Novel dandelion-like beta-manganese dioxide microstructures and their

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Novel dandelion-like beta-manganese dioxide microstructures and their magnetic propertiesThis article has been downloaded from IOPscience. Please scroll down to see the full text article.2006 Nanotechnology 17 947(http://iopscience.iop.org/0957-4484/17/4/018)

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Nanotechnology17(2006)947–951doi:10.1088/0957-4484/17/4/018

Noveldandelion-likebeta-manganesedioxidemicrostructuresandtheirmagneticproperties

BoTang,GuangliWang,LinHaiZhuoandJiechaoGeCollegeofChemistry,ChemicalEngineeringandMaterialsScience,ShandongNormalUniversity,Jinan,Shandong250014,People’sRepublicofChina

E-mail:tangb@sdnu.edu.cnReceived1November2005,infinalform28November2005Published30January2006Onlineatstacks.iop.org/Nano/17/947

AbstractSingle-crystallinedandelion-likeβ-MnO2three-dimensionalmicrostructures

havebeensuccessfullypreparedforthefirsttimeviaasimplehydrothermalprocessbasedonthedirectreactionbetweenMn(NO3)2andH2O2.H2O

2

playsanimportantroleintheformationofthedandelion-likemorphology.

Theformationmechanismofthedandelion-likenanostructureswasinvestigatedanddiscussedbasedontheexperimentalresults.MagneticmeasurementsshowthattheN´eeltemperatureoftheas-obtainedproductis100K,whichisabout6Khigherthanthatofthecorrespondingbulkβ-MnO

2crystals.

1.IntroductionItisgenerallyrecognizedthatsize,shapeanddimensionalityarecriticalfactorsthatmaybringsomenovelandunexpectedproperties:forexample,isotropicoranisotropicbehaviourandregiondependentsurfacereactivity,whichmayextendtheapplicationareaofnanomaterials[1–3].Therefore,thesynthesisofthree-dimensional(3D)nanostructuresisbecominganexcitingfieldbecauseoftheirgreatpotentialapplicationssuchasoptical[4],electronicandoptoelectronicdevices[5].Differentconformational3Dnano-andmicro-crystalssuchasfractal-shapedPt[6],dandelion-likeanddumbbell-shapedZnO[7],SnO2andInNnanoflowers[8],

dendriticCu(OH)2[9],leaf-likeMg2SiO4[10]anddendriticmicro-pinesα-Fe2O3[11]havebeensuccessfullysynthesized.

Manganesedioxidecanformmanykindsofpolymorphs,suchasα-,β-,γ-andδ-type,offeringdistinctivepropertiesandwideapplicationsasmolecularsieves,ionsieves,catalysts,cathodematerialsofsecondaryrechargeablebatteries,andnewmagneticmaterials[12–16].IthasbeenespeciallypointedoutthattheelectrochemicalpropertiesofMnO2strongly

dependonparameterssuchaspowdermorphology,crystallinestructure,bulkdensityetc[17].So,thesynthesisofmanganesedioxidewithdiversemorphologyispotentiallyimportantforbothbasicscienceandtechnologicalapplications.Apartfromnanoparticles,nanorod-shapedandnanofibrousα-andTokorokite-typeMnO2[18],β-MnO2nanorods[19],γ-MnO2nanowires[20]andδ-MnO2nanofibres[21]havebeenpreparedbyseveralresearchgroups.Althoughtherewerereportsonthesynthesisofα-andγ-MnO2three-dimensionalstructures[22],thesynthesisofothercrystallographicforms(suchasβ-orδ-)ofMnO23Dstructuresundermildconditionsisstillachallenge.Thehydrothermalprocessappearstooffersomeadvantagesofmildsyntheticconditions,simplemanipulationandgoodcrystallizationoftheproducts.Employingfacilehydrothermalmethods,nanomaterialswithdifferentmorphologiessuchasnanorods,nanospheresandnanowireshavebeensuccessfullysynthesizedinourlaboratory[23–26].Herein,noveldandelion-likeβ-MnO23Dmicrostructuresweresynthesizedforthefirsttimeviaafacileandfasthydrothermalmethodthroughthedirectreactionbetweenmanganesenitrateandhydrogenperoxide.Thesenovel3Dpatternswerecreatedonself-generatedhomogeneoussubstrates,withoutanyorganicadditivestodirectthestructuregrowth,whichwillensurehighpurityoftheproducts.Theas-obtainedmaterialisanexcitingadditiontoanewlyemergingfamilyofthree-dimensional(3D)structures.ThemagneticmeasurementsshowthattheN´eeltemperatureoftheas-synthesizedproductis6Khigherthanthatofthebulkβ-MnO2crystals.

0957-4484/06/040947+05$30.00©2006IOPPublishingLtdPrintedintheUK947BTangetal2.Experimentalsection

2.1.MaterialsManganesenitrate(Mn(NO3)2·6H2O,70%aqueoussolution);hydrogenperoxide(H2O2,30%).Allchemicalsusedwereofanalyticalgradeandpurchasedfromthecommercialmarketwithoutfurtherpurification.

2.2.ExperimentalprocedureThechemicalreactionsweemployedforthesynthesisofthree-dimensionalmicrostructurecanbeillustratedasfollows[27]:

Mn2++H2O2+2H+→Mn4++2H2O(1)Mn4++xH2O+2OH−→MnO2·xH