MOF教學(xué)講解課件

奇妙的金屬有機(jī)骨架材料MagicMetal-OrganicFrameworks.奇妙的金屬有機(jī)骨架材料MagicMetal-Organic1根據(jù)聯(lián)合國政府間氣候變化專門委員會（IPCC）規(guī)定，目前由人類活動引起的大量聚集在大氣中的溫室氣體主要是二氧化碳、甲烷、一氧化氮、六氟化硫和兩組工業(yè)氣體氫氟烴(HFCs)和全氟烴(PFCs)

溫室氣體效應(yīng)環(huán)境污染與能源危機(jī).根據(jù)聯(lián)合國政府間氣候變化專門委員會（IPCC）規(guī)定，目前由人2解決辦法1，捕獲并存儲排放的氣體2，開發(fā)基于氫的清潔能源新材料存儲金屬有機(jī)骨架材料MOFs.解決辦法新材料存儲金屬有機(jī)骨架材料MOFs.3什么是金屬有機(jī)骨架材料MOFs？CuAg.什么是金屬有機(jī)骨架材料MOFs？CuAg.4..5配體的種類.配體的種類.6..7..8..9金屬有機(jī)骨架材料MOFs的奇妙之處：有大的表面積與質(zhì)量比，能象海綿吸水那樣吸收大量氣體，比沸石和活性碳好，能用于氣體存儲、氣體分離。能用作傳感器、緩釋藥品的給藥載體。能用作發(fā)光材料、磁性材料。能將存儲功能與催化作用結(jié)合，將捕獲的二氧化碳轉(zhuǎn)化為有用的燃料如甲醇，能用作車載儲氫材料.金屬有機(jī)骨架材料MOFs的奇妙之處：有大的表面積與10國際能源暑（IEA）提出的氫能源實用化的目標(biāo)：質(zhì)量儲氫率5%，體積儲氫率50g/L，美國能源部（DOE）提出的氫能源實用化的目標(biāo)：質(zhì)量儲氫率6.5%，體積儲氫率62g/L，車用儲氫能力3.1kg.國際能源暑（IEA）提出的氫能源實用化的目標(biāo)：美11Ferey,G.etal,Science,2005,309,2040-2042MIL100andMIL101MIL101,H2,77K,6.1wt%poresize,30-40angstromsLangmuirsurfaceareaforN2,5900m2/gCO2,400m3perm3MIL101

氣體吸附與存儲.Ferey,G.etal,Science,200512Ferey,G.etal,Science,2007,315,1828-1831MIL88DSelectivityadsorptionforCO2overCH4inMIL53.Ferey,G.etal,Science,200713MOF-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.,2008,130,11580.MOF-5,Zn4O(BDC)3MOF-177,Zn4O14..15Yaghi,O.M.,J.Am.Chem.Soc.,2008,130,11580.Yaghi,O.M.,J.Am.Chem.Soc.16..17Alargeseriesofisoreticularmetal-organic(IRMOFs)wereproducedbyYaghigroup.Alargeseriesofisoreticular18Yaghi,O.M.,Science,2008,319,939-943Zeoliticimidazolateframeworks(ZIFs)1,tetrahedralframeworks2,highthermalstability(upto390degree)3,highporosity(>1970m2/g)4,unusualselectivityforCO2capturefromCO2/COmixturesZIF-69,83LCO2/perLat273K.Yaghi,O.M.,Science,2008,31919Yaghi,O.M.,Science,2008,319,939-943.Yaghi,O.M.,Science,2008,31920N2adsorptionisothermsat77KTheCO2/COadsorptionisothermsforZIF-69at273KGasadsorptionisothermsofZIF-95(77K)andZIF-100(87K)Yaghi,O.M.,Nature,2008,453,207-211ZIF95,1240m2/g,0.43cm3/gZIF100,780m2/g,0.37cm3/g.N2adsorptionisothermsat77K21Yaghi,O.M.,Nature,2008,453,207-211.Yaghi,O.M.,Nature,2008,453,22Yaghi,O.M.,Science,2005,310,1166-1170Covalentorganicframeworks(COFs)COF1,poresize7angstroms,500degree,711m2/g.Yaghi,O.M.,Science,2005,31023COF5,poresize27angstroms,600degree,1590m2/g.COF5,poresize27angstroms,24Yaghi,O.M.,J.Am.Chem.Soc.,2009,8875-8883.Yaghi,O.M.,J.Am.Chem.Soc.25COF102,72mg/gH277K;187mg/gCH4,1180mg/gCO2,298K.COF102,72mg/gH277K;187mg/26Low-pressureH2isothermsat77KHigh-pressureH2isothermsat77KHigh-pressureCH4isothermsat298KH2-storagecapacitiesfordifferentMOFs.Low-pressureH2isothermsat727Yaghi,O.M.,Science,2010,329,424-428MOF-177MOF-180.Yaghi,O.M.,Science,2010,32928MOF-200MOF-205.MOF-200MOF-205.29MOF-210.MOF-210.30Chen,X.M.,Inorg.Chem.,2009,3882-3889Langmuirsurfacearea195m2/gBETsurfacearea155m2/g1.56CO2moleculesperunitpore.Chen,X.M.,Inorg.Chem.,20031Langmuirsurfacearea,1100m2/g,BETsurfacearea,914m2/gPorevolume,0.39cm3/gN2adsorbedinthepore,337mg/g

