019.107880</style></electronic-resource-num></record></Cite></EndNote>[73]基于两种三芳基胺单体的Suzuki聚合反应设计了一种共价有机骨架，并进一步用硫代氨基脲修饰合成了TNPP，同时将TNPP应用于溶液Hg2+的吸附。结果表明吸附过程中TNPP上的N和S原子与Hg2+发生相互作用。研究也将硫醇基团接枝于含反应性乙炔基的共价有机骨架进一步合成TPB-DMTP-COF-SH（图1.4），结果表明TPB-DMTP-COF-SH通过硫醇或三唑基团与Hg2+的协同鳌合作用，在10min内就可以使溶液中Hg2+浓度从10mg/L降低到1.5ug/LADDINEN.CITE<EndNote><CiteExcludeYear="1"><Author>Merí-Bofí</Author><RecNum>125</RecNum><DisplayText><styleface="superscript">[59]</style></DisplayText><record><rec-number>125</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1575555165">125</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Merí-Bofí,Laura</author><author>Royuela,Sergio</author><author>Zamora,Felix</author><author>Ruiz-Gonzales,Luisa</author><author>Segura,Jose</author><author>Mu?oz-Olivas,Riansares</author><author>Manche?o,MaríaJosé</author></authors></contributors><titles><title>ThiolGraftedImine-BasedCovalentOrganicFrameworkforWaterRemediationThroughSelectiveRemovalofHg(II)</title><secondary-title>JournalofMaterialsChemistryA</secondary-title></titles><pages>10.1039.C7TA05588A</pages><dates></dates><urls></urls></record></Cite></EndNote>[59]。Sun等ADDINEN.CITE<EndNote><CiteExcludeYear="1"><Author>Sun</Author><RecNum>228</RecNum><DisplayText><styleface="superscript">[74]</style></DisplayText><record><rec-number>228</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1584467122">228</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Sun,Qi</author><author>Aguila,Briana</author><author>Perman,Jason</author><author>Earl,LyndseyD.</author><author>Abney,CarterW.</author><author>Cheng,Yuchuan</author><author>Wei,Hao</author><author>Nguyen,Nicholas</author><author>Wojtas,Lukasz</author><author>Ma,Shengqian</author></authors></contributors><titles><title>PostsyntheticallyModifiedCovalentOrganicFrameworksforEfficientandEffectiveMercuryRemoval</title><secondary-title>JournaloftheAmericanChemicalSociety</secondary-title></titles><periodical><full-title>JournaloftheAmericanChemicalSociety</full-title><abbr-1>J.Am.Chem.Soc.</abbr-1><abbr-2>JAmChemSoc</abbr-2></periodical><pages>2786-2793</pages><volume>139</volume><number>7</number><dates><year>2017</year></dates><urls></urls></record></Cite></EndNote>[74]也通过硫醇-烯“点击反应”合成COF-S-SH，对Hg2+吸附容量高达1350mg/g，研究结果表明Hg2+在COF-S-SH材料上快速扩散并与巯基配位引起的协同效应有利于COF-S-SH对Hg2+的吸附。图1.4TPB-DMTP-COF-SH的合成示意图Figure1.4SyntheticschemediagramofTPB-DMTP-COF-SH.除了含硫基团，富氮和富氧基团也能为缺电子的Hg2+提供电子。Li等ADDINEN.CITE<EndNote><CiteExcludeYear="1"><Author>Li</Author><RecNum>229</RecNum><DisplayText><styleface="superscript">[75]</style></DisplayText><record><rec-number>229</rec-number><foreign-keys><keyapp="EN"db-id="v5xzzxr2z02stmeepv9x5rf6xe2pdpx9ddwr"timestamp="1584467122">229</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Li,Ya</author><author>Wang,Chang</