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MOFs在多相催化中的應(yīng)用MOFs在多相催化中的應(yīng)用Outline

About“MOFs”ⅱMOFsinHeterogeneousCatalysis

IntroductionRecentProgressandProspect

OutlineⅰAbout“MOFs”可調(diào)控的孔結(jié)構(gòu)及表面功能基團(tuán)高比表面多孔材料所屬領(lǐng)域相關(guān)材料最大比表面積(m2g-1)有序結(jié)構(gòu)沸石904無序碳結(jié)構(gòu)2030MOFs金屬有機(jī)骨架由含氧、氮等的多齒有機(jī)配體與過渡金屬離子自組裝而成的配位聚合物MOFs:metal-organicframeworksPCPs:porouscoordinationpolymersMOCNs:metal-organiccoordinationnetworks相互作用:配位鍵(CB)氫鍵(HB)金屬鍵(MB)π-π鍵(PP)可調(diào)控的孔結(jié)構(gòu)及表面功能基團(tuán)多孔材料所屬領(lǐng)域相關(guān)材Zn4O(BDC)3(DMF)8-(C6H5Cl)MOF-5----Zn4O(BDC)3所屬領(lǐng)域相關(guān)--Yaghietal.Science2002,295,469.Zn4O(BDC)3(DMF)8-(C6H5Cl)MOF-所屬領(lǐng)域相關(guān)合成方法:金屬+有機(jī)配體+溶劑

擴(kuò)散法均相條件控制多相(緩釋)釜式自組裝水熱溶劑熱離子熱潛在應(yīng)用:磁性材料、光學(xué)材料、吸附分離、氣體存儲(chǔ)催化材料所屬領(lǐng)域相關(guān)合成方法:金屬+有機(jī)配體+溶劑催化MOFsinHeterogeneousCatalysisCoordinativelyunsaturatedmetalcenters(UMCs)CatalysismaterialscompletelyisolatedanduniformArrangementofUMCsMOFssynthesisstrategyMOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysis--Fujitaetal.J.Am.Chem.Soc.1994,116,115[Cd(4,4’-bpy)2](NO3)21994,F(xiàn)ujitaetal.firstreportedMOFsappliedinHeterogeneousCatalysis.Benzaldehyde+cyanotrimethylsilane

2-(trimethylsiloxy)phenylacetonitrile

Cat.Yield77%MOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysisPapers20Patents10

reactions:oxidation,epoxidation,carbonylation,hydration,alkoxylation,dehydrogenation,hydrogenation,isomerization,acylation,oligo-/polymerization,photocatalysis,asymmetriccatalysis

role:

catalyst(Lewisacid、base)

supportMOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysis--Kimetal.Nature2000,404,9821-phenyl-2-propanolee.8%MOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysis--W.Linetal.J.Am.Chem.Soc.2005,127,8940[Cd3Cl6L3]·4DMF·6MeOH·3H2OMOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysis--W.Linetal.J.Am.Chem.Soc.2005,127,8940MOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysis--W.Linetal.J.Am.Chem.Soc.2005,127,8940MOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysis[Cd(4-btapa)2(NO3)2]·6H2O·2DMF--Kitagawaetal.J.Am.Chem.Soc.2007,129(9),2607.MOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysis--Kitagawaetal.J.Am.Chem.Soc.2007,129(9),2607.Knoevenagelcondensation

MOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysis--Morietal.J.Catal.2005,232,186MOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysisReactionmechanismprioritycoordinationofolefinsontometalloporphyrinsintramoleculartransferofhydrogenfromarhodiumcentertoaolefinmoleculecoordinatedontometalloporphyrin--Morietal.J.Catal.2005,232,186MOFsinHeterogeneousCatalysi

MOFs在多相催化中的應(yīng)用MOFs在多相催化中的應(yīng)用Outline

About“MOFs”ⅱMOFsinHeterogeneousCatalysis

IntroductionRecentProgressandProspect

OutlineⅰAbout“MOFs”可調(diào)控的孔結(jié)構(gòu)及表面功能基團(tuán)高比表面多孔材料所屬領(lǐng)域相關(guān)材料最大比表面積(m2g-1)有序結(jié)構(gòu)沸石904無序碳結(jié)構(gòu)2030MOFs金屬有機(jī)骨架由含氧、氮等的多齒有機(jī)配體與過渡金屬離子自組裝而成的配位聚合物MOFs:metal-organicframeworksPCPs:porouscoordinationpolymersMOCNs:metal-organiccoordinationnetworks相互作用:配位鍵(CB)氫鍵(HB)金屬鍵(MB)π-π鍵(PP)可調(diào)控的孔結(jié)構(gòu)及表面功能基團(tuán)多孔材料所屬領(lǐng)域相關(guān)材Zn4O(BDC)3(DMF)8-(C6H5Cl)MOF-5----Zn4O(BDC)3所屬領(lǐng)域相關(guān)--Yaghietal.Science2002,295,469.Zn4O(BDC)3(DMF)8-(C6H5Cl)MOF-所屬領(lǐng)域相關(guān)合成方法:金屬+有機(jī)配體+溶劑

擴(kuò)散法均相條件控制多相(緩釋)釜式自組裝水熱溶劑熱離子熱潛在應(yīng)用:磁性材料、光學(xué)材料、吸附分離、氣體存儲(chǔ)催化材料所屬領(lǐng)域相關(guān)合成方法:金屬+有機(jī)配體+溶劑催化MOFsinHeterogeneousCatalysisCoordinativelyunsaturatedmetalcenters(UMCs)CatalysismaterialscompletelyisolatedanduniformArrangementofUMCsMOFssynthesisstrategyMOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysis--Fujitaetal.J.Am.Chem.Soc.1994,116,115[Cd(4,4’-bpy)2](NO3)21994,F(xiàn)ujitaetal.firstreportedMOFsappliedinHeterogeneousCatalysis.Benzaldehyde+cyanotrimethylsilane

2-(trimethylsiloxy)phenylacetonitrile

Cat.Yield77%MOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysisPapers20Patents10

reactions:oxidation,epoxidation,carbonylation,hydration,alkoxylation,dehydrogenation,hydrogenation,isomerization,acylation,oligo-/polymerization,photocatalysis,asymmetriccatalysis

role:

catalyst(Lewisacid、base)

supportMOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysis--Kimetal.Nature2000,404,9821-phenyl-2-propanolee.8%MOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysis--W.Linetal.J.Am.Chem.Soc.2005,127,8940[Cd3Cl6L3]·4DMF·6MeOH·3H2OMOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysis--W.Linetal.J.Am.Chem.Soc.2005,127,8940MOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysis--W.Linetal.J.Am.Chem.Soc.2005,127,8940MOFsinHeterogeneousCatalysiMOFsinHeterogeneousCatalysis[Cd(4-btapa)2(NO3)2]·6H2O·2DMF--Kitagawaetal.

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