MOF研究状况

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 鲁班奖评选办法下载鲁班奖评选办法下载鲁班奖评选办法下载企业年金办法下载企业年金办法下载 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,2007,315,1828-1831MIL88DSelectivityadsorptionforCO2overCH4inMIL53MOF-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-likemotifFacetedpolyhedraTetrahedralandoctahedralcoordinationmodelMOFsasarts美丽而多才多艺的晶体金刚石，三维骨架结构，坚硬，不导电石墨，层状结构，柔软，导电球烯，60个碳组成足球结构，具超导性碳纳米管，细管径小至1个纳米左右，硬度极高，导体、半导体认识晶体开发晶体 设计 领导形象设计圆作业设计ao工艺污水处理厂设计附属工程施工组织设计清扫机器人结构设计 晶体石墨烯晶体已知材料中最薄的一种，还非常牢固坚硬；作为单质，它在室温下传递电子的速度比已知导体都快,石墨烯结构非常稳定，迄今为止，研究者仍未发现石墨烯中有碳原子缺失的情况。石墨烯中各碳原子之间的连接非常柔韧，当施加外部机械力时，碳原子面就弯曲变形,石墨烯最大的特性是其中电子的运动速度达到了光速的1/300