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TheStructureofFerrihydrite,aNanocrystallineMaterialF.MarcMichel,1,2*LarsEhm,1,2SytleM.Antao,3PeterL.Lee,3PeterJ.Chupas,3GangLiu,1,4DanielR.Strongin,1,4MartinA.A.Schoonen,1,2BrianL.Phillips,1,2JohnB.Parise1,2,51CenterforEnvironmentalMolecularScience(CEMS),StonyBrookUniversity,StonyBrook,NY11794,USA.2DepartmentofGeosciences,StonyBrookUniversity,StonyBrook,NY11794,USA.3AdvancedPhotonSource,ArgonneNationalLaboratory,Argonne,IL60439,USA.4DepartmentofChemistry,TempleUniversity,Philadelphia,PA19122,USA.5DepartmentofChemistry,StonyBrookUniversity,StonyBrook,NY11794,USA.*Towhomcorrespondenceshouldbeaddressed.E-mail:fmichel@ic.sunysb.eduDespitetheubiquityofferrihydriteinnaturalsedimentsWithregardtostructure,mostofthedisagreementcentersonanditsimportanceasanindustrialsorbent,thethepossiblepresenceofmultiplestructuralphasesandthenanocrystallinityofthisironoxyhydroxidehashamperedlocalenvironmentofiron(7–10),andhasimplicationsforaccuratestructuredeterminationbytraditionalmethodsunderstandingitsreactivity,magneticproperties,andoverallwhichrelyonlong-rangeorder.Hereweuncoverthechemicalcomposition.Nosingleformulaiswidelyacceptedatomicarrangementbyreal-spacemodelingofthepairforferrihydriteandthisisattributedtovariablewatercontentdistributionfunction(PDF)derivedfromdirectFourierandalackofaknowncrystalstructure(11).Ferrihydriteistransformationofthetotalx-rayscattering.ThePDFforcommonlydesignatedas“2-line”or“6-line”onthebasisofferrihydritesynthesizedusingdifferentroutesisthenumberofpoorlydefined,broadenedmaximaobservedinconsistentwithasinglephase(hexagonalspacegroupx-raydiffraction(XRD)patterns.DeterminingastartingP63mc;a=~5.95,c=~9.06Angstroms).Initsidealform,structuralmodelforthisphaseisparticularlychallengingthisstructurecontains20%tetrahedrallyand80%becauseferrihydritehasnoknownwell-crystallineoctahedrallycoordinatedironandhasabasicstructuralcounterpartthatcanbesynthesizedinthelaboratoryorfoundmotifcloselyrelatedtotheBaker-Figgisδ-Keggincluster.innature.Were
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