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HandbookofSelf-CleaningSurfacesandMaterials
HandbookofSelf-CleaningSurfacesand Materials
FromFundamentalstoApplications
Volume1
EditedbyAkiraFujishima,HiroshiIrie,XintongZhang,and DonaldA.Tryk
Editors
Prof.AkiraFujishima TokyoUniversityofScience PhotocatalysisInternationalResearch Center 2641Yamazaki,Noda Chiba278-8510
Japan and InstituteofPhotochemistryand Photomaterials UniversityofShanghaiforScienceand Technology Shanghai200093
P.R.China
Prof.HiroshiIrie UniversityofYamanashi CleanEnergyResearchCenter 4-3-11Takeda,Kofu Yamanashi400-8511
Japan
Prof.XintongZhang NortheastNormalUniversity SchoolofPhysics Changjun,Jilin130024
China
Prof.DonaldA.Tryk UniversityofYamanashi HydrogenandFuelCellNanomaterials Center 6-43Miyamae-cho,Kofu Yamanashi400-0021
Japan
CoverImage: ©akirbs/GettyImages
Allbookspublishedby WILEY-VCH arecarefully produced.Nevertheless,authors,editors,and publisherdonotwarranttheinformation containedinthesebooks,includingthisbook, tobefreeoferrors.Readersareadvisedtokeep inmindthatstatements,data,illustrations, proceduraldetailsorotheritemsmay inadvertentlybeinaccurate.
LibraryofCongressCardNo.: appliedfor BritishLibraryCataloguing-in-PublicationData Acataloguerecordforthisbookisavailable fromtheBritishLibrary.
Bibliographicinformationpublishedby theDeutscheNationalbibliothek TheDeutscheNationalbibliothekliststhis publicationintheDeutsche Nationalbibliografie;detailedbibliographic dataareavailableontheInternetat <http://dnb.d-nb.de>
©2023WILEY-VCHGmbH,Boschstraße12, 69469Weinheim,Germany
Allrightsreserved(includingthoseof translationintootherlanguages).Nopartof thisbookmaybereproducedinanyform–by photoprinting,microfilm,oranyother means–nortransmittedortranslatedintoa machinelanguagewithoutwrittenpermission fromthepublishers.Registerednames, trademarks,etc.usedinthisbook,evenwhen notspecificallymarkedassuch,arenottobe consideredunprotectedbylaw.
PrintISBN: 978-3-527-35136-7
ePDFISBN: 978-3-527-82486-1
ePubISBN: 978-3-527-82485-4
oBookISBN: 978-3-527-69068-8
Typesetting Straive,Chennai,India
Contents
Volume1:BackgroundandFundamentals
Preface xiii
1Introduction:PhotoprocessesOverview 1 XintongZhang,HiroshiIrie,DonaldTryk,andAkiraFujishima
1.1General 1
1.1.1Photoelectrochemistry 3
1.2FundamentalBackground 12
1.2.1PresentStatus 12
1.2.2Mechanism 12
1.2.3RoleofOxygenReductionandReducedOxygenSpecies 12
1.2.4RemotePC 16
1.2.5Photo-InducedHydrophilicity 17
1.2.5.1History 17
1.2.5.2Mechanisms 24
1.2.5.3PresentStatus 26
1.3Summary 32 References 33
2MechanismsofPhotoinducedOxidativeDecomposition 47 YoshioNosakaandAtsukoY.Nosaka
2.1Introduction 47
2.2SurfaceStructuresofTiO2 andAdsorbedWater 47
2.3TrappedHolesandTrappedElectrons 51
2.4ReactiveOxygenSpecies 53
2.5DetectionofOHRadical 57
2.6FormationMechanismofOHRadical 60
2.7OxidationMechanismofOrganicCompounds 62 References 69
3ReactionMechanismsforTiO2 PowderPhotocatalyzed Systems 75
AndrewMillsandChristopherO’Rourke
3.1Introduction 75
3.2AUsefulvs.RealReactionMechanism 76
3.3CommonAssumptions 76
3.4Datasets 77
3.5KeyReactionProcesses 79
3.6PopularKineticModels 84
3.7EarlyRateEquations:Langmuir-TypeKinetics 87
3.8EarlyRateEquations:Quadratic-TypeKinetics 90
3.9DisruptiveDatasetsandNewKineticModels 93
3.10TheDirect–Indirect(DI)KineticModel 96
3.11APhotocatalyticModelwithaBackReaction:theMarinModel 101
3.12NonequilibratedAdsorption–theOllisDisruptedAdsorptionKinetic Model 101
3.13DTModifiedOllisDisruptedAdsorptionModel 104
3.14TestingReactionMechanismModelswiththeDatasets 104
3.15Conclusions 106 References 107
4MechanismofPhoto-InducedSuperhydrophilicity 111
HiroshiIrie,DonaldA.Tryk,KazuhitoHashimoto,andAkiraFujishima
4.1Introduction 111
4.2WettabilityontheSurface 111
4.3Photo-InducedSuperhydrophilicConversion 112
4.3.1WhatIsSuperhydrophilicity? 112
4.3.2Applications 114
4.4MechanismforSuperhydrophilicConversion 116
4.4.1CharacteristicsofPhoto-InducedSuperhydrophilicState 116
4.4.1.1DifferenceinHydrophilicPropertiesofTiO2 andSrTiO3 Surfaces 116
4.4.1.2RelationshipBetweenAdsorbedSurfaceStainsandWaterContact Angles 116
4.4.1.3HydrophobicConversionintheDarkConditionbyExternal Perturbation 118
4.4.1.4PressureandTemperatureDependencesofBackReactioninthe Dark 118
4.4.2StructuralChangesonTiO2 SurfacesUnderUVLightIrradiation 120
4.4.2.1DomainFormationAfterUVLightIrradiation 120
4.4.2.2ChangeinSurfaceHardnessAfterUVLightIrradiation 120
4.4.3WhatIstheMetastableState? 120
4.4.4MechanismforSuperhydrophilicConversion 122
4.5HighSensitizationUnderWeakUVLightBasedfromtheMechanistic Approach 123
4.5.1ControloftheSurfaceNanostructure 123
4.5.2IntroductionofResidualTensileStress 124
4.6Conclusions 125 References 125
5TheoreticalInvestigationonOpticalSignaturesand PhotochemicalPropertiesofPhotocatalyticTiO2 Surfaces 129 GiacomoGiorgiandKoichiYamashita
5.1Introduction 129
5.2ExcitonicCouplesattheReactiveSurfaceofTiO2 132
5.3SolvatedElectronsatH2 O–TiO2 InterfaceswithO-Vacancies 139
5.4Conclusions 147
Acknowledgments 148 References 148
6ScientificEvaluationMethodsinPhotocatalysisStudies 157 BunshoOhtani
6.1Introduction 157
6.2PrincipleofPhotocatalyticReaction 157
6.2.1BandGapExcitation 158
6.2.2NarrowBandgapSemiconductors 159
6.2.3UseofNon-BandgapExcitation 159
6.3ActionSpectrumAnalysis 159
6.3.1MonochromaticIrradiationandLightIntensityMeasurement 160
6.3.2CalculationofApparentQuantumEfficiency 161
6.3.3MeaningofActionSpectrum 162
6.3.4ImportanceofActionSpectrumAnalyses 162
6.3.5WavelengthDependenceofElectron–HoleUtilization 163
6.3.6AbsorptionSpectrum 163
6.3.7PseudoActionSpectrum 164
6.4PhotoacousticSpectroscopicAnalyses 165
6.4.1ProblemsinMeasuringPhotoabsorptionofSolids 165
6.4.2PrincipleofPhotoacousticSpectroscopy 165
6.4.3PhotoacousticSpectroscopicMeasurements 166
6.4.4CharacteristicFeaturesofPhotoacousticSpectroscopy 167
6.4.5AnalysisofPhotocatalystsbyPhotoacousticSpectroscopy 168
6.5ConcludingRemarks 168 Acknowledgments 169 References 169
7PhotocatalystActivityIndicatorInks(Paii’s) 173 AndrewMills,DanielHawthorne,andNathanWells
7.1Introduction 173
7.2TheReductionofDyesbySemiconductorPC 178
7.3TestingCommercialSPCProducts 181
7.4PhotocatalystActivityIndicatorInks: Paiis and Paiirs183
7.5 Paiir: TheRzInk 185
7.6TheDCIP Paiir Ink 187
7.7TheMB+ Paiir Ink 189
7.8TheRzInkandDigitalPhotography 191
7.9RepeatabilityandReproducibility 193
7.10Kineticsof Paiir SPC 193
7.11Applicationsof Paiirs194
7.12Conclusions 197 References 200
8FabricationofTiO2 ThinFilmsbySolutionProcessesand PreparationofCoatingSolutions 207
TakayukiBanandYutakaOhya
8.1Introduction 207
8.2Sol–GelCoatingofTiO2 ThinFilmsUsingAlcoholicSols 208
8.2.1PreparationofAlcoholicSols 208
8.2.2MicrostructureofTiO2 ThinFilms 210
8.3Sol–GelCoatingofTiO2 ThinFilmsUsingAqueousSols 212
8.3.1PreparationofAqueousSols 212
8.3.2PreparationofAqueousColloidsofLayeredTitanateNanocrystalsand TitanateNanosheets 213
8.3.3FabricationofTiO2 ThinFilmsbySol–GelMethodUsingAqueous Sols 215
8.3.4TiO2 FilmsHydrothermallySynthesizedfromAqueousSols 215
8.3.5AqueousSolsofColloidalAnataseNanocrystals 218
8.4Conclusions 220 References 220
9MorphologyControlofTiO2 ParticlesTowardHighlyActive DecompositionUnderUVorVisibleLight 227 TeruhisaOhnoandNaoyaMurakami
9.1Introduction 227
9.2PreparationofMorphology-ControlledTiO2 228
9.3PreparationofAnataseTiO2 NanoparticleswithExposedCrystal Phases 229
9.4PreparationofRutileTiO2 NanoparticleswithExposedCrystal Phases 231
9.5PreparationofBrookiteTiO2 NanoparticleswithExposedCrystal Phases 235
9.6Visible-Light-ResponsiveRutileTiO2 RodbySite-SelectiveModification ofFe(III)Ionon{111}ExposedCrystalFaces 239
9.7Conclusion 241 References 242
