金屬-有機(jī)骨架材料(MOF)的分類教學(xué)文稿

金屬-有機(jī)骨架材料（MOF）的分類及其在計(jì)算化學(xué)的發(fā)展和前景李鵬李芳2024/9/26ContentA.常見的金屬-有機(jī)骨架材料分類及其特點(diǎn)B.MOF材料的計(jì)算化學(xué)研究方法及應(yīng)用C.MOF材料應(yīng)用的前景通過使用含更長的二羧酸配體反應(yīng)物，IRMOF系列化合物的孔道尺寸可以增大到28.8?，孔隙率從55.8%增大到91.1%，大大超過了沸石的孔隙率。IRMOF材料用于合成IRMOF系列材料的不同配體IRMOF是由分離的次級(jí)結(jié)構(gòu)單元[Zn4O]6+無機(jī)基團(tuán)與一系列芳香羧酸配體，以八面體形式橋連自組裝而成的微孔晶體材料。MohamedEddaoudi,JaheonKim,NathanielRosi,DavidVodak,JosephWachter,MichaelO’Keeffe,OmarM.Yaghi*.SystematicDesignofPoreSizeandFunctionalityinIsoreticularMOFsandTheirApplicationinMethaneStorage.Science,2003,300,1127ZIF材料ZIF，即類沸石咪唑酯骨架材料，是利用Zn(Ⅱ)或Co(Ⅱ)與咪唑配體反應(yīng)，合成出的類沸石結(jié)構(gòu)的MOF材料。BoWang,AdrienP.Co?te′,HiroyasuFurukawa,MichaelO’Keeffe&OmarM.Yaghi.Nature,2008,(453)207.ANHPHAN,CHRISTIANJ.DOONAN,FERNANDOJ.URIBE-ROMO,CAROLYNB.KNOBLER,MICHAELO’KEEFFE,ANDOMARM.YAGHI*.ACCOUNTSOFCHEMICALRESEARCH.2010(43).58-67.CPL系列材料CPL材料的結(jié)構(gòu)由六配位金屬元素與中性的含氮雜環(huán)類的2,2’-聯(lián)吡啶、4,4’-聯(lián)吡啶、苯酚等配體配位而成。其中的四個(gè)配位位置是金屬和吡嗪類羧酸配體鏈接而成的二維平面結(jié)構(gòu)，剩下的兩個(gè)位置是金屬與線形二齒有機(jī)配體配位形成。Angew.Chem.Int.Ed.1999,38,No.1-2,140-143Angew.Chem.Int.Ed.2008,120,3978–3982MIL系列材料MIL材料是使用不同的過渡金屬元素和琥珀酸、戊二酸等二羧酸配體合成。其最大的一個(gè)特點(diǎn)就是在外界因素的刺激下，材料結(jié)構(gòu)會(huì)在大孔和窄孔兩種形態(tài)之間轉(zhuǎn)變，即呼吸現(xiàn)象。PCN材料PCN系列材料含有多個(gè)立方八面體納米孔籠，并在空間上形成孔籠-孔道狀拓?fù)浣Y(jié)構(gòu)。這種材料在氣體存儲(chǔ)方面有巨大潛力。J.AM.CHEM.SOC.2008,130,1012-1016UiO系列材料UiO材料由含Zr（鋯）的正八面體[Zr6O4(OH)4]與12個(gè)對苯二甲酸(BDC)有機(jī)配體相連，形成包含八面體中心孔籠和八個(gè)四面體角籠的三維微孔結(jié)構(gòu)。J.AM.CHEM.SOC.2008,130,13850–13851Chem.Commun.,2011,47,9603–9605B.MOF材料的計(jì)算化學(xué)研究方法及應(yīng)用量子力學(xué)方法分子模擬方法分子力學(xué)方法第一性原理方法、密度泛函理論蒙特卡羅方法、分子動(dòng)力學(xué)方法Experimental?ComputationalcombinationThemethanemoleculeusingtheTransferablePotentialsforPhaseEquilibriaUnitedAtom(TraPPE-UA)forcefield,inwhichCH4ismodeledasasingle,unchargedLJspherelocatedonthecarbonatom.FortheZIFatoms,weuseLJparameterstakenfromtheOptimizedPotentialsforLiquidSimulationsAllAtom(OPLS-AA)forcefield,UFFforZn.GCMC→Complex

ChemicalSystems(MCCCS)Towheeprogram.

Bindingenergies→Large-scaleAtomic/MolecularMassivelyParallelSimulator

(LAMMPS)J.Phys.Chem.C2013,117,10326?10335ThecorrespondingisothermsfromtheGCMCsimulation,whichagreewithexperimentallymeasuredvaluestowithin13%,validatingourchosenOPLSparametersforthesesystems.TheCH4adsorptions:ZIF-71<-97<-93<-96<-25.TheseresultssuggestthatthedominantinfluenceonadsorptionofCH4intheZIFsisBETsurfaceareaorfreevolume,consistentwithresultsobtainedbytheSnurrgroupandWangetal.低壓高壓RSCAdv.,2014,4,16503GCMCsimulationmethodsProgram:MultipurposeSimulationCode(MuSiC-4.0)developedbytheSnurrgroup.Interconversionoffugacityandpressure:Peng–Robinsonequationofstate(PREOS).Model:ZIF-8frameworksweretreatedasrigidwithfrozenatom,H2andCH4wererepresentedbyaunited–atommodel,N2andCO2weremimickedasathree-siterigidmodel.CutoffradiusofLJinteractions:1.4nmLong-rangeelectrostaticinteractions:EwaldmethodSteps:107,50%forequilibration,50%forcalculatingtheensembleaverages.Forcefieldparameters:?=0.635?UFF

andσ=1.0σUFFForcefieldvalidationTheeffectofstructureontheexcessCH4uptakefollowstheorderZIF8HL>ZIF-8>ZIF8_55CH4UC>ZIF8_ja3AdsorptionsitesAt1barand77K,alittleamountofH2moleculesareadsorbedonZIF-8frameworkandtheirpreferentialadsorptionsitesareclosetotheimidazolerings.Withincreasingofgaspressure,moreH2moleculesareadsorbedinthemiddleofthefacesoftheaccessiblesurfaceareaofZIF-8framework.TheCH4adsorptionisothermsforfourdifferentinitialstructuresofZIF-8at298KhavebeencomputedusingGCMCsimulationswiththeproposedforcefieldadsorptionisothermsforfourgasessuchasCH4,H2,CO2

and

N2

atdifferenttemperatureswerecomputedusingGCMCsimulationandwerefoundtobeinagoodagreementwiththeexperimentaldata.InthecaseofH2,theprobabilitydensitydistributionprofilesindicatethatthepreferentialadsorption

sitesofH2molecules