Novel Concepts in Catalysis and Chemical Reactors: Improving the Efficiency for the Future

392 Pages·2010·6.69 MB·English

by  Andrzej Cybulski

Editedby
AndrzejCybulski,JacobA.Moulijn,
andAndrzejStankiewicz
NovelConceptsinCatalysisand
ChemicalReactors
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Edited by Andrzej Cybulski, Jacob A. Moulijn,
and Andrzej Stankiewicz
Novel Concepts in Catalysis and
Chemical Reactors
Improving the Efficiency for the Future
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V
‘‘InmemoryofourtooearlydeceasedfriendAndrzejCybulski,theinspiringinitiatorof
thisbook.’’
JacobMoulijn
AndrzejStankiewicz
NovelConceptsinCatalysisandChemicalReactors:ImprovingtheEfficiencyfortheFuture.
EditedbyAndrzejCybulski,JacobA.Moulijn,andAndrzejStankiewicz
Copyright2010WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim
ISBN:978-3-527-32469-9
VII
Contents
Preface XVII
ListofContributors XXI
1 MolecularCatalyticKineticsConcepts 1
RutgerA.vanSanten
1.1 KeyPrinciplesofHeterogeneousCatalysis 1
1.2 ElementaryRateConstantsandCatalyticCycle 1
1.3 LinearActivationEnergy–ReactionEnergyRelationships 2
1.4 MicrokineticExpressions;DerivationofVolcanoCurve 6
1.5 CompensationEffect 12
1.6 HydrocarbonConversionCatalyzedbyZeolites 14
1.7 StructureSensitiveandInsensitiveReactions 17
1.8 TheNonmetalAtomSharingRuleofLow-BarrierTransition
States 22
1.8.1 Introduction 22
1.8.2 AmmoniaOxidation 24
1.9 Summary 29
References 29
2 HierarchicalPorousZeolitesbyDemetallation 31
JohanC.GroenandJavierPe´rez-Ram´ırez
2.1 ZeolitesandCatalystEffectiveness 31
2.2 HierarchicalZeolites 33
2.3 MesoporousZeolitesbyDemetallation 34
2.4 Desilication 36
2.4.1 Introduction 36
2.4.2 RoleoftheTrivalentCation 37
2.4.2.1 FrameworkAluminum 37
2.4.2.2 NonframeworkAluminum 38
2.4.2.3 DistributionofAluminumintheFramework 39
2.4.2.4 DifferentZeoliteFrameworkTopologies 39
2.4.2.5 FrameworkTrivalentCationsDifferentfromAluminum 40
NovelConceptsinCatalysisandChemicalReactors:ImprovingtheEfficiencyfortheFuture.
EditedbyAndrzejCybulski,JacobA.Moulijn,andAndrzejStankiewicz
Copyright2010WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim
ISBN:978-3-527-32469-9
VIII Contents
2.4.3 AccessibilityandTransport 40
2.4.3.1 CharacterizationofHierarchicalStructures:fromArgon
AdsorptiontoMIP 40
2.4.3.2 VisualizationbyTomography 41
2.4.3.3 DiffusionStudies 41
2.4.4 DesignofHierarchicalZeolites 42
2.4.4.1 CombinationofPost-synthesisTreatments 42
2.4.4.2 TunableIntracrystallineMesoporositybyPartial
Detemplation–Desilication 42
2.4.4.3 NanocrystalsofZero-DimensionalZeolites 43
2.4.4.4 HollowZeoliteCrystals 44
2.4.5 Functionality 45
2.4.5.1 CatalystPreparation:ImprovedIon-Exchange 45
2.4.5.2 Catalysis 45
2.5 ConclusionsandOutlook 45
References 47
3 PreparationofNanosizedGoldCatalystsandOxidationatRoom
Temperature 51
TakashiTakei,TamaoIshida,andMasatakeHaruta
3.1 Introduction 51
3.2 PreparationofNanosizedGoldCatalysts 52
3.2.1 DepositionofGoldNanoparticlesandClustersontoMetalOxides 52
3.2.1.1 Coprecipitation(CP) 52
3.2.1.2 Deposition–PrecipitationofHydroxide(DP) 53
3.2.1.3 Gas-PhaseGrafting(GG) 55
3.2.1.4 PhysicalVaporDeposition(PVD) 56
3.2.2 DepositionofGoldNanoparticlesandClustersontoCarbonsand
Polymers 58
3.2.2.1 GoldColloidImmobilization(CI) 58
3.2.2.2 Deposition–Reduction(DR) 59
3.2.2.3 SolidGrinding(SG) 60
3.3 Gas-PhaseOxidationAroundRoomTemperature 62
3.3.1 OxidationofMethanol 62
3.3.2 OxidationofFormaldehyde 64
3.3.3 OxidationofCarbonMonoxide 65