10DevelopmentofVisible-Light-DrivenSuper-HydrophilicThin Film 245
MasahiroMiyauchi
10.1Introduction 245
10.2WO3 -BasedThinFilms 246
10.2.1OptimumStructureforSuper-HydrophilicWO3 Film 246
10.2.2Site-SelectiveDepositionofCo-CatalystsonWO3 NanotreesFilm 247
10.2.3LayeredWO3 /Sn-DopedIn2 O3 (ITO)/CaFe2 O4 Film 250
10.3TiO2 -BasedThinFilms 255
10.3.1InterfacialChargeTransferProcessinCu(II)AmorphousOxideGrafted TiO2 255
10.3.2ThinFilmsofCu(II)AmorphousOxide-GraftedRutileTiO2 Nanorods 256
10.4Conclusion 260
Acknowledgment 260
References 260
11NitrogenDopingintoTiO2 andLoadingofCo-Catalystsfor EnhancedPhotocatalysisUnderVisible-LightIrradiation 263 TakeshiMorikawa,RyojiAsahi,andTakeshiOhwaki
11.1Preface 263
11.2PastResearchinto“Visible-Light-Responsive”TiO2 263
11.3AnionDopingofTiO2 264
11.3.1MaterialDesignBasedonDFTCalculations 264
11.3.2SynthesizingN-DopedTiO2 FilmsandPowders 265
11.3.3NStatesinN-DopedTiO2 266
11.3.4OpticalPropertiesofN-DopedTiO2 268
11.3.5ChargeCarrierDynamicsinN-DopedTiO2 268
11.4PhotocatalyticReactionsOverN-DopedTiO2 271
11.4.1ActionSpectrumforPhotocatalyticReactions 271
11.4.2PhotooxidationofVolatileOrganicCompounds 271
11.4.3AntibacterialProperties 273
11.5N-DopedTiO2 LoadedwithMetallicIons 274
11.5.1PhotocatalystsLoadedwithMetallicIonCo-Catalysts 274
11.5.2SynthesizingN-DopedTiO2 PowdersLoadedwithMetallicIons 274
11.5.3PhotocatalyticActivityOverN–TiO2 LoadedwithCu,Fe,orPt 275
11.6Charge-CarrierDynamicsofN-DopedTiO2 LoadedwithCopper Ions 278
11.7PracticalApplicationsofN–TiO2 Photocatalysts 279 References 279
12ElectronicStatesinPureandDopedAnataseTiO2 : ATheoreticalPerspective 285 CristianaDiValentin,GianfrancoPacchioni,andAnnabellaSelloni
12.1Introduction 285
x Contents
12.2ElectronicStructureofPureAnataseTiO2 286
12.2.1Bandgap:TheoreticalIssues 286
12.2.2ReducedTiO2 :Ti3+ Species 287
12.2.2.1IntrinsicDefects 289
12.2.2.2OxygenVacancies 289
12.2.2.3TiInterstitials 291
12.2.2.4TemperatureEffects 292
12.2.3PhotoexcitedCarriers 294
12.3ElectronicStructureofDopedAnataseTiO2 296
12.3.1DopingwithNonmetalAtoms 296
12.3.1.1SubstitutionalDoping:Boron,Carbon,Nitrogen,andFluorine 297
12.3.1.2InterstitialDoping:Boron,Carbon,andNitrogen 298
12.3.2DopingwithMetalAtoms 300
12.3.2.1CrDoping 300
12.3.2.2NbandSbDoping 303
12.3.3Co-Doping 305
12.3.3.1N–FCo-Doping 305
12.3.3.2Cr–SbCo-Doping 307
12.4Conclusions 309 Acknowledgments 310 A.ComputationalMethods 310 References 311
13Visible-LightPhotocatalysisbyTwo-CenterSurface CoordinationComplexeswithTitaniaasLigand 321 HorstKisch
13.1Introduction 321
13.2Results 323
13.2.1Titania-Chloridoplatinum(IV)SurfaceComplexes 324
13.2.2Titania-Halogenidorhodium(III)SurfaceComplexes 327
13.3Discussion 328
13.4SummaryandOutlook 330 References 330
14MetalIonGraftsTowardVisible-LightResponse 333
HiroshiIrieandKazuhitoHashimoto
14.1Introduction 333
14.2DesignofTiO2 PhotocatalystsSensitivetoVisibleLight 334
14.3PreparationsandCharacterizationsoftheDesignedTiO2 Photocatalysts 335
14.3.1Cu(II)/TiO2 335
14.3.2Fe(III)/TiO2 340
14.3.3Cux O/TiO2 ,CuO/TiO2 343
14.4Visible-LightSensitiveTiO2 PhotocatalystInitiatedbyAnotherTypeof IFCT 344
14.5AnotherDesignofTiO2 PhotocatalystSensitivetoVisibleLight 347
14.6Visible-LightSensitivePhotocatalystsOtherthanTiO2 350
14.7Summary 352 Acknowledgments 353 References 353
15Self-CleaningSurfacesinPlants:TheDiscoveryoftheLotus EffectasaKeyInnovationforBiomimeticTechnologies 359 WilhelmBarthlott References 367
16Self-CleaningPropertyofPlantLeavesandBioinspiredSuper UnwettingSurfaces 371 MeirongSongandLeiJiang
16.1LotusEffectandBioinspiredSuperhydrophobicSurface 373
16.1.1TheUpperSideofLotusLeaf(Nelumbonucifera) 373
16.1.2OtherNaturalTypesofExamples 374
16.1.3TheRoleofAnisotropicArrangementinSelf-CleaningProperty 375
16.1.4Theories 377
16.1.5BioinspiredSuperhydrophobicSurfaces 380
16.1.6SuperamphiphobicSurface 387
16.2Lady’sMantleandBioinspiredUltrahydrophobicStructures 390
16.2.1Lady’sMantle 390
16.2.2AttemptsforBioinspiredHairyUltrahydrophobicSurface 391
16.3TheLowerSideofLotusLeavesandBioinspiredUnderwater SuperoleophobicSurface 393
16.3.1TheLowerSideofLotusLeaves 393
16.3.2OtherNaturalUnderwaterSuperoleophobicExamples 394
16.3.3TheoreticalAnalysis 395
16.3.4BioinspiredSuperoleophobicSurface(InWater) 397
16.4PitcherPlant–BioinspiredSlipperySurfaces 400
16.5ConclusionsandOutlook 404 References 405
17Self-CleaningDryAdhesives 411 JonathanB.PuthoffandKellarAutumn
17.1FibrillarAdhesivesandContamination 411
17.2Self-CleaninginBiologicalFibrillarAdhesives 414
17.3PrinciplesofSelf-CleaninginDryFibrillarAdhesiveSystems 417
17.4Self-CleaninginArtificialArrays 424 References 427
Volume2:Applications
Preface xv
18Self-CleaningGlassinUrbanEnvironment 431 AnneChabasandTizianaLombardo
19Self-CleaningGlass 449
TetsuoMinaaiandKevinD.Sanderson
20Nbx Oy NanosheetFilmforSelf-CleaningGlass 461
Ken-ichiKatsumataandAkiraFujishima
21Self-Cleaning-CoatedFabricsforArchitecturalMembrane Structures 481
HiroshiToyoda,KazuhiroAbe,andTokuyoshiSaitoh
22Photocatalytic-MediatedSelf-CleaningofNaturaland ArtificialFibersUnderDaylightIrradiationatAmbient Temperature 499
JohnKiwiandSamiRtimi
23ApplicationofSelf-CleaningCeramicandGlassInsulatorsfor ElectricityTransmission 545
WenxinDai,PingLiu,XunChen,ZhaohuiLi,JiandongZhuang,XuxuWang, andXianzhiFu
24TiO2 –AgAntibacterialCoatingsforBiomedicalUses 563
HitoshiIshiguro,YanyanYao,andYoshinobuKubota
25TiO2 NanotubesandTheirPhotocatalyticApplications 579
YanyanSong,KiyoungLee,IndhumatiParamasivam,DoohunKim, BenjaminP.Wilson,andPatrikSchmuki
26NoIceLeftBehind 647
AlisonGrinthal,LidiyaMishchenko,andJoannaAizenberg
27SurfaceFactorsforStatic/DynamicHydrophobicityandTheir Evaluation 669
AkiraNakajimaandMunetoshiSakai
28SuperhydrophobicAnticorrosionCoating 689
TakahiroIshizaki,TakuyaFurukawa,NaosumiKamiyama,NagahiroSaito, andOsamuTakai
29RegenerableHydrophobic–HydrophilicPatternedSurfacesfor Printing 723
KazuyaNakata,ShunsukeNishimoto,XintongZhang,andAkiraFujishima
Index 737
Preface
Thepresenttwo-volumesetrepresentsanoverviewofthestatusofself-cleaning surfacesandmaterials,withawiderangeoftopics,frominorganictoorganicand livingorganisms.Theideaof“self-cleaning”isanattractiveone,implyingthatno interventionisrequired.Volume1coversthebackgroundandfundamentalaspects inchapters1through17,whileVolume2focusesonapplicationsinchapters18 through29.
Inthefirstchapter,Zhang,Irie,TrykandFujishimafocusoninorganicmaterials suchastitaniumdioxideandthephotocatalyticprocess.Thelattercanincludeboth photoinducedoxidationandthephotoinducedhydrophiliceffect,bothofwhichare discussedinfurtherdetailthroughoutthetwovolumes.Wealsotouchonthetopic ofpresentinterestinthephotocatalyticdeactivationofviruses.
Thesecondchapterprovidesadetailedaccountofthemechanismsofthe photocatalyticprocess,particularly,photooxidation,byoneofthepremierresearch groupsinthisarea,thatofNosakaandNosaka.
Thethirdchapteralsodealswiththephotocatalyticprocess,inauniquefashion, whichiscomplementarytothatpresentedinchapter2.MillsandO’Rourkefocus onpowderphotocatalystsandtheiractivityinaqueousenvironments.
Inthefourthchapter,thefascinatingtopicofphotoinducedhydrophilicityis discussed,byIrie,Tryk,Hashimoto,andFujishima,particularlyasitrelatesto self-cleaningsurfaces.
Inthefifthchapter,twoofthepremiertheoreticalandcomputationalgroups, thoseofGiorgiandYamashita,discussesphotocatalysisfromanatomic-levelperspective,outliningtheeffectsofvariousdopantsandstructuresontheproperties andphotoprocessesoftitaniumdioxide.
Inthesixthchapter,Ohtanidiscussesoneofthemostimportantbutlessappreciatedtopicsinphotocatalysis,whichisthequantitativeevaluationofphotocatalytic activity.
Intheseventhchapter,Mills,HawthorneandWellsalsodiscusstheevaluation ofphotocatalyticactivityintermsofaconvenient,rapidmethodinvolvingthe bleachingofdyes.
Intheeighthchapter,BanandOhyapresentdetailsonthemethodsofpreparingcoatingsolutionsofpowderphotocatalystsandmethodsofpreparingthinfilms fromthem.
Intheninthchapter,OhnoandMurakamiprovideanoverviewofsomeelegant workonthepreparationandcharacterizationofpropertiesandphotocatalytic reactionsonsingle-crystallinenanoparticles.
Inthetenthchapter,Miyauchidealswitheffortstopreparethin,visible light-responsivesuperhydrophilicfilms,whichareinherentlyself-cleaning.
Theeleventhchapter,byMorikawa,Asahi,andOhwaki,discussescombined theoreticalandexperimentalworkthathasbeenaimedatdevelopingvisible light-responsivephotocatalysts,particularlywithnitrogendoping,andalsowith addedcocatalysts.
Thetwelfthchapter,byDiValentin,PacchioniandSelloni,providesanoverview ofeleganttheoreticalworkonvariousformsofdopedtitaniumdioxideandtheir predictedresponsestovisiblelight.
Chapter13,byKisch,describesanovelapproachtowardthedevelopmentof visiblelight-responsivephotocatalyticsurfacesusingcoordinationcomplexes.
Inchapter14,IrieandHashimotodescribepromisingeffortstodevelopvisible light-responsivephotocatalystsbymakinguseofcopper–titaniagrafts,whichhave alsobeenshowntobehighlyactiveforthedeactivationofcoronaviruses.
Chapter15outlinesthedevelopmentofoneofthemostintriguingstoriesin science,whichisthatofthediscoveryofsuperhydrophobicsurfacesinnature,by therecognizedpioneerinthisarea,Barthlott.
Inchapter16,SongandJiangsummarizeawiderangeofstudieswithvarious typesofself-cleaningplantleaves,withstunningimages.
Inchapter17,PuthoffandAutumndescribefascinatingworkontheself-cleaning capabilityofadhesivesurfacesinspiredbythegecko.
InthefirstchapterinVolume2,onapplications,chapter18,ChabasandLombardodescribeworkonthedevelopmentofself-cleaningglassandthemeasurement ofitspropertiesinEurope.
Inchapter19,MinaaiandSandersondescribeworkonthedevelopmentof self-cleaningglassandthemeasurementofitspropertiesinJapan.
Inchapter20,KatsumataandFujishimadescribenovelworkonthedevelopment ofniobiananosheetstoprepareself-cleaningcoatings.
Chapter21,byToyoda,Abe,andSaitoh,presentsoneofthemostattractiveapplicationsofphotocatalyticself-cleaningsurfaces,thatofthearchitecturalmembrane.
Inchapter22,KiwiandRtimidescribethedevelopmentofthehighlypractical applicationofself-cleaningtextilesandfabrics.
Chapter23,byDai,Liu,Chen,Li,Zhuang,WangandFu,describesthedevelopmentofanotherhighlypracticalapplicationofself-cleaningsurfaces,thatofceramic andglassinsulatorsforelectricaltransmissionlines.
Chapter24,byIshiguro,Yao,andKubota,describesthedevelopmentofoneofthe mostimportantapplicationsofphotocatalysis,thatoftheself-sterilizingsurface,by oneoftheleadgroupsinthisarea.
Chapter25,bySong,Lee,Paramasivam,Kim,WilsonandSchmuki,presentsnovel workonthedevelopmentoftitaniananotube-basedsurfaces.
Inchapter26,Grinthal,Mishchenko,andAizenbergpresentworkonanother extremelyimportantpracticalapplicationofengineeredsuperhydrophobicsurfaces, theanti-icingsurface.
Chapter27,byNakajimaandSakai,discussesthefundamentalaspectsof superhydrophobicsurfaces.
Inchapter28,Ishizaki,Furukawa,Kamiyama,Saito,andTakaidiscussthe extremelypracticalapplicationofanticorrosionsurfaces.
Chapter29,byNakata,Nishimoto,Zhang,andFujishima,discussesthevery interestingandnovelapplicationofpatternedhydrophilic–hydrophobicsurfaces foroffsetprinting.
HandbookofSelf-CleaningSurfacesandMaterials
HandbookofSelf-CleaningSurfacesand Materials
FromFundamentalstoApplications
Volume2
EditedbyAkiraFujishima,HiroshiIrie,XintongZhang,and DonaldA.Tryk
Editors
Prof.AkiraFujishima TokyoUniversityofScience PhotocatalysisInternationalResearch Center 2641Yamazaki,Noda Chiba278-8510
Japan and InstituteofPhotochemistryand Photomaterials UniversityofShanghaiforScienceand Technology Shanghai200093
P.R.China
Prof.HiroshiIrie UniversityofYamanashi CleanEnergyResearchCenter 4-3-11Takeda,Kofu Yamanashi400-8511
Japan
Prof.XintongZhang NortheastNormalUniversity SchoolofPhysics Changjun,Jilin130024
China
Prof.DonaldA.Tryk UniversityofYamanashi HydrogenandFuelCellNanomaterials Center 6-43Miyamae-cho,Kofu Yamanashi400-0021
Japan
CoverImage: ©akirbs/GettyImages
Allbookspublishedby WILEY-VCH arecarefully produced.Nevertheless,authors,editors,and publisherdonotwarranttheinformation containedinthesebooks,includingthisbook, tobefreeoferrors.Readersareadvisedtokeep inmindthatstatements,data,illustrations, proceduraldetailsorotheritemsmay inadvertentlybeinaccurate.
LibraryofCongressCardNo.: appliedfor BritishLibraryCataloguing-in-PublicationData Acataloguerecordforthisbookisavailable fromtheBritishLibrary.
Bibliographicinformationpublishedby theDeutscheNationalbibliothek TheDeutscheNationalbibliothekliststhis publicationintheDeutsche Nationalbibliografie;detailedbibliographic dataareavailableontheInternetat <http://dnb.d-nb.de>
©2023WILEY-VCHGmbH,Boschstraße12, 69469Weinheim,Germany
Allrightsreserved(includingthoseof translationintootherlanguages).Nopartof thisbookmaybereproducedinanyform–by photoprinting,microfilm,oranyother means–nortransmittedortranslatedintoa machinelanguagewithoutwrittenpermission fromthepublishers.Registerednames, trademarks,etc.usedinthisbook,evenwhen notspecificallymarkedassuch,arenottobe consideredunprotectedbylaw.
PrintISBN: 978-3-527-35138-1
ePDFISBN: 978-3-527-82486-1
ePubISBN: 978-3-527-82485-4
oBookISBN: 978-3-527-69068-8
Typesetting Straive,Chennai,India
Contents
Volume1:BackgroundandFundamentals
Preface xiii
1Introduction:PhotoprocessesOverview 1 XintongZhang,HiroshiIrie,DonaldTryk,andAkiraFujishima
2MechanismsofPhotoinducedOxidativeDecomposition 47 YoshioNosakaandAtsukoY.Nosaka
3ReactionMechanismsforTiO2 PowderPhotocatalyzed Systems 75 AndrewMillsandChristopherO’Rourke
4MechanismofPhoto-InducedSuperhydrophilicity 111 HiroshiIrie,DonaldA.Tryk,KazuhitoHashimoto,andAkiraFujishima
5TheoreticalInvestigationonOpticalSignaturesand PhotochemicalPropertiesofPhotocatalyticTiO2 Surfaces 129 GiacomoGiorgiandKoichiYamashita
6ScientificEvaluationMethodsinPhotocatalysisStudies 157 BunshoOhtani
7PhotocatalystActivityIndicatorInks(Paii’s) 173 AndrewMills,DanielHawthorne,andNathanWells
8FabricationofTiO2 ThinFilmsbySolutionProcessesand PreparationofCoatingSolutions 207 TakayukiBanandYutakaOhya
9MorphologyControlofTiO2 ParticlesTowardHighlyActive DecompositionUnderUVorVisibleLight 227
TeruhisaOhnoandNaoyaMurakami
10DevelopmentofVisible-Light-DrivenSuper-HydrophilicThin Film 245
MasahiroMiyauchi
11NitrogenDopingintoTiO2 andLoadingofCo-Catalystsfor EnhancedPhotocatalysisUnderVisible-LightIrradiation 263
TakeshiMorikawa,RyojiAsahi,andTakeshiOhwaki
12ElectronicStatesinPureandDopedAnataseTiO2 : ATheoreticalPerspective 285
CristianaDiValentin,GianfrancoPacchioni,andAnnabellaSelloni
13Visible-LightPhotocatalysisbyTwo-CenterSurface CoordinationComplexeswithTitaniaasLigand 321 HorstKisch
14MetalIonGraftsTowardVisible-LightResponse 333 HiroshiIrieandKazuhitoHashimoto
15Self-CleaningSurfacesinPlants:TheDiscoveryoftheLotus EffectasaKeyInnovationforBiomimeticTechnologies 359 WilhelmBarthlott
16Self-CleaningPropertyofPlantLeavesandBioinspiredSuper UnwettingSurfaces 371 MeirongSongandLeiJiang
17Self-CleaningDryAdhesives 411 JonathanB.PuthoffandKellarAutumn
Volume2:Applications
Preface xv
18Self-CleaningGlassinUrbanEnvironment 431 AnneChabasandTizianaLombardo
18.1Introduction 431
18.2FieldExperiment 433
18.3Results 434
18.3.1OpticalImpairmentoftheUncoatedandTiO2 -CoatedGlasses 434
18.3.1.1FirstFieldCampaign 434
18.3.1.2SecondFieldCampaign 435
18.3.2ComparisonoftheAir-SuspendedParticulateMatterwithDeposit OccurringontheUncoatedGlassDuringthe2-YearExperiment 437
18.3.2.1NumberandSizeDistributionofParticles 437
18.3.2.2MassProportions 438
18.3.3ComparisonBetweenUncoatedandCoatedGlasses 439
18.3.3.1TheDestructionofCarbonaceousParticulatebyTiO2 439
18.3.3.2TheEnhancementofSaltNeocrystallizationsbyTiO2 441
18.3.4ChemicalDurabilityofTiO2 Duringthe2-YearExperiment 443
18.4Conclusion 444
Acknowledgment 444
References 444
19Self-CleaningGlass 449
TetsuoMinaaiandKevinD.Sanderson
19.1Introduction 449
19.2CharacteristicsofPhotocatalysis 450