.Langmuirsurfacearea,1100m2/32Bai,J.F.Chem.Commun.,2009,7551-7553Asmallcage8.5angAlargepore8.8*21.5angMOF-505analog.Cu2(EBTC)Langmuirsurfacearea2844m2/gBETsurfacearea1852m2/g286cm3/gH2at77K2.58wt%178cm3/gCO2at273K252cm3/gC2H2at273KC2H2.Bai,J.F.Chem.Commun.,200933Bu,X.H.,Chem.J.Eur.,2008,2771-2776.Bu,X.H.,Chem.J.Eur.,2008,34TheselectivesorptionofO2andCO2overN2Diameter,O23.46?;CO23.3?;N23.64?;H22.8?;CO3.76?

79.3cm3/gO2at77K98.8cm3/gCO2at195KLangmuirsurfacearea279and390m2/gforO2andCO2;BETsurfacearea246and313m2/gforO2andCO2.TheselectivesorptionofO2a35MOF作為發(fā)光材料RepresentationofemissionpossibilitiesinaporousMOF.MOF作為發(fā)光材料Representationofemi36StructureandluminescencepropertiesofZn3L3(DMF)2(left)andZn4OL3(right)[Cd3L6](BF4)2(SiF6)(OH)2+13.5H2OLis2,6-di(4-triazolyl)pyridineLuminescencespectraofcomplexeswithincreasingdehydrationandpartiallyrehydrated.Structureandluminescencepro37Cu6L6+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)2atdifferentconcentrationComparisonofdifferentmetalionsCoordinationtometal.Cu6L6+H2O+DMSO,1Dnanotubular38a,1DInO4(OH)2Chainin1b,fourTBAPytoanIn(III)c,eightIntooneTBAPyd,e,f,3Dviewalong[001][010]directionsIn(NO3)3850CDMF+dioxane+H2O[In2(OH)2(TBAPy)]+guests1.a,1DInO4(OH)2Chainin1In(N39Theframeworkstructureoftoluene-loaded1`Fluorescence(blue)andexcitation(red)1+1`+TBAPy.Theframeworkstructureoftol40N2adsorptionisothermof1`at77Kand1barEffectofDMFmoleculesonthefluorescenceof1Guest-dependentfluorescenceemissionof1.N2adsorptionisothermof1`a41Fujita,M.etal,J.Am.Chem.Soc.,2008,1578-1579Directobservationofthelabileimineformationthroughsingle-crystal-to-single-crystalreactionintheporesofaPorouscoordinationnetwork.Fujita,M.etal,J.Am.Chem.S42ChangesincolorandmagneticpropertiesofCo[Cr(CN)6]2/3+zH2Odependonthehumidity.Changesincolorandmagnetic43UnsaturatedmetalconnectingpointsasactivecatalyticsitesActivecatalyticsitesintothebridgingligandsofMOFsMOFsascatalyst.Unsaturatedmetalconnectingp441Dtriangularshapechannelwithasizeof13.4ang,ShowingthecatalyticcentreandthechiralpocketTransesterificationreactioncatalyzedby8.1Dtriangularshapechannelwi452Dinfiniteframework[Cu2(L8)2(H2O)2]MeOH.H2O.Thewatermoleculesterminatingthecopperwereremoveduponheating,allowingtheexposedcoppercenterstofunctionasLewisacidcatalyticreactioncentersTheasymmetricring-openingofepoxideswithamines,Yield54%,enantiomericexcess45%[Cd3Cl6(L14)3],Enantioselectivelycatalyzediethylzineadditionstoaromaticaldehydes.2Dinfiniteframework[Cu2(L8)46Paddle-wheelcopper(II)tetracarboxylatebuildingblockfor[Cu3(C9O6H3)2(H2O)3]ShowingnanochannelswithfourfoldsymmetryandtemperaturedependentmagneticsusceptibilityMOFsasmagnets.Paddle-wheelcopper(II)tetrac47Cu3(PTMTC)2(py)6(EtOH)2(H2O)Reversiblesolvatomagneticeffectsindynamicporousmagnets.Cu3(PTMTC)2(py)6(EtOH)2(H2O)Re48Reversiblesolvatomagneticeffectsindynamicporousmagnets[Co3(OH)2(C2O4)2]3H2O.Reversiblesolvatomagneticeff49Fujita,M.etal,Chem.Commun.,2009,1638-1640Fujita,M.etal,Science,2006,313,1273-1276.Fujita,M.etal,Chem.Commun50Kitagawa,S.,etal,J.Am.Chem.Soc.,2009,12790-12800.Kitagawa,S.,etal,J.Am.Chem.51Cubicdiamondoid,HexagonaldiamondoidOctahedralmetalnodes,Squaregrid,octahedralnetworkMetal-organicoctahedraljoinedthroughPerchlorateanionsintoacyclohexane-likemotifFacetedpolyhedraTetrahedralandoctahedralcoordinationmodelMOFsasarts.Cubicdiamondoid,Hexagonaldia52美麗而多才多藝的晶體

金剛石，三維骨架結(jié)構(gòu)，堅硬，不導(dǎo)電石墨，層狀結(jié)構(gòu)，柔軟，導(dǎo)電球烯，60個碳組成足球結(jié)構(gòu)，具超導(dǎo)性碳納米管，細(xì)管徑小至1個納米左右，硬度極高，導(dǎo)體、半導(dǎo)體認(rèn)識晶體開發(fā)晶體設(shè)計晶體.美麗而多才多藝的晶體金剛石，三維骨架結(jié)構(gòu)，堅硬，不導(dǎo)電石墨53石墨烯晶體已知材料中最薄的一種，還非常牢固堅硬；作為單質(zhì)，它在室溫下傳遞電子的速度比已知導(dǎo)體都快,石墨烯結(jié)構(gòu)非常穩(wěn)定，迄今為止，研究者仍未發(fā)現(xiàn)石墨烯中有碳原子缺失的情況。石墨烯中各碳原子之間的連接非常柔韌，當(dāng)施加外部機(jī)械力時，碳原子面就彎曲變形,石墨烯最大的特性是其中電子的運(yùn)動速度達(dá)到了光速的1/300.石墨烯晶體已知材料中最薄的一種，還非常牢固堅硬；作為單質(zhì)，它54..55奇妙的金屬有機(jī)骨架材料MagicMetal-OrganicFrameworks.奇妙的金屬有機(jī)骨架材料MagicMetal-Organic56根據(jù)聯(lián)合國政府間氣候變化專門委員會（IPCC）規(guī)定，目前由人類活動引起的大量聚集在大氣中的溫室氣體主要是二氧化碳、甲烷、一氧化氮、六氟化硫和兩組工業(yè)氣體氫氟烴(HFCs)和全氟烴(PFCs)