3.3.4 OxidationofNH andTrimethylamine 66
3
3.4 Conclusions 67
References 69
4 TheFascinatingStructureandthePotentialofMetal–Organic
Frameworks 73
LucAlaertsandDirkE.DeVos
4.1 Introduction 73
4.2 PreparationandStructure 73
Contents IX
4.2.1 Definition,Synthesis,andPropertiesofMOFs 73
4.2.2 DiscoveryInsteadofDesign 76
4.3 Applications 78
4.3.1 Catalysis 79
4.3.1.1 ActiveMetalCenters 79
4.3.1.2 FunctionalizedOrganicLigands 82
4.3.1.3 ChiralMOFCatalysts 84
4.3.1.4 MOFLatticesasHostsforCatalyticFunctionalities 85
4.3.2 Separation 86
4.4 Conclusion 88
Acknowledgments 90
Abbreviations 90
References 90
5 EnzymaticCatalysisTodayandTomorrow 95
PiotrKiełbasin´ski,RyszardOstaszewski,andWiktorSzyman´ski
5.1 Introduction 95
5.1.1 Chemoselectivity 96
5.1.2 Regioselectivity 96
5.1.3 Stereoselectivity 96
5.2 EnzymaticCatalysisToday 98
5.2.1 RecentDevelopmentsinHeterogeneousBiocatalysis 98
5.2.2 DeracemizationProcesses 101
5.2.2.1 DynamicProcesses(CombinationofEnzymesandChemical
Catalysts,DKR) 102
5.2.2.2 OtherDeracemizationProcesses 105
5.2.3 NovelReactionMedia 107
5.2.3.1 IonicLiquidsasDesignerSolventsforBiotransformations 107
5.2.3.2 SupercriticalFluidsasGreenSolventsforBiotransformations 109
5.3 EnzymaticCatalystsofTomorrow 109
5.3.1 BioconjugatesofCompatibleEnzymesasFunctionalCatalystsfor
MultistepProcesses 109
5.3.2 DirectedEvolution – EnzymeTuningTowardHigherSelectivity 110
5.3.3 IntroductionofNonproteinogenicAminoAcids – TowardMore
Selective,Stable,andEasilyHandledBiocatalysts 112
5.3.4 EnzymeCatalyticPromiscuity – OldEnzymesforNew
Challenges 112
5.4 ConcludingRemarks 116
References 116
6 OxidationToolsintheSynthesisofCatalystsandRelatedFunctional
Materials 121
IgnacioMelia´n-CabreraandJacobA.Moulijn
6.1 Introduction 121
6.2 PreparationStrategiesInvolvingChemicalOxidativeApproaches 121
X Contents
6.2.1 CalcinationinOxidativeAtmospheres 121
6.2.2 AerosolFlameTechnologies 122
6.2.3 SolutionCombustionSynthesis 123
6.2.4 SulfonicAcidFunctionalizationofOrderedMesoporousMaterialsand
PeriodicOrganosilicas 123
6.2.5 SurfaceOxidationofCarbonNanofibersPriorto
Functionalization 125
6.2.6 Purification,Opening,andSizeReductionofCarbonNanotubesby
OxidativeTreatments 125
6.2.7 Metal-FreeCatalysisbyOxygen-ContainingCarbonNanotubes 127
6.3 ACatalyticOxidationTool.FentonChemistryinSolidCatalyst
Synthesis 127
6.3.1 WhatistheFentonReaction? 127
6.3.2 CanWeUseFentonChemistryinSolidCatalystSynthesis? 128
6.3.3 KineticsofFentonChemistry 129
6.4 FirstConceptinCatalystDesign.ShiftingComplexationEquilibriafor
Ion-ExchangebyOxidationoftheOrganicChelates 130
6.5 SecondConceptinCatalystDesign.One-PotSynthesisofFeZeolite
Catalysts 131
6.6 ThirdConceptinCatalystDesign.FentonDetemplation.MildOrganic
TemplateRemovalinMicro-andMesoporousMolecularSieves 132
6.6.1 RoleofOrganicTemplatesandDrawbacksAssociatedto
Calcination 132
6.6.2 AlternativeApproaches 133
6.6.3 FentonDetemplation.ConceptandProof-of-Principle 133
6.7 ConcludingRemarks 136
References 137
7 ChallengesinCatalysisforSustainability 143
RiittaL.Keiski,TanjaKolli,MikaHuuhtanen,SatuOjala,
andEvaPongra´cz
7.1 Introduction 143
7.2 PopulationandHumanResources 144
7.3 FoodSecurity 144
7.4 SpeciesandEcosystem 144
7.5 Energy 145
7.5.1 SustainableFuelsthroughCatalysis 145
7.5.2 HydrogenProductionforFuelCells 146
7.5.2.1 Case – UseofCarbonNanotube-BasedCatalystsinHydrogen
Production 147
7.6 Industry 147
7.6.1 CatalysisforSustainableProduction 148
7.6.2 CatalyticCO UtilizationTechnologies 149
2
7.6.3 NO EmissionsReduction 150
x