奇妙的金属有机骨架材料

奇妙的金属有机骨架材料MagicMetal-OrganicFrameworks根据联合国政府间气候变化专门委员会（IPCC）规定，目前由人类活动引起的大量聚集在大气中的温室气体主要是二氧化碳、甲烷、一氧化氮、六氟化硫和两组工业气体氢氟烃(HFCs)和全氟烃(PFCs)温室气体效应环境污染与能源危机解决办法1，捕获并存储排放的气体2，开发基于氢的清洁能源新材料存储金属有机骨架材料MOFs什么是金属有机骨架材料MOFs？CuAg配体的种类金属有机骨架材料MOFs的奇妙之处：有大的表面积与质量比，能象海绵吸水那样吸收大量气体，比沸石和活性碳好，能用于气体存储、气体分离。能用作传感器、缓释药品的给药载体。能用作发光材料、磁性材料。能将存储功能与催化作用结合，将捕获的二氧化碳转化为有用的燃料如甲醇，能用作车载储氢材料国际能源暑（IEA）提出的氢能源实用化的目标：质量储氢率5%，体积储氢率50g/L，美国能源部（DOE）提出的氢能源实用化的目标：质量储氢率6.5%，体积储氢率62g/L，车用储氢能力3.1kgFerey,G.etal,Science,2005,309,2040-2042MIL100andMIL101MIL101,H2,77K,6.1wt%poresize,30-40angstromsLangmuirsurfaceareaforN2,5900m2/gCO2,400m3perm3MIL101气体吸附与存储Ferey,G.etal,Science,2007,315,1828-1831OOHOHOMIL88DSelectivityadsorptionforCO2overCH4inMIL53MOF-5,Zn4O(BDC)3MOF-177,Zn4O(BTB)3Secondarybuildingunits(SBUs)a,thesqure“paddlewheel”cluster.b,theoctahedral“basiczincacetate”cluster.c,thetrigonalprismaticoxo-centeredtrimer.ShapedbodiesmadefromMOFmaterialsYaghi,O.M.,J.Am.Chem.Soc.,2008,130,11580Yaghi,O.M.,J.Am.Chem.Soc.,2008,130,11580Alargeseriesofisoreticularmetal-organic(IRMOFs)wereproducedbyYaghigroupYaghi,O.M.,Science,2008,319,939-943Zeoliticimidazolateframeworks(ZIFs)1,tetrahedralframeworks2,highthermalstability(upto390degree)3,highporosity(1970m2/g)4,unusualselectivityforCO2capturefromCO2/COmixturesZIF-69,83LCO2/perLat273KYaghi,O.M.,Science,2008,319,939-943N2adsorptionisothermsat77KTheCO2/COadsorptionisothermsforZIF-69at273KGasadsorptionisothermsofZIF-95(77K)andZIF-100(87K)Yaghi,O.M.,Nature,2008,453,207-211ZIF95,1240m2/g,0.43cm3/gZIF100,780m2/g,0.37cm3/gYaghi,O.M.,Nature,2008,453,207-211Yaghi,O.M.,Science,2005,310,1166-1170Covalentorganicframeworks(COFs)COF1,poresize7angstroms,500degree,711m2/gCOF5,poresize27angstroms,600degree,1590m2/gYaghi,O.M.,J.Am.Chem.Soc.,2009,8875-8883COF102,72mg/gH277K;187mg/gCH4,1180mg/gCO2,298KLow-pressureH2isothermsat77KHigh-pressureH2isothermsat77KHigh-pressureCH4isothermsat298KH2-storagecapacitiesfordifferentMOFsYaghi,O.M.,Science,2010,329,424-428MOF-177MOF-180MOF-200MOF-205MOF-210Chen,X.M.,Inorg.Chem.,2009,3882-3889Langmuirsurfacearea195m2/gBETsurfacearea155m2/g1.56CO2moleculesperunitporeLangmuirsurfacearea,1100m2/g,BETsurfacearea,914m2/gPorevolume,0.39cm3/gN2adsorbedinthepore,337mg/gBai,J.F.Chem.Commun.,2009,7551-7553Asmallcage8.5angAlargepore8.8*21.5angMOF-505analog.Cu2(EBTC)Langmuirsurfacearea2844m2/gBETsurfacearea1852m2/g286cm3/gH2at77K2.58wt%178cm3/gCO2at273K252cm3/gC2H2at273KC2H2Bu,X.H.,Chem.J.Eur.,2008,2771-2776TheselectivesorptionofO2andCO2overN2Diameter,O23.46Å;