MetalOrganicFrameworksApplicationsinSeparati

Metal-OrganicFrameworksMetal-OrganicFrameworksApplicationsinSeparationsandCatalysisEditedbyHermenegildoGarcíaandSergioNavalónEditorsProf.HermenegildoGarcíaTechnicalUniversityofValenciaAv.delosNaranjoss/n46022ValenciaSpainDr.SergioNavalónTechnicalUniversityofValenciaC/CaminodeVera,s/n46022ValenciaSpainCover:Thecoverpicturewaskindlyprovidedby Dr.FilipeA.AlmeidaPaz.AllbookspublishedbyWiley-VCHarecarefullyproduced.Nevertheless,authors,editors,andpublisherdonotwarranttheinformationcontainedinthesebooks,includingthisbook,tobefreeoferrors.Readersareadvisedtokeepinmindthatstatements,data,illustrations,proceduraldetailsorotheritemsmayinadvertentlybeinaccurate.LibraryofCongressCardNo.:appliedforBritishLibraryCataloguing-in-PublicationDataAcataloguerecordforthisbookisavailablefromtheBritishLibrary.BibliographicinformationpublishedbytheDeutscheNationalbibliothekTheDeutscheNationalbibliothekliststhispublicationintheDeutscheNationalbibliografie;detailedbibliographicdataareavailableontheInternetat©2018Wiley-VCHVerlagGmbH&Co.KGaA,Boschstr.12,69469Weinheim,GermanyAllrightsreserved(includingthoseoftranslationintootherlanguages).Nopartofthisbookmaybereproducedinanyform–byphotoprinting,microfilm,oranyothermeans–nortransmittedortranslatedintoamachinelanguagewithoutwrittenpermissionfromthepublishers.Registerednames,trademarks,etc.usedinthisbook,evenwhennotspecificallymarkedassuch,arenottobeconsideredunprotectedbylaw.PrintISBN:978-3-527-34313-3ePDFISBN:978-3-527-80912-7ePubISBN:978-3-527-80910-3MobiISBN:978-3-527-80911-0oBookISBN:978-3-527-80909-7CoverDesignWileyTypesettingSPiGlobalPrivateLimited,Chennai,IndiaPrintingandBindingPrintedonacid-freepaper10987654321ffirs.indd42/13/20182:15:12PMContentsPrefacexiii1TheStabilityofMetal–OrganicFrameworks1GeorgesMouchaham,SujingWang,andChristianSerre1.1Introduction11.2ChemicalStability21.2.1Strengtheningthe CoordinationBond41.2.1.1High-ValenceCationsand Carboxylate-BasedLigands41.2.1.2Low-ValenceCationsand HighlyComplexingLigands91.2.1.3High-ValenceCationsand HighlyComplexingLigands111.2.2Protectingthe CoordinationBond121.2.2.1IntroducingBulkyand/orHydrophobicGroups121.2.2.2CoatingMOFswith HydrophobicMatrices131.3ThermalStability141.4MechanicalStability171.5ConcludingRemarks19Acknowledgments20References202TuningthePropertiesofMetal–OrganicFrameworksbyPost-syntheticModification29AndrewD.Burrows,LauraK.Cadman,WilliamJ.Gee,HarinaAmerHamzah,JaneV.Knichal,andSébastienRochat2.1Introduction292.2Post-syntheticModificationReactions302.2.1CovalentPost-syntheticModification312.2.2InorganicPost-syntheticModification322.2.3Extentofthe Reaction332.3PSMfor EnhancedGasAdsorptionand Separation342.3.1PSMfor CarbonDioxideCaptureand Separation342.3.2PSMfor HydrogenStorage352.4PSMfor Catalysis372.4.1Catalysiswith MOFsPossessingMetalActiveSites372.4.2Catalysiswith MOFscontaining ReactiveOrganicFunctionalGroups392.4.3Catalysiswith MOFsas HostMatrices41Contentsvi2.5PSMfor Sequestrationand SolutionPhaseSeparations422.5.1MetalIonSequestration422.5.2AnionSequestration432.5.3Removalof OrganicMoleculesfrom Solution432.6PSMfor BiomedicalApplications442.6.1TherapeuticMOFsand Biosensors442.6.2PSMbyChangeof PhysicalProperties462.7Post-syntheticCross-Linkingof Ligandsin MOFMaterials462.7.1Pre-syntheticallyCross-LinkedLigands472.7.2Post-syntheticCross-Linkingof MOFLinkers472.7.3Post-syntheticallyModifyingthe Natureof Cross-LinkedMOFs492.8Conclusions51References513SynthesisofMOFsattheIndustrialScale57AnaD.G.Firmino,RicardoF.Mendes,JoãoP.C.Tomé,andFilipeA.AlmeidaPaz3.1Introduction573.2MOFPatentsfrom Academiaversusthe IndustrialApproach583.3IndustrialApproachto MOFScale-up643.4Examplesof Scaled-upMOFs663.5IndustrialSyntheticRoutestowardMOFs693.5.1ElectrochemicalSynthesis693.5.2ContinuousFlow703.5.3Mechanochemistryand Extrusion723.6ConcludingRemarks74Acknowledgments75ListofAbbreviations75References764FromLayeredMOFstoStructuringattheMeso-/MacroscopicScale81DavidRodríguez-San-Miguel,PilarAmo-Ochoa,andFélixZamora4.1Introduction814.2DesigningBidimensionalNetworks824.3MethodologicalNotesRegardingCharacterizationof 2DMaterials844.3.1Morphologicaland StructuralCharacterization844.3.2Spectroscopicand DiffractometricCharacterization884.4Preparationand Characterization924.4.1Bottom-UpApproaches924.4.1.1On-SurfaceSynthesis924.4.1.2SynthesisatWater/AirorSolvent-to-SolventInterface924.4.1.3Synthesisatthe Liquid–LiquidInterface1004.4.2Miscellaneous1044.4.2.1DirectColloidalFormation1044.4.2.2SurfactantMediated1044.4.3Top-DownApproaches1054.4.3.1LiquidPhaseExfoliation(LPE)106Contentsvii4.4.3.2MicromechanicalExfoliation1104.5Propertiesand PotentialApplications1114.5.1GasSeparation1114.5.2ElectronicDevices1124.5.3Catalysis1134.6Conclusionsand Perspectives115Acknowledgments116References1165ApplicationofMetal–OrganicFrameworks(MOFs)forCO2Separation123MohannedMohamedali,HussameldinIbrahim,andAmrHenni5.1Introduction1235.2FactorsInfluencingthe Applicabilityof MOFsfor CO2Capture1245.2.1OpenMetalSites1255.2.2AmineGraftingon MOFs13