19.2.1DirtonGlass 450
19.2.2CharacteristicsofSelf-CleaningGlass 450
19.2.2.1HydrophilicEffect 450
19.2.2.2PhotocatalyticActivity 451
19.2.3OtherCharacteristicsofPhotocatalysis 452
19.3ManufacturingMethodsofSelf-CleaningGlass 453
19.3.1Sol–GelMethod 453
19.3.2SputteringMethod 454
19.3.3CVDMethod 456
19.4PracticalExamplesofPhotocatalysisCleaningGlass 456
19.5FutureOutlook 458 References 458
20Nbx Oy NanosheetFilmforSelf-CleaningGlass 461
Ken-ichiKatsumataandAkiraFujishima
20.1Introduction 461
20.1.1Nanosheet 461
20.1.2Self-CleaningGlasswithPhotocatalyst 463
20.2Nbx Oy Nanosheet 464
20.3SynthesisofNbx Oy NanosheetsandCoatingTechniques 466
20.4CharacterizationofNbx Oy Nanosheet-CoatedGlass 467
20.4.1PhotocatalyticActivityofNb3 O8 Nanosheet-CoatedGlass 467
20.4.2PropertiesofNb3 O8 Nanosheet-CoatedGlass 469
20.4.3Self-CleaningPropertiesofNb3 O8 Nanosheet-CoatedGlass 471
References 473
21Self-Cleaning-CoatedFabricsforArchitecturalMembrane Structures 481
HiroshiToyoda,KazuhiroAbe,andTokuyoshiSaitoh
21.1Introduction 481
21.2DirtAdhesionofCoatedFabric 481
21.2.1DirtAdhesiononPVC 481
21.2.2DirtAdhesiononPTFEMembrane 481
21.3EffectofTitaniumDioxide(TiO2 )PhotocatalystontheCoated Fabrics 482
21.4TiO2 Top-CoatingSolutionforCoatedFabrics 483
21.4.1PVCMembranes 483
21.4.1.1NecessaryConditionsforCoatedFabrics 483
21.4.1.2Top-CoatingSolutionsfortheTiO2 Layer 483
21.4.1.3Under-CoatingSolutionsfortheProtectiveAdhesiveLayer 484
21.4.2PTFEMembrane 484
21.5MechanismofSelf-CleaningEffectbyTiO2 Top-Coating 484
21.5.1PVCMembrane 484
21.5.2PTFEMembrane 485
21.6AirPurificationforthePTFEMembranewithTiO2 486
21.7DurabilityofTiO2 Performance 486
21.7.1PVCMembrane 486
21.7.2PTFEMembrane 488
21.8AdvantagesofPVCMembraneswithTiO2 489
21.8.1BrightandComfortableRoom 489
21.8.2EnergySavingSpace 490
21.9Summary 491
21.10ProjectsofArchitecturalMembraneStructuresUsingTiO2 -Coated Fabrics 491 References 497
22Photocatalytic-MediatedSelf-CleaningofNaturaland ArtificialFibersUnderDaylightIrradiationatAmbient Temperature 499 JohnKiwiandSamiRtimi
22.1Introduction 499
22.2ExperimentalSection 500
22.2.1RF-PlasmaPretreatmentofTextileSurfaces 500
22.2.2PretreatmentofTextilesbyUVC 500
22.2.3X-rayPhotoelectronSpectroscopy(XPS)ofTiO2 -ModifiedSurfaces 501
22.2.4High-ResolutionTransmissionElectronMicroscopy(HRTEM) 501
22.2.5X-rayFluorescenceDeterminationofTiContentontheCotton Surface 501
22.2.6ContactAngleMeasurements 502
22.2.7IrradiationProceduresandEvaluationoftheTextileCleaning Action 502
22.2.8DiffuseReflectanceSpectroscopy(DRS)andX-rayDiffraction(XRD) MeasurementsofTiO2 -LoadedTextiles 502
22.2.9InfraredSpectroscopy(ATR–FTIR) 502
22.3Self-CleaningofTextiles 503
22.3.1RF-PlasmaandUVCPretreatmentofTextilesIncreasingtheAmountof TiO2 BindingSites 503
22.3.2PreparationofTiO2 :Colloids,Suspensions,andStepwiseAdditionof Both 504
22.3.3SiO2 –TiO2 LayersonTextilesPrecludingtheCorrosiveOxidationbyh+ vb GeneratedbyTiO2 UnderLightIrradiation 505
22.3.4Cotton–TiO2 CovalentBondingbySpacersandMaleicAnhydride 506
22.3.5Self-CleaningDynamicsforColorlessandColoredStainsonNatural Textiles(Cotton)ModifiedbyTiO2 UnderSolarSimulated Irradiation 508
22.3.6SurfaceCharacterizationofPhotocatalyticTiO2 -ModifiedCotton 510
22.4PreparationofTiO2 -ModifiedArtificialTextiles:Polyamide,Polyester, andNylonTextiles 514
22.5Self-CleaningDynamicsforStainsonTiO2 -ModifiedArtificialTextiles UnderSolar-SimulatedIrradiation 514
22.6SurfaceCharacterizationofPhotocatalyticTiO2 -Artificial-Modified Textiles 515
22.7Transparent,Non-ScatteringPretreatedTiO2 Polyethylene(PE)Films IncreasingDyeFluidityDuringtheDiscolorationofMBUnderSunlight Irradiation 519
22.8CuPromotionoftheWideBandgapBinaryOxideTiO2 –ZrO2 Film AcceleratingSelf-CleaningofArtificialTextiles 531
22.9EvidenceforSelf-CleaningMediatedbyGF–TiO2 –CuMatsUnder Solar/VisibleLightinMildOxidativeConditions 536 Acknowledgments 540 References 540
23ApplicationofSelf-CleaningCeramicandGlassInsulatorsfor ElectricityTransmission 545 WenxinDai,PingLiu,XunChen,ZhaohuiLi,JiandongZhuang,XuxuWang, andXianzhiFu
23.1Introduction 545
23.2PreparationofTiO2 -CoatedInsulator 547
23.3Self-CleaningPerformanceofTiO2 -CoatedInsulator 548
23.4MechanicalandElectricPerformancesofTiO2 -CoatedInsulator 550
23.5AntipollutionFlashoverPerformanceofTiO2 -CoatedInsulator 552
23.6DistributionoftheElectricFieldoverTiO2 -CoatedInsulator 553
23.7MechanismofSelf-CleaningInsulatorforAntipollutionFlashover 555
23.8DifferenceBetweenTiO2 -CoatedInsulatorsandSemiconductor Insulators 557
23.9Applications 558
x Contents
23.10Conclusion 559 Acknowledgment 560 References 560
24TiO2 –AgAntibacterialCoatingsforBiomedicalUses 563 HitoshiIshiguro,YanyanYao,andYoshinobuKubota
24.1Introduction 563
24.2TiO2 PhotocatalystCoatingonSiliconeSurface 564
24.3TiO2 CoatingandAgDepositiononElastomericMaterials 565
24.4UV-DependentAgDeposition 566
24.5AnalysisofAntibacterialEffectsofAg/TiO2 -CoatedSilicone 568
24.6InVitroandInVivoSafetyofTiO2 -CoatedSiliconeand Ag/TiO2 -DepositedSilicone 570
24.7TrialofClinicalApplicationTiO2 -CoatedSiliconeCatheters 571
24.8DevelopmentofNewIndoor-Lighting-ActivePhotocatalyticMaterials andTheirApplication 574
24.9ISOTestMethodforAntibacterialActivityofPhotocatalyticMaterials (Appendix) 574
24.10Conclusions 575 References 575
25TiO2 NanotubesandTheirPhotocatalyticApplications 579 YanyanSong,KiyoungLee,IndhumatiParamasivam,DoohunKim, BenjaminP.Wilson,andPatrikSchmuki
25.1Introduction 579
25.2ElectrochemicalAnodizationandSelf-Organization 581
25.2.1Overview 581
25.2.2ConditionsforTubeGrowth 582
25.2.3SomeFactorsAffectingGeometryandComposition 585
25.2.4AdvancedGeometries 588
25.2.5TubeGrowthIrregularities 589
25.2.6OrderedAnodicMesoporousandNanochannelarStructures 591
25.3PropertiesofTiO2 Nanotubes 592
25.3.1Structure 592
25.3.2Composition 594
25.3.3OpticalandElectricalProperties 595
25.3.4ElectrochemicalProperties 598
25.4ModificationofTiO2 NanotubeProperties 599
25.4.1Doping 599
25.4.2ConversionofTubes(Titanates,SemimetallicPhases) 600
25.4.3FillingandDecoration 600
25.4.4Monolayers 603
25.5KeyFactorsinthePhotocatalyticUseofTiO2 Nanotubes 603
25.5.1AnnealingConditions 605
25.5.2EffectofTiO2 NanotubeLength,Diameter,andStructureson PhotocatalyticActivity 608
25.5.3ExcitationWavelengthandIntensity 609
25.5.4AppliedVoltage 611
25.6ModificationofPhotocatalyticProperties 611
25.6.1DopedTiO2 Nanotubes 611
25.6.2AcceleratedPhotocatalysisbySurfaceEffects 613
25.6.2.1ParticleDecoration,Heterojunctions,ChargeTransferCatalysis 613
25.7ApplicationsofPhotocatalysis 614
25.7.1PollutionDegradation 614
25.7.2WaterSplitting 615
25.7.3SelectivityandHarvestingReactions 617
25.7.4CO2 Reduction 618
25.7.5DrugDeliveryandPayloadRelease 619
25.7.6SensingPlatforms 621
25.7.7Membranes 623
25.7.8BacteriaInactivation 624
25.7.9ScaffoldforCells 625
25.7.10Self-CleaningDevices 625
25.7.11EnergyStorage 626
25.8SummaryandOutlook 628 References 628
26NoIceLeftBehind 647
AlisonGrinthal,LidiyaMishchenko,andJoannaAizenberg
26.1Introduction 647
26.2DesignofIce-FreeNanostructuredSurfaces 649
26.2.1DropletImpactBehavioronSub-FreezingSurfaces 649
26.2.2PredictiveModelBasedonDropletDynamics,Heterogeneous Nucleation,andHeatTransfer 653
26.2.3LowAdhesionofNonwettingIce 656
26.2.4RationalDesignandFabrication 658
26.3SlipperyLiquid-InfusedPorousSurfaces 660
26.4PerspectiveandOutlook 663
Acknowledgment 664 References 665
27SurfaceFactorsforStatic/DynamicHydrophobicityandTheir Evaluation 669
AkiraNakajimaandMunetoshiSakai
27.1HydrophobicityofaSolid 669
27.2TwoWettabilitiesonaSolidSurface 670
27.2.1StaticWettability 670
27.2.2LimitofStaticWettability 671
27.2.3DynamicWettability 672
27.3FactorsAffectingtheWettabilityofaSolid 674
27.3.1SurfaceRoughness 674
27.3.2SurfaceChemicalComposition 675
27.3.3AlignmentorHeterogeneityofSurfaceEnergy 676
27.3.4SurfaceTopographyandRoughnessAlignment 678
27.4SuperhydrophobicSurface 679
27.5MotionofaWaterDropletonaHydrophobicSurface 682
27.5.1DropletMotionbyControllingSolidSurface 682
27.5.2DropletMotionUsingExternalField 682
27.6Summary 683
References 684
28SuperhydrophobicAnticorrosionCoating 689
TakahiroIshizaki,TakuyaFurukawa,NaosumiKamiyama,NagahiroSaito, andOsamuTakai
28.1Introduction 689