CO23.3Å;N23.64Å;H22.8Å;CO3.76Å79.3cm3/gO2at77K98.8cm3/gCO2at195KLangmuirsurfacearea279and390m2/gforO2andCO2;BETsurfacearea246and313m2/gforO2andCO2MOF作为发光材料RepresentationofemissionpossibilitiesinaporousMOFStructureandluminescencepropertiesofZn3L3(DMF)2(left)andZn4OL3(right)[Cd3L6](BF4)2(SiF6)(OH)2+13.5H2OLis2,6-di(4-triazolyl)pyridineLuminescencespectraofcomplexeswithincreasingdehydrationandpartiallyrehydratedCu6L6+H2O+DMSO,1Dnanotubularchannels1.2nmLis5,6-diphenyl-1,2,4-triazine-3-thiolLuminiscencespectraoftheporoussolidandafterImmersingthissolidinanaqueoussolutionoftoluene[Eu(pdc)1.5(dmf)](DMF)0.5(H2O)0.5pdcispyridine-3,5-dicarbrateCu(NO3)2atdifferentconcentrationComparisonofdifferentmetalionsCoordinationtometala,1DInO4(OH)2Chainin1b,fourTBAPytoanIn(III)c,eightIntooneTBAPyd,e,f,3Dviewalong[001][010]directionsIn(NO3)3850CDMF+dioxane+H2O[In2(OH)2(TBAPy)]+guests1Theframeworkstructureoftoluene-loaded1`Fluorescence(blue)andexcitation(red)1+1`+TBAPyN2adsorptionisothermof1`at77Kand1barEffectofDMFmoleculesonthefluorescenceof1Guest-dependentfluorescenceemissionof1Fujita,M.etal,J.Am.Chem.Soc.,2008,1578-1579Directobservationofthelabileimineformationthroughsingle-crystal-to-single-crystalreactionintheporesofaPorouscoordinationnetworkChangesincolorandmagneticpropertiesofCo[Cr(CN)6]2/3+zH2OdependonthehumidityUnsaturatedmetalconnectingpointsasactivecatalyticsitesActivecatalyticsitesintothebridgingligandsofMOFsMOFsascatalyst1Dtriangularshapechannelwithasizeof13.4ang,ShowingthecatalyticcentreandthechiralpocketTransesterificationreactioncatalyzedby82Dinfiniteframework[Cu2(L8)2(H2O)2]MeOH.H2O.Thewatermoleculesterminatingthecopperwereremoveduponheating,allowingtheexposedcoppercenterstofunctionasLewisacidcatalyticreactioncentersTheasymmetricring-openingofepoxideswithamines,Yield54%,enantiomericexcess45%[Cd3Cl6(L14)3],EnantioselectivelycatalyzediethylzineadditionstoaromaticaldehydesPaddle-wheelcopper(II)tetracarboxylatebuildingblockfor[Cu3(C9O6H3)2(H2O)3]ShowingnanochannelswithfourfoldsymmetryandtemperaturedependentmagneticsusceptibilityMOFsasmagnetsCu3(PTMTC)2(py)6(EtOH)2(H2O)ReversiblesolvatomagneticeffectsindynamicporousmagnetsReversiblesolvatomagneticeffectsindynamicporousmagnets[Co3(OH)2(C2O4)2]3H2OFujita,M.etal,Chem.Commun.,2009,1638-1640Fujita,M.etal,Science,2006,313,1273-1276Kitagawa,S.,etal,J.Am.Chem.Soc.,2009,12790-12800Cubicdiamondoid,HexagonaldiamondoidOctahedralmetalnodes,Squaregrid,octahedralnetworkMetal-organicoctahedraljoinedthroughPerchlorateanionsintoacyclohexane-l