溫室氣體效應(yīng)環(huán)境污染與能源危機(jī).根據(jù)聯(lián)合國政府間氣候變化專門委員會（IPCC）規(guī)定，目前由人57解決辦法1，捕獲并存儲排放的氣體2，開發(fā)基于氫的清潔能源新材料存儲金屬有機(jī)骨架材料MOFs.解決辦法新材料存儲金屬有機(jī)骨架材料MOFs.58什么是金屬有機(jī)骨架材料MOFs？CuAg.什么是金屬有機(jī)骨架材料MOFs？CuAg.59..60配體的種類.配體的種類.61..62..63..64金屬有機(jī)骨架材料MOFs的奇妙之處：有大的表面積與質(zhì)量比，能象海綿吸水那樣吸收大量氣體，比沸石和活性碳好，能用于氣體存儲、氣體分離。能用作傳感器、緩釋藥品的給藥載體。能用作發(fā)光材料、磁性材料。能將存儲功能與催化作用結(jié)合，將捕獲的二氧化碳轉(zhuǎn)化為有用的燃料如甲醇，能用作車載儲氫材料.金屬有機(jī)骨架材料MOFs的奇妙之處：有大的表面積與65國際能源暑（IEA）提出的氫能源實用化的目標(biāo)：質(zhì)量儲氫率5%，體積儲氫率50g/L，美國能源部（DOE）提出的氫能源實用化的目標(biāo)：質(zhì)量儲氫率6.5%，體積儲氫率62g/L，車用儲氫能力3.1kg.國際能源暑（IEA）提出的氫能源實用化的目標(biāo)：美66Ferey,G.etal,Science,2005,309,2040-2042MIL100andMIL101MIL101,H2,77K,6.1wt%poresize,30-40angstromsLangmuirsurfaceareaforN2,5900m2/gCO2,400m3perm3MIL101

氣體吸附與存儲.Ferey,G.etal,Science,200567Ferey,G.etal,Science,2007,315,1828-1831MIL88DSelectivityadsorptionforCO2overCH4inMIL53.Ferey,G.etal,Science,200768MOF-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.,2008,130,11580.MOF-5,Zn4O(BDC)3MOF-177,Zn4O69..70Yaghi,O.M.,J.Am.Chem.Soc.,2008,130,11580.Yaghi,O.M.,J.Am.Chem.Soc.71..72Alargeseriesofisoreticularmetal-organic(IRMOFs)wereproducedbyYaghigroup.Alargeseriesofisoreticular73Yaghi,O.M.,Science,2008,319,939-943Zeoliticimidazolateframeworks(ZIFs)1,tetrahedralframeworks2,highthermalstability(upto390degree)3,highporosity(>1970m2/g)4,unusualselectivityforCO2capturefromCO2/COmixturesZIF-69,83LCO2/perLat273K.Yaghi,O.M.,Science,2008,31974Yaghi,O.M.,Science,2008,319,939-943.Yaghi,O.M.,Science,2008,31975N2adsorptionisothermsat77KTheCO2/COadsorptionisothermsforZIF-69at273KGasadsorptionisothermsofZIF-95(77K)andZIF-100(87K)Yaghi,O.M.,Nature,2008,453,207-211ZIF95,1240m2/g,0.43cm3/gZIF100,780m2/g,0.37cm3/g.N2adsorptionisothermsat77K76Yaghi,O.M.,Nature,2008,453,207-211.Yaghi,O.M.,Nature,2008,453,77Yaghi,O.M.,Science,2005,310,1166-1170Covalentorganicframeworks(COFs)COF1,poresize7angstroms,500degree,711m2/g.Yaghi,O.M.,Science,2005,31078COF5,poresize27angstroms,600degree,1590m2/g.COF5,poresize27angstroms,79Yaghi,O.M.,J.Am.Chem.Soc.,2009,8875-8883.Yaghi,O.M.,J.Am.Chem.Soc.80COF102,72mg/gH277K;187mg/gCH4,1180mg/gCO2,298K.COF102,72mg/gH277K;187mg/81Low-pressureH2isothermsat77KHigh-pressureH2isothermsat77KHigh-pressureCH4isothermsat298KH2-storagecapacitiesfordifferentMOFs.Low-pressureH2isothermsat782Yaghi,O.M.,Science,2010,329,424-428MOF-177MOF-180.Yaghi,O.M.,Science,2010,32983MOF-200MOF-205.MOF-200MOF-205.84MOF-210.MOF-210.85Chen,X.M.,Inorg.Chem.,2009,3882-3889Langmuirsurfacearea195m2/gBETsurfacearea155m2/g1.56CO2moleculesperunitpore.Chen,X.M.,Inorg.Chem.,20086Langmuirsurfacearea,1100m2/g,BETsurfacearea,914m2/gPorevolume,0.39cm3/gN2adsorbedinthepore,337mg/g