28.2CorrosionResistanceandChemicalStabilityofSuperhydrophobicFilm DepositedonMagnesiumAlloyAZ31byMicrowavePlasma-Enhanced ChemicalVaporDeposition 691
28.2.1FabricationofaSuperhydrophobicSurfaceonMagnesiumAlloy AZ31 691
28.2.2AnticorrosivePerformance 694
28.2.3AnticorrosionMechanism 700
28.2.4ChemicalStabilityofSuperhydrophobicSurfaceonMagnesiumAlloy AZ31 701
28.3CorrosionResistanceandDurabilityofSuperhydrophobicSurface FormedonMagnesiumAlloyCoatedwithNanostructuredCerium OxideFilmandFluoroalkylsilaneMoleculesinCorrosiveNaClAqueous Solution 703
28.3.1FabricationoftheSuperhydrophobicSurfaceUsingChemical Conversion 703
28.3.2ChemicalPropertiesoftheSuperhydrophobicSurfaceAfterImmersion in5wt%NaClAqueousSolution 704
28.3.3Corrosion-ResistantPerformanceoftheSuperhydrophobicSurfaceon MagnesiumAlloy 709
28.3.4CorrosionMechanismonSuperhydrophobicFilm-CoveredMagnesium Alloy 716
28.4SummaryandOutlook 718 References 718
29RegenerableHydrophobic–HydrophilicPatternedSurfacesfor Printing 723
KazuyaNakata,ShunsukeNishimoto,XintongZhang,andAkiraFujishima
29.1Introduction 723
29.2PatterningUsingTiO2 Photocatalysis 724
29.3PhotocatalyticOffsetPrintingPlate 726
29.3.1DrawbacksofGeneralOffsetPrintingSystem 726
29.3.2ApplicationofTiO2 inOffsetPrinting 728
29.3.3ApplicationofSAMandInk-JetPatternsofWater-BasedInk 729
29.3.4ColorOffsetPrinting 731
29.3.5PhotocatalyticOffsetPrintingPlateBasedonTitaniumSubstrate 731
29.4Conclusions 734
Acknowledgments 734
References 735
Index 737
Introduction:PhotoprocessesOverview
XintongZhang 1 ,HiroshiIrie 2 ,DonaldTryk 3 ,andAkiraFujishima 4,5
1 NortheastNormalUniversity,SchoolofPhysics,5268RenminStreet,Changchun,Jilin130024,P.R.China
2 UniversityofYamanashi,CleanEnergyResearchCenter,4-3-11Takeda,Kofu,Yamanashi400-8511,Japan
3 UniversityofYamanashi,HydrogenandFuelCellNanomaterialsCenter,6-43Miyamae-cho,Kofu, Yamanashi400-0021,Japan
4 TokyoUniversityofScience,ResearchCenterforSpaceSystemInnovation,2641Yamazaki,Noda,Chiba 278-8510,Japan
5 UniversityofShanghaiforScienceandTechnology,InstituteofPhotochemistryandPhotomaterials,516 JungongRd.,Shanghai200093,P.R.China
1.1General
Fromthestandpointofbothphotocatalysis(PC)andphoto-inducedhydrophilicity(PIH),wewouldliketopresentageneralintroductiontothefundamentaland appliedaspectsofself-cleaningsurfacesbasedontitaniumdioxideandsimilarmaterials.InthedecadesinceourcomprehensivereviewofPCandrelatedphenomena [1],muchresearchanddevelopmenthasbeencarriedoutglobally.Thepublicationsthathaveusedthekeywords“photocatalytic,”“photocatalysis,”or“photocatalyst”haveskyrocketedandnownumberapproximately313,000through2018 (Figure1.1).Thenumbershavegrownliterallyexponentially,whichmakesitnecessarytoplotthemonalogarithmicscale.Thisispartlyduetothestronginterestin theuseofsolarradiationasarenewableresource.
Inthisfigure,wehaveplottedthenumbersofcitationsofthe1972 Nature paper[2] onthephotoelectrochemicaldissociationofwater.Interestingly,thetwocurvesare somewhatlinearandparallel,whichshowsthatthereisadeep,underlyingrelationshipbetweenwaterphotoelectrolysisandPCingeneral,whichmanyresearchers haverecognized.Thisideawillbediscussedinmoredetaillater.
Theapplicationshaveincludedbothenergy-orientedandenvironmentally orientedtechnologies.Thelatterhasincludedairandwatercleanup,aswellasthe cleaningofsurfacesandmaterials,whichisthesubjectofthischapter.Publicationshavingtodowith“self-cleaning”havealsobeenproliferatingexponentially (Figure1.2).Wehavesearchedfor“self-cleaning”plus“titaniumdioxide”and variationsthereof,withatotalofapproximately10,500through2018.Wehave plottedthenumbersofcitationsofthe1997 Nature paper[3]onthePIHeffectin thesamefigure.Interestingly,thetwocurvesnearlyoverlap,atleastintheinitial HandbookofSelf-CleaningSurfacesandMaterials:FromFundamentalstoApplications,FirstEdition. EditedbyAkiraFujishima,HiroshiIrie,XintongZhang,andDonaldA.Tryk. ©2023WILEY-VCHGmbH.Published2023byWILEY-VCHGmbH.
Figure1.1 Citationsperyearfor*photocataly**(bluedots,312,971totalcitationsthrough 2018)andthe1972Fujishima–Hondapaper[2](orangedots,17,292totalcitationsthrough 2018).Forthe2000–2010decade,therewasanaverage6.2%factor.Intotal,therewasa 5.5%factor.Citationsofthe1997 Naturepaper [3].
Figure1.2 Citationsperyearfor“self-cleaning”AND“titaniumdioxideORTiO2 ORtitania ORanataseORrutile”(bluedots,10,542totalcitationsthrough2018)andthe1997Wang etal.paper[3](orangedots,2,574totalcitationsthrough2018).Forthe1997–2007 decade,thenumberswereverysimilar.Source:AdaptedfromWangetal.[3].
decade,whichsuggeststhatnearlyeverystudywasinspiredbythispaper.Thereare manymorepublicationsonself-cleaning,ofcourse,makinguseofawidevariety ofmaterials,but,forthepurposesofthischapter,wehavelimitedourattention mostlytotitaniumdioxide.
GiventhehugenumbersofpublicationsnowavailableinthePCandself-cleaning areas,itisonlypossibletoscratchthesurface.Severalnoteworthyreviewshave appearedduringthepastseveralyears[4–16].Inthischapter,wepresentashort overviewofphotoelectrochemistry(PEC),sinceitprovidesaconceptualfoundation forPCandthePIHeffect.Then,webrieflyexaminetheinsightsofferedfromthis approach,inparticular,theroleofthecathodicreaction,especiallytheoxygen
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clever; the Gordian knot of every question might easily be solved in this way.
Bearing in mind that the question we are now trying to solve is this, “What is the evidence afforded by Geology, as to the history of creation, and in what way does the geological age of the world affect the supposed statement of Scripture, that the world is only 6,000 years old?” I reply thus, and I prefer to use the words of others rather than my own, lest it should be supposed that I am introducing mere novelties of opinion on this subject:—“That the first sentence in Genesis is a simple, independent, all-comprehending axiom to this effect; that matter, elementary or combined, aggregated only or organized, and dependent, sentient and intellectual beings have not existed from eternity, either in self-continuity or in succession: but had a beginning; that their beginning took place by the all-powerful will of One Being, the self-existent, independent and infinite in all perfection, and that the date of that beginning is not made known.”
These are the words of Dr. Pye Smith,[123] of whose name as an authority, both in matters of science and philology, no one need be ashamed.
Dr. Redford says, “We ought to understand Moses as saying, indefinitely, far back, and concealed from us in the mystery of eternal ages, prior to the first moment of mundane time, ‘God created the heavens and the earth.’”
“My firm persuasion is,” says Dr. Harris, “that the first verse of Genesis was designed by the Divine Spirit to announce the absolute origination of the material universe by the Almighty Creator, and that it is so understood in the other parts of Holy Writ; that, passing by an indefinite interval, the second verse describes the state of our planet immediately prior to the Adamic creation; and that the third verse begins the account of the six days’ work.”
Dr. Davidson, in his “Sacred Hermeneutics,” says,—“If I am reminded, in a tone of animadversion, that I am making science, in this instance, the interpreter of Scripture, my reply is, that I am simply making the works of God illustrate His word in a department in which they speak with a distinct and authoritative voice; that it is all the same whether our geological or theological investigations have been prior, if we have not forced the one into accordance with the other. And it may be deserving consideration whether or not the
conduct of those is not open to just animadversion who first undertake to pronounce on the meaning of a passage of Scripture, irrespective of all appropriate evidence, and who then, when that evidence is explored and produced, insist on their à priori interpretation as the only true one.”
But I quote no more: such are some of the eminent theological contributions to this department of science:—satisfactory in this respect, that a fair interpretation of Scripture does not require us to fix any precise date, much less the inconsiderable one of six thousand years, as the period of the earth’s formation.
