A New MappingExploration Approach for HT Synthesis of Zeolites
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ANewMapping/ExplorationApproachforHTSynthesisofZeolites
AvelinoCorma,*ManuelMoliner,JoseM.Serra,PedroSerna,Marı´aJ.Dı´az-Caban˜as,andLaurentA.Baumes
InstitutodeTecnologı´aQuı´mica,UPV-CSIC,UniVersidadPolite´cnicadeValencia,AVda.delosNaranjoss/n,46022Valencia,Spain
ReceiVedMarch15,2006.ReVisedManuscriptReceiVedMay4,2006
Thisworkshowsamethodologyforthesynthesisofself-assembledorganic-inorganicmaterialswhichintegrateshigh-throughputtoolsforthesynthesisandcharacterizationofsolidmaterialsanddata-miningtechniquesinmaterialsscience.ThisisillustratedbyadetailedexplorationofthehydrothermalsynthesisinthesystemSiO2:GeO2:Al2O3:F-:H2O:N(16)methylsparteinium.Dataanalysisanddimensionalreductionwereconductedbyusingprincipalcomponentsanalysisandclusteringalgorithms,allowingthedefinitionofanewandsuitablestructuralvectorwhichsummarizestheX-raydiffractioncharacterizationdataaswellasanimprovementofdatavisualizationandinterpretation.Differentmodelingtechniqueswereappliedforthepredictionofthepropertiesofthematerialsconsideringthesynthesisdescriptorsasinputofthemodel.Furthermore,different“materialproperty”descriptorswereconsideredasoutcomeofthemodel,thatis,thecrystallinityoftheformedphases,structuralprincipalcomponentscomputedbyprincipalcomponentanalysis,orclusteringresults.Itwasfoundthatthefinalpropertiesofthematerialscouldbesuccessfullymodeledusingartificialneuralnetworksanddecisiontrees.
1.Introduction
Theapplicationofcombinatorialandhigh-throughput(HT)
techniquestomaterialssciencecanhelpchemiststoincrease
thenumberofvariablesofagivenprocessthatcanbestudied
inareasonabletimeperiodaswellastoincreasethenumber
ofsamplesproducedandcharacterized.1-3Moreover,data
mininganddatabasetechnologyareappliedfortheanalysis
andmodelingofthelargeamountsofdatagenerated,
allowinginturnaspeedingupofthediscoveryand
optimizationprocesswhileestablishingscientificprinciples.
Inrecentyears,theusefulnessofHTmethodshasbeen
provenforthediscoveryofsolidfunctionalmaterials.4-8
Indeed,thesemethodsallowthesimultaneousstudyof
numeroussynthesisandprocessingvariables,thisbeing
especiallyimportantwhendealingwithhighlynonlinearand
multidimensionalsystemsasisthecaseforthesynthesisof
microporousmolecularsievesystems.
Thehydrothermalcrystallizationprocessesofmicroporous
materialsaregovernedbyalargenumberofparameters
whichdeterminethephasesformedandthecrystallizationkinetics.Despitethenotableeffortsmadetorationalizethe
synthesisofzeolites,9-12therelationshipbetweensynthesis
variablesandthezeoliticstructureformedisnotclearly
understood,becauseofthemetastablenatureofzeolitesand
thecomplexityoftheinvolvedsynthesismechanisms.Asa
resultofthis,thediscoveryofnewmicroporousmaterialsis
stillpredominantlyanempiricalprocess,thoughstrongly
helpedbyaccumulatedexperience.High-throughputmethods
shouldbeusefulinthisfield13-17todeterminetheeffectof
differentsynthesisparametersandtohelpinthediscovery
ofnewzeolites.
Veryrecently,anewzeolite,namedITQ-21,containing
Si,Ge,andoptionallyAlasframeworkcationswas
reported.18Thismaterialpresentsauniqueporetopology
formedbynearlysphericallargecavitiesof1.18nmdiameter
joinedtosixotherneighboredcavitiesbycircular12-ring
porewindowswithanapertureof0.74nm,whichresultsin
athree-directionalchannelsystemoffullyinterconnected
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