.Langmuirsurfacearea,1100m2/87Bai,J.F.Chem.Commun.,2009,7551-7553Asmallcage8.5angAlargepore8.8*21.5angMOF-505analog.Cu2(EBTC)Langmuirsurfacearea2844m2/gBETsurfacearea1852m2/g286cm3/gH2at77K2.58wt%178cm3/gCO2at273K252cm3/gC2H2at273KC2H2.Bai,J.F.Chem.Commun.,200988Bu,X.H.,Chem.J.Eur.,2008,2771-2776.Bu,X.H.,Chem.J.Eur.,2008,89TheselectivesorptionofO2andCO2overN2Diameter,O23.46?;CO23.3?;N23.64?;H22.8?;CO3.76?

79.3cm3/gO2at77K98.8cm3/gCO2at195KLangmuirsurfacearea279and390m2/gforO2andCO2;BETsurfacearea246and313m2/gforO2andCO2.TheselectivesorptionofO2a90MOF作為發(fā)光材料RepresentationofemissionpossibilitiesinaporousMOF.MOF作為發(fā)光材料Representationofemi91StructureandluminescencepropertiesofZn3L3(DMF)2(left)andZn4OL3(right)[Cd3L6](BF4)2(SiF6)(OH)2+13.5H2OLis2,6-di(4-triazolyl)pyridineLuminescencespectraofcomplexeswithincreasingdehydrationandpartiallyrehydrated.Structureandluminescencepro92Cu6L6+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)2atdifferentconcentrationComparisonofdifferentmetalionsCoordinationtometal.Cu6L6+H2O+DMSO,1Dnanotubular93a,1DInO4(OH)2Chainin1b,fourTBAPytoanIn(III)c,eightIntooneTBAPyd,e,f,3Dviewalong[001][010]directionsIn(NO3)3850CDMF+dioxane+H2O[In2(OH)2(TBAPy)]+guests1.a,1DInO4(OH)2Chainin1In(N94Theframeworkstructureoftoluene-loaded1`Fluorescence(blue)andexcitation(red)1+1`+TBAPy.Theframeworkstructureoftol95N2adsorptionisothermof1`at77Kand1barEffectofDMFmoleculesonthefluorescenceof1Guest-dependentfluorescenceemissionof1.N2adsorptionisothermof1`a96Fujita,M.etal,J.Am.Chem.Soc.,2008,1578-1579Directobservationofthelabileimineformationthroughsingle-crystal-to-single-crystalreactionintheporesofaPorouscoordinationnetwork.Fujita,M.etal,J.Am.Chem.S97ChangesincolorandmagneticpropertiesofCo[Cr(CN)6]2/3+zH2Odependonthehumidity.Changesincolorandmagnetic98UnsaturatedmetalconnectingpointsasactivecatalyticsitesActivecatalyticsitesintothebridgingligandsofMOFsMOFsascatalyst.Unsaturatedmetalconnectingp991Dtriangularshapechannelwithasizeof13.4ang,ShowingthecatalyticcentreandthechiralpocketTransesterificationreactioncatalyzedby8.1Dtriangularshapechannelwi1002Dinfiniteframework[Cu2(L8)2(H2O)2]MeOH.H2O.Thewatermoleculesterminatingthecopperwereremoveduponheating,allowingtheexposedcoppercenterstofunctionasLewisacidcatalyticreactio