Geology teaches the same thing.—Of the various formations that compose the earth’s trust, to the ascertained extent of ten miles, suppose we select two,—the Old Red Sandstone and the Chalk formations. Laborious and scientific men have been at the pains to calculate the gradual increase of some of these now proceeding deposits,—such as the Deltas, in course of formation at the mouth of the Nile, and at the gorges of the Ganges; and they find that the progress of the depth of increase is exceedingly small,—probably not more than a foot in many years. Mr. Maculloch, a name standing very high for accurate investigation, states, from his own observation, that a particular Scottish lake does not form its deposit at the bottom, and hence raise its level, at the rate of more than halfa-foot in a century; and he observes, that the country surrounding that lake presents a vertical depth of far more than 3,000 feet, in the single series of the Old Red Sandstone formation; and no sound geologist, he hence concludes, will, therefore, accuse the computer of exceeding, if, upon the same ratio as the contiguous lake, he allows 600,000 years for the production of this series of rock alone.
A last instance which may here be adduced, of the apparent length of time required for the construction of a particular rock, offers itself in the Chalk formation. The enormous masses of this rock, presenting their tall white precipices in such simple grandeur to our view, might well excite our astonishment at the periods which would seem needful for their collection and deposition, even if they were mere inorganic concretions of calcareous matter. But what shall we say when the investigations of the microscope have lately revealed to us that these mountains of chalk, instead of being formed of mere inert matter, are, on the contrary, mighty congeries of decayed
animal life,—the white apparent particles, of which the chalk masses are composed, being each grain a well-defined organized being, in form still so perfect, their shells so entire, and all their characteristics so discoverable, as to cause no doubt to naturalists as to the species in the animal economy to which they belonged. How justly does Sir Charles Lyell, who in his “Elements” records at length this surprising discovery, exclaim,—
“The dust we tread upon was once alive!”
“Look at the lofty precipices which lay naked a slight section of the Chalk at the Culvers, or the Needles in the Isle of Wight, or the still loftier Shakspeare Cliff at Dover, and let the mind form a conception, if it can, of the countless generations of these minutest of living creatures it must have required to build up, from their decayed bodies and their shelly exuviæ, layer on layer, those towering masses thus brought to our view. Who shall dare to compute the time for this entire elaboration? The contemplation almost advances us a step towards forming a conception of infinitude.”[124]
I need not dwell longer on the antiquity of the globe:—Geology and Scripture present no conflicting testimonies on this subject. Our interpretation of Scripture has, undoubtedly, been modified; but the living Word itself abideth, in all its grandeur and purity, for ever. And “the time is not far distant when the high antiquity of the globe will be regarded as no more opposed to the Bible than the earth’s revolution round the sun and on its axis. Soon shall the horizon, where geology and revelation meet, be cleared of every cloud, and present only an unbroken and magnificent circle of truth.”[125]
The reader shall not be detained so long on the second point of inquiry, which is
II. “Was death introduced into the world before the fall of man? and if it was, how are the statements of Scripture, on this question, to be explained?” To this I have replied by anticipation, that, in my opinion, death, upon a most extensive scale, prevailed upon the earth, and in the waters that are under the earth, countless ages before the creation of man. Into the proof of this position allow me to go very briefly, although I am well aware that I run the risk of incurring the charge of heterodoxy, when I state my full conviction, that death, as well as the world, was pre-Adamite. The general
impression is the contrary; but general impressions are not always right:—“general impression” is a very unsubstantial ghost to deal with, very like that cant phrase we spoke of at the beginning of this lecture,—“the intelligence of the age.” “General impression” has it, that death was not pre-Adamite; that there was no death before the fall; and that, to say the contrary, is, at least, to tread on very dangerous ground. In vain does Geology—“now happily a true science, founded on facts, and reduced to the dominion of definite laws”—lay bare the Silurian rocks, and discover even there extinct forms of life in exquisitely beautiful preservation. In vain does Geology, after showing us the fossil trilobite and coral, unfold the volume of the Old Red Sandstone, and show us there the fossil remains of fish—so perfect that we might imagine them casts rather than fossils. In vain does Geology open its vast Oolitic system, and show us there other forms of extinct life in fossil insects, tortoises, mighty saurians, and huge iguanodons. In vain does Geology lay bare the Chalk, with its marine deposits; and the Tertiary formation, with its enormous theroid mammalia, far surpassing in size the largest animals we are acquainted with. In vain are all these fossil remains exhibited imbedded in the earth; and in vain do we search, amidst all these, for one fossil remain of man, or one fossil vestige of man’s works. The easy, the cheap, the unreflective answer is, “Oh! these things were created there, or else Noah’s flood left them there.”
Of course, we can fall back upon a miracle as having done all this; but to have recourse to miracles when no miracle is recorded, is just to shake our faith in that all-inspired testimony, that supernatural Book, the existence of which is the great miracle of time. But there are the fossils! How did they come there if the forms of animal life, once inhabiting those remains, had not previously lived and died? Created! What? Created fossils? Then why not, when the Almighty created man, did he not create, at the same time, some skeletons of man, and place them in the earth, as he put skeletons of trilobites, fishes, reptiles, and mammals there? Our common sense and reverence both reject the idea. As to the puerile notion that Noah’s flood put them there, did not Noah’s flood overwhelm man as well as animals? and as the bones of man are as durable as the bones of animals, how is it that we never meet with a fossil human skull or thigh bone, or house?
We believe that death was a part of the divine plan of God’s creation; that death is a law of all organic life—a necessary law and a most benevolent provision; that the living structure of all animals derives its substance from dead organic matter. We believe that, altogether apart from human sin, preceding and successive generations must be the order of being; for if there were no death, animals would soon pass beyond the limit of provision sufficient for nutritive support, or of localities for suitable habitations. We believe that if there had been no death prior to man’s sin, it would involve the supposition that all animals were herbivorous; whereas, even the little ladybird cannot live without its meal of aphides; and, so believing, we find our faith in Scripture deepened when, seeing on every hand the extensive proofs of death, we find man, the moment he lost his lordship and proud eminence, and reduced himself voluntarily to the condition of animalism, immediately brought penally within the influence of that law of death, whose existence he must have recognised in the death of animals from the first day of his creation.
Does any one reply, “This is contrary to Scripture?” I ask them what Scripture teaches that the death of animals is the result of man’s sin?—rather would not Scripture sanction the thought that death was a part of the divine plan of God’s creation, and that the certainty of man’s transgression was the reason for giving this constitution to nature? True, Milton sings, in his noble poem, that will live as long as the English language lives—
“Of man ’ s first disobedience, and the fruit
Of that forbidden tree, whose mortal taste
Brought death into the world, and all our woe: ”
but we are not obliged to call the Paradise Lost our Bible; or to quote Milton as a physiological authority, although the prevalence of the opinion that death was not pre-Adamite, and a good deal of theology besides, is more of Miltonic than of Scripture teaching.
I leave this branch of my subject far before it is exhausted: so far from that, each of the three points enumerated might easily be expanded into a lecture; and I can only hope that my brevity in treating these topics will not be misconstrued into a desire to shirk any of the difficulties with which their investigation is surrounded.
III. I come, lastly, to the question of the Noachian Deluge, and shall again repeat my own words: “What was the character of the Noachian Deluge?—was it partial or universal? and what are the apparent discrepancies, in this case, between science and the Bible?” And I have added to this my belief that the Noachian Deluge was quite partial in its character, and very temporary in its duration: that it destroyed only those animals that were found in those parts of the earth habitable by man, and that it has not left a single shell or fossil, or any drift boulders or pebbles, or any other remains that may be traced to its action.
Very briefly we shall try and prove this; and perhaps the most popular way will be the best remembered,—only that the reader will bear in mind that this little book does not pretend to exhaust the subject, but only to realize the idea expressed at the beginning of this chapter. Presuming, that all have in their recollection the Scriptural account of the Noachian Deluge, instead of quoting words with which all are familiar, I will only remark, as the basis of my illustrations, that rain descended, and probably the ocean overflowed, for forty days; that the waters lay upon the land, and covered them one hundred and fifty days; that at the end of that time they began to subside, and that in twelve months and twenty-seven days they were gone from the face of the earth, and the Noachian family liberated from the ark.
The question is, was this flood universal, and were all kinds of animals preserved in the ark? To which my answer, as involving my belief, is this, that the flood was local, and that only the animals peculiar to Armenia were provided for in Noah’s ark.
“Oh! but the Bible says it was universal,” says everybody. Yes; but that, you know, is just the question between us. The terms “all the earth” seem to imply universality, but they do not necessarily involve this. “All countries came to Egypt to buy corn;” certainly not all the world literally, but all the surrounding countries. So there were once dwelling at Jerusalem devout Jews “from out of every nation under heaven;” but not literally out of every nation, for the names of the nations are immediately given, and we find the nations to have been a few between Egypt and the Black Sea, and between Italy and Palestine. There are many other illustrations of a similar character: these will suffice: I only adduce these to show that at the beginning
Scripture does not oblige us to consider “all” as meaning “every one;” or to understand literally “all the inhabitants of the earth” as meaning every creature.
Now, looking at the structure and composition of the earth’s crust, especially its fossiliferous rocks, I am driven to one of three conclusions, each of them involving difficulty, I acknowledge, but the one that involves the least is, of course, the most preferable. Either I must admit—
1. That the fossils in these rocks were all deposited in order and in succession, without injury, through a crust of rocks ten miles in thickness, during twelve months’ violent diluvial action:
2. Or that they were all deposited there during the 15,000 or 16,000 years that had elapsed since the creation of man prior to the Deluge; that is, supposing the creation of man and the creation of the earth to have been synchronous. Or, lastly, which theory I accept—
3. That the date of the earth’s physical being is unknown to us, and that the fossiliferous rocks were deposited in decades of ages before the creation of man.
For, on the other hand, let us suppose the flood to have been universal, in the strict and literal sense of the term; then let me suggest some of the consequences and difficulties of such a theory.
1. One consequence would be that some remains of man or of his works would have been found; but nothing of this kind has occurred. Even Armenia has been geologically examined, and no human remains have been found; and surely man’s bones would last as long as the shells of a trilobite or terebratula?
2. And, secondly, the organic remains, the fossils themselves, would have been found confusedly heaped together; whereas, the remains in the crust of the earth are as carefully arranged as the contents of a well-ordered cabinet. We know always to a certainty what fossils will be found in any rock before we examine that rock.
3. Besides which, some, at least, of the organic remains found ought to correspond with existing beings and species: yet the contrary is the case, except only a few fossils found near the surface of the earth, in that portion of the earth’s crust occupied by the tertiary system.
Nor is this all. Consider the vast difficulties the universal flood theory has to contend with, all of which are removed by the theory we have adopted.
1. There is the quantity of water required. If all over the earth the water rose twenty-two feet six inches above the tops of the highest mountains, the quantity of water required would be eight times the whole quantity of water now existing. Where all this could have come from first and gone to afterwards, are prodigious stumbling-blocks. Of course we can resort to miracle; but this is not the way to get rid of difficulty in a manly and honest spirit.
2. Then consider the number of animals the ark must have contained. There are 1,000 species of mammalia, 5,000 species of birds, 2,000 species of reptiles, and 120,000 well-ascertained and distinct species of insects. Do we pretend that all these were housed and fed for nearly thirteen months in a vessel that was only 450 feet long, 75 feet broad, and 45 feet high; and that such a vessel contained room for them, and their food, besides that of man, for such a long period. The little toys of Noah’s ark are certainly pretty, but very mischievous, and most of the popular notions of the flood have grown up from our nurseries as much from the use of this toy in this case, as from the reading of Paradise Lost in the other: and the result is, the Bible is made responsible for it all.
3. Then consider the subsequent distribution of animals: the polar bear and the tropical elephant, the ferocious tiger and a young fawn, going out together in order, and without violence: of course we can suppose another miracle to repress passions and violence. Besides which, in addition to the fauna, the animal kingdom, we must ask what became of the flora or vegetable kingdom during this period, if the flood were universal? We have at least twenty-five botanical provinces, with their peculiar and numberless farms of vegetable life; what became of them? Were they preserved in the ark, or under the water?—for such questions must be answered by those who charge us with inconsistency in attempting to reconcile the facts of science with the words of Scripture. And as a last difficulty, (suggested first, I believe, by Dr. Pye Smith, and which I shall therefore state in his words, lest it should seem that I use “plainness of speech,”) let us look at the descent from Ararat out of the ark, into Armenia, with all these animals, birds, insects, plants and trees. “That mountain is
17,000 feet high, and perpetual snow covers about 5,000 feet from its summit. If the water rose, at its liquid temperature, so as to overflow that summit, the snows and icy masses would be melted; and on the retiring of the flood, the exposed mountain would present its pinnacles and ridges, dreadful precipices of naked rock, adown which the four men and the four women, and with hardly any exception the quadrupeds, would have found it utterly impossible to descend. To provide against this difficulty, to prevent them from being dashed to pieces, must we again suppose a miracle? Must we conceive of the human beings and the animals as transported through the air to the more level regions below; or that, by a miracle equally grand, they were enabled to glide unhurt adown the wet and slippery faces of the rock?”
Such are some of the difficulties and some of the consequences that must flow from an acceptance of any other theory than the one I have proposed: that the flood was partial in its character, extending only over the habitable parts of the earth; and that it was so temporary in its character as not to have left a single trace of its influence visible on rock or fossil.
I have thus endeavoured to suggest points of reconciliation between the accepted facts of Geology and the recorded statements of Scripture; and if this slight contribution be accepted as an aid to faith, and a proof of candour on my part to meet those who linger on the border land of doubt, my purpose will be fully answered.
Let me add, in the words of Chenevix Trench—words uttered in the University of Cambridge not long since: “May we in a troubled time be helped to feel something of the grandeur of the Scriptures, and so of the manifold wisdom of that Eternal Spirit by whom it came; and then petty objections and isolated difficulties, though they were multiplied as the sands of the sea, will not harass us. For what are they all to the fact, that for more than 1,000 years the Bible collectively taken, has gone hand in hand with civilization, science, law—in short, with the moral and intellectual cultivation of the species, always supporting and often leading the way? Its very presence as a believed book, has rendered the nations emphatically a chosen race; and this, too, in exact proportion as it is more or less generally studied. Of those nations which in the highest degree enjoy its influences, it is not too much to affirm that the differences, public
and private, physical, moral, and intellectual, are only less than what might be expected from a diversity in species. Good and holy men, and the best and wisest of mankind, the kingly spirits of history enthroned in the hearts of mighty nations, have borne witness to its influence, and have declared it to be beyond compare the most perfect instrument and the only adequate organ of humanity: the organ and instrument of all the gifts, powers, and tendencies, by which the individual is privileged to rise beyond himself, to leave behind and lose his dividual phantom self, in order to find his true self in that distinctness where no division can be,—in the Eternal I , the ever-living W , of whom all the elect, from the archangel before the throne to the poor wrestler with the Spirit until the breaking of day, are but the fainter and still fainter echoes.”
M. CLAY, PRINTER HEAD STREET HILL.
1. Whewell’s Astronomy and Physics, p. 48.
2. From παλαιός, ancient, and ζωόν, life; ancient-life period.
3. Hughes, Physical Geography. 3d ed. p. 21.
4. Hughes, Physical Geog. p. 22.
5. Dr. Pye Smith.
6. As Chimborazo in South America, 21,414; Ararat, 16,000; Dhawalagiri, in the Himalayas, 28,000 feet above the level of the sea; compared with which what a mole-hill is Vesuvius, only 8,947 feet; or Blue Mountain Peak, 8,600, or even Mont Blanc, that monarch of mountains, which is 15,816 feet above the sea!
7. Hughes, p. 16.
8. Chambers’ Rudiments of Geology, p. 71.
9. These wells are so frequently spoken of as to need no explanation, further than to remind the reader that they are so called from having been first introduced in the province of Artois, the ancient Artesium in France.
10. The deepest Artesian well is the famous one in the Plaine de Grenelle, Paris. This well yields 516 gallons a minute; its temperature is 81° Fahr.; and its depth is nearly 1,800 feet.
11. How truly hieroglyphics sacred carvings; (ieros, sacred, glupho, I carve;) and in this sense there is a holier meaning than Shakspeare could have dreamt of in his well-known lines, when applied by the geologist to his researches:
“And this our life, exempt from public haunt, Finds tongues in trees, books in the running brooks, Sermons in stones, and good in everything.”
12. And I may say, my friend also, to whom, during my residence in Jamaica, I was frequently indebted for contributions on natural history to the Jamaica Friendly Instructor, of which I was Editor.
13. A Naturalist’s Sojourn in Jamaica, by P. H. Gosse, Esq. pp. 496–7.
14. So called because of its grained or granular appearance.
15. First brought from Syene, in Egypt.
16. Feld-spar, written also felspar, a compound of feld, field, and spar.
17. See Ansted’s Ancient World, p. 21.
18. Memnon, or Ramesis. This famous head is in the British Museum; the body is of greenstone, the head of syenite, and the bust one continuous mass.
19. From dis and integer. The separation of the whole parts of a rock, without chemical action, by means of the light, the air, or the rain, is called disintegration.
20. Lieut. Portlock on Geology, p. 93.
21. Ansted’s Geology, Descriptive and Practical, vol. ii. pp. 290, 291.
22. Ansted’s Geology, p. 291.
23. As the ancients did not know or use the compound metal brass, though bronze was common amongst them, we must in this verse, and all others in which the word “brass” is used, understand it to mean copper. Hughes’ Scripture Geography, Art. Geology of Palestine, p. 133.
24. Murray’s Hand-book for Cornwall, p. 199.
25. Ansted, vol. ii. p. 418.
26. Whewell, Anniversary Address to Geol. Society, 1839.
27. In Memoriam.
28. Dr. Pye Smith says 140,000 feet.
29. See a valuable map of fossils published by the Christian Knowledge Society.
30. Trilobite: treis, three, and lobos, a lobe; having three lobes.
31. Bridgewater Treatise, vol. i. p. 396.
32. A fossil shell allied to the Argonauta and Carinaria.
33. “Man has no tail, quantum mutatus; but the notion of a much-ridiculed philosopher of the last century is not altogether without foundation; for the bones of a caudal extremity exist in an undeveloped state in the os coccygis of the human subject.” Poor man! Vestiges of Creation, p. 71.
34. Sedgwick, p. 216, “On the Studies of the University of Cambridge.”
35. “My School and Schoolmasters,” by Hugh Miller.
36. “Old Red Sandstone; or, New Walks in an Old Field;” by Hugh Miller, p. 48.
37. “By mind, by hand, and by hammer.”
38. “Old Red Sandstone,” p. 66.
39. Ichthyolite: ichthus, a fish, lithos, a stone: fossil fish, or the figure or impression of a fish in the rock.
40. “Old Red Sandstone,” pp. 41, 42.
41. “Old Red Sandstone,” p. 69.
42. From akanthos, a thorn, and pterugion, the fin.
43. From malakos, soft, and pterugion, the fin.
44. 1. Ganoid, from ganos, splendour, because the scales are coated with a bright enamel.
45. 2. Placoid, from plax, a plate; sometimes large, sometimes reduced to a point; e.g. shark.
46. 3. Ctenoid, from kteis (gen. ktenos, a comb); scales jagged like a comb.
47. 4. Cycloid, from kuklos, a circle; scales smooth and simple: e.g. salmon, &c.
48. From kephalē, the head; aspis, a buckler.
49. Coccosteus, from kokkos, a berry, and osteon, a bone.
50. “Old Red Sandstone,” p. 86.
51. Pterichthys: pteron, a wing, and ichthus, a fish.
52. “Old Red Sandstone,” pp. 80, 81.
53. Osteolepis: osteon, a bone, and lepis, a scale.
54. Operculum, the flap which covers the gill.
55. “Old Red Sandstone,” p. 111.
56. “Vast quantities:” let any reader go and turn over the non-bituminous shale lying on the waste heaps of every coalpit, and he will see that this is no exaggeration.
57. Capillus Veneris.
58. Corruption of arrière-dos, a fire-place. See a view and description of one in “A Visit to Penshurst,” in Howitt’s “Visits to Remarkable Places,” Second Series.
59. Juicy and soft, as peas, beans, plantains, bananas, &c.
60. “Ancient World,” pp. 76, 77.
61. This may seem strange at first; but I have journeyed through tropical forests that realized completely this sketch, so far as stillness and silence are concerned. A modern and most accomplished naturalist says of a Jamaica virgin forest, “Animal life is almost unseen; the solitude is scarcely broken by the voices of birds, except that now and then the rain-bird or the hunter (large cat-tailed cuckoos that love the shade) sound their startling rattle, or the mountain partridge utters those mournful cooings which are like the moans of a dying man. ” Gosse’s Jamaica, p. 198.
62. From κάλαμος (calamus), a reed.
63. Ansted’s “Ancient World,” p. 82.
64. Mesozoic: i.e. middle life period; mesos, middle, zoos, life.
65. The Religious Tract Society.
66. Lyell’s “Manual of Elementary Geology.” Postscript, p. 13.
67. Ansted’s Geology, vol i. p. 306.
68. Ichnites; from ichnon, a footstep, and eidos, like.
69. Ornithos, a bird, and ichnon.
70. Marsupial, from marsupium, a pouch; animals of the fourth order of Cuvier, that have a pouch in which the young are carried.
71. Batrachian, from batrachos, a frog; animals in Cuvier’s fourth class of reptiles.
72. Cheir, the hand, therion, a wild beast; a wild beast with a foot like a hand.
73. From labyrinthus, a labyrinth, and odous, a tooth; so called from the labyrinthine structure of the tooth.
74. In some cases we find, corresponding to a set of footmarks, a continuous furrow, presumed to be the impression of a tail dragged along the sand by the animal while walking.
75. Ansted’s Ancient World, pp. 125–127.
76. Knight’s Cyclopædia of Arts, &c.
77. Quarterly Review, May, 1852. Article on Roger de Coverley.
78. This is a corruption, we are inclined to think, of the word “layers;” one of those provincial corruptions of the Queen’s English that get stereotyped.
79. Buckland’s Bridgewater Treatise. pp. 351, 352.
80. A fossil bivalve, allied to the oyster, and very abundant in the secondary strata.
81. Belemnite, from belemnos, a dart, and so called from its arrow-headed shape.
82. Saurian, from sauros, a lizard, the name by which the great family of lizards is designated.
83. From ichthus, a fish, and sauros, a lizard; so called from its resemblance to both.
84. Heteroclite; heteros, another, and klitos, inclining; a word applied to any thing or person deviating from common forms.
85. Very unlike the alligator, whose eyes are placed at a considerable distance behind the nose.
86. From pleiōn, more, and sauros, a lizard; because it is more like a lizard than the Ichthyosaurus.
87. Mantel’s Fossils of the British Museum, p. 341.
88. This formation is sometimes called the Jurassic system.
89. Lyell’s Manual of Elementary Geology, p. 12, ed. 1852.
90. “So vast an expanse!” Mr. Darwin traced coral reefs in the Pacific, 4,000 miles long and 600 broad. Between the coasts of Malabar and Madagascar there is a chain of coral reefs, called the Maldives and Laccadives, 480 miles long and 50 miles wide. On the east coast of Australia there is an unbroken reef of 350 miles long; and between Australia and Guinea, coral reefs extend 700 miles in length. Truly the coral animals, like the “conies,” are a “feeble folk,” but their habitations survive our proudest monuments.
91. Hugh Miller’s First Impressions, pp. 203, 204.
92. Brash is s Wiltshire word for short or brittle; and thus a quick-tempered, irritable person, is said to have a brashy temper.
93. Geology for Beginners (Weale’s Series), p. 147.
94. Juke’s Popular Geology, pp. 42–44.
95. From krinos, a lily, and eidos, like; lily-shaped animals of the Radiated division, forming a link between the animal and vegetable world.
96. From trochos, a wheel; wheel-shaped crinoideans.
97. From pteron, a wing, and dactulos, a finger; the wing-fingered animal.
98. The term Weald or Wold is the old Saxon for our present Wood; and now, altered by pronunciation, is found in connexion with many words and names of places: e.g. Waltham (Weald-ham), the wood house or home; Walthamstow, the wood house store, and so on. Thus it is that words are “fossil poetry.”
99. Alison’s description of South America, in History of Europe (Article, South American Revolution); vol. viii.
100. “Our disposition is, and has been, not to multiply miracles after the sort in which this has been done by many more zealous than wise friends of revelation. In all cases we allow the miracle without question, which is distinctly claimed to be such in the Scriptures, and where the circumstances clearly indicate that a miracle was necessary, we say ‘ necessary, ’ because we are persuaded that the Almighty has almost invariably chosen to act through natural agencies, and under the laws which he has imposed on nature, whenever they are adequate to produce the required result. We believe it is one of the beautiful peculiarities of the Bible, that it has none of those gratuitous and barren wonders, which form the mass of the pretended miracles which the various systems of false religion produce.... For our own part, we do not wish to hear of small miracles, which leave us doubtful whether there be any miracle at all. If we are to have miracles, let them be decidedly miraculous, and let not our veneration for the Divine character be offended by exhibitions of the Almighty, as laying bare his holy arm to remove the small remaining difficulty which theorists leave him to execute.” Dr. Kitto’s Biblical History of Palestine.
101. We have a fine specimen before us which we brought from Demerara, answering well to Gosse’s description of the iguana found in Jamaica. “In the eastern parts of the island the great iguana (Cyclura lophoma), with its dorsal crest, like the teeth of a saw, running all down its back, may be seen lying out on the branches of the trees, or playing bo-peep from a hole in the trunk.” It is considered a great delicacy by many, but it never seemed Christian food to us, and we never ventured to provoke our palate with a taste.
102. Enaliosaurians are sea lizards, such as those found in the Lias; and deinosaurians are terrible lizards, such as those found in the Wealden.
103. Ansted’s Ancient World, pp. 164–168.
104. Just published by Bohn, in his valuable “Scientific Library;” a marvel of cheapness and value.
105. Since writing the above we have met with the following, which proves that this origin of chalk is not so fabulous as some think it: “Lieut. Nelson, Mr. Dance, and others have shown, that the waste and débris derived from coral reefs produces a substance exactly resembling chalk. I can corroborate this assertion from my own observations, both on some very white chalky limestones in Java and the neighbouring islands, which I believe to be nothing else than raised fringing coral reefs, and on the substance brought up by the lead over some hundreds of miles in the Indian Archipelago, and along the north-east coast of Australia, and the coral sea of Flinders,” Juke’s Physical Geology, p. 263.
106. We take the origin of the word Folkstone to mean, that that old town was once built of the brick that may be made of the galt: it was the folk’s-stone.
107. “The Religion of Geology,” &c., by E. Hitchcock, LL.D. &c. p. 70.
108. Mantell’s “Geological Excursions,” p. 145.
109. Richardson, p. 391.
110. Under-borne rocks; upo, below, and ginomai, to be formed.
111. Middle life period: mesos, middle, and zoos, life.
112. Recent-life period: kainŏs, recent, and zoos, life.
113. Juke’s Practical Geology, p. 265.
114. Lyell’s Manual of Geology, pp. 97, 98.
115. Ansted’s Geology, vol. ii. p. 14.
116. Even Hitchcock’s good book is sadly disfigured and damaged, by trying to make geology prove too much. How can geology teach or suggest sin and the resurrection?
117. British Quarterly, Feb. 1852.
118. Owen’s British Fossil Mammals and Birds, p. 255.
119. Mantell, pp. 477–479.
120. Mantell, p. 471.
121. The skeleton is not more than 150 years old, and is probably one of an Indian who fell in war; and has been covered with carbonate of lime, held in solution in some spring.
122. Hugh Miller’s “First Impressions of England and its People,” p. 362.
123. No sooner did geology give signs of being able to speak from her subterranean abode, and say something new about the history of this old world, than Dr. Smith was among the foremost of the geologists, intent upon the interpretation of these mysterious, and at first incoherent sounds. At times the sounds seemed unscriptural, but his faith never failed; at other times it seemed in confirmation of Scripture, and he was filled with delight. There were sepulchres older than what he had accounted the era of death, and he must solve the mystery. Mineralogy, to which from his youth he had given considerable attention, became to him history more ancient than that of Moses, and poetry more fascinating than that of Homer. His minerals became books of wonderful tales; his fossils, before riddles of nature, the pictures of things in ancient worlds. The earth was a land of monuments, and the rock which before seemed nothing more than the solid masonry of the foundation on which men might build their dwellings, became the enduring chronicle of the millions of years in which extinct ages had risen, flourished and decayed. From that time he suffered no discovery of the geologists to escape his attention; and every valuable book upon the subject in English, German, or French, contributed its supplies to mitigate his insatiate craving after further information.
Dr. Smith had another reason for devoting a large proportion of his time to geological studies. The new science had something to say about Holy Scripture. It threatened, as many understood its first ambiguous words, to contradict the book of Genesis.
Whatever affected theology was of supreme importance in the estimation of the Homerton professor. Having full confidence in the truth of God’s word, he was sure that nature and revelation, however they appeared to superficial observers, could not be really at variance. In that confidence he patiently listened to every word the new science had to say about the creation of the world. To him belongs the honour, in the opinion of the most eminent geologists, of having relieved their science of every appearance of hostility to Scripture. Of his book on this subject, Dr. Mantell said, “It is, indeed, the dove sent out from the ark of modern geology; and it has returned with the olive branch in its mouth.” British Quarterly, Jan. 1854. Art. D . P S .
124. Gray’s Antiquity of the Globe, pp. 57–59.
125. Hitchcock, p. 70.
August, 1854.
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BALLADS FOR THE TIMES, now first collected. American Lyrics, Geraldine, Modern Pyramid, Hactenus, A Thousand Lines, and Other Poems, by M F. T , D.C.L. F.R.S. Third Edition, with Vignette and Frontispiece, uniform with “Proverbial Philosophy,” fcap. cloth, 7s. 6d.
“With smoothness of measure, Mr. Tupper’s design is always excellent, and his versification is brought to bear upon things of no transient interest. It is one of the best characteristics of his labours, that he does not write for praise, but for the benefit of his fellow-men—not merely for time, but for eternity.”—Bell’s Messenger.
BAPTISMAL FONT (T ), an Exposition of the N and O of C B . With an A . By the Rev. J C , D.D. Fourth Edition, fcap. cloth, gilt edges, 2s.
BARBAULD’S (M .), LEÇONS POUR DES ENFANS, depuis l’âge de Deux Ans junqu’à ’Cinq. Avec une Interprétation Anglais. New Edition, 18mo. cloth, 2s.
BARTLETT (W. H.),—FOOTSTEPS OF OUR LORD AND HIS APOSTLES, in Syria, Greece, and Italy. A succession of Visits to the Scenes of New Testament Narrative. With Twenty-three Steel Engravings, and several Woodcuts. Third Edition, superroyal 8vo. cloth, gilt edges, 14s.; morocco elegant, 26s.
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FORTY DAYS IN THE DESERT, on the Track of the Israelites; or, a Journey from Cairo by W F to Mount Sinai and Petra, with Twenty-seven Engravings on Steel, a Map, and numerous Woodcuts. Fifth Edition, super-royal 8vo. cloth full gilt, morocco elegant, 21 s.