[Article]doi:202106161微波輔助溶劑熱合成In-Si共改性iO2的增強(qiáng)光催化性能田紅1王會香1史衛(wèi)梅[Article]doi:202106161微波輔助溶劑熱合成In-Si共改性iO2的增強(qiáng)光催化性能田紅1王會香1史衛(wèi)梅2徐耀1,*(1中國科學(xué)院山西煤炭化學(xué)研究所,煤轉(zhuǎn)化國家重點(diǎn)實(shí)驗(yàn)室,太原030001;2中國工程物理研究院化工材料研究所,四川綿陽621900)摘要:利用微波輔助溶劑熱法合成了In-Si共改性的iO2光催化劑.粉末X射線衍射(XRD)激光拉曼(Raman)光譜N2吸脫附(BET)X射線光電子能譜(XPS)光致發(fā)光(PL)光譜和紫外-可見漫反射光譜(U-isDRS)等實(shí)驗(yàn)說明,盡管摻雜和改性后iO2結(jié)晶度略有降低,但不影響光催化劑銳鈦相的形成.Si摻雜入iO2晶格使顆粒變小,比外表積變大.In不能進(jìn)入iO2晶格,在iO2外表形成了In2O3.羅丹明B(RhB)降解實(shí)驗(yàn)顯示,In-Si共改性iO2表現(xiàn)出很高的紫外和可見光催化活性,Si:In:i的摩爾比為0.03:0.02:1的樣品(IS-2)光催化活性最高,紫外光下3min即可將RhB降解完全,可見光下120minRhB降解率為97%,這是由材料的高外表積,In2O3-iO2復(fù)合半導(dǎo)體之間高效電荷轉(zhuǎn)移及染料敏化等共同作用所致.對于苯酚,光催化降解那么相對緩慢,700min內(nèi)尚不能降解完全.關(guān)鍵詞:二氧化鈦;氧化銦;光催化;改性;摻雜中圖分類號:O643Microwave-AssistedSolvothermalSynthesisofIn-SiCo-ModifiediO2PhotocatalystswithEnhancedPhotocatalyticActivityTIANHong1ANGHui-Xiang1SHIei-Mei2XUao1,*(1StateKeyLaboratoryofCoalConversion,InstituteofCoalChemistr,ChineseAcademyofSciences,aiyuan030001,.R.China;2InstituteofChemicalMaterials,ChinaAcademyofEngineeringPhysics,Mianyang621900,SichuanPovince,.R.China)Abstract:In-Sico-modifiediO2photocatalystsweresynthesizedviaamicrowave-assistedsolvothermalmethod.TheobtainedmaterialswerecharacterizedbyX-raydifraction(XRD),Ramanspectroscop,N2ad-desorption(BET),X-rayphotoelectronspectroscopy(XPS),photoluminescence(PL)spectroscop,andU-isieley-is.elsllitinne,iethefactthatthecrystallinityslightlydecreaseduponmodificationoftheiO2photocatalysts.Si-modificationdnrsdrce.-ndoenfn3neef,htntre2,goterneds3d.nfeB)dt-i-d2snthcyrhtde.etysdr-i-d2hnirof1-,hhBsltlyrditin3inrltriltlitdre%fBsrdftr0minundervisiblelight.TheimprovedphotocatalyticactivityofIn-Sico-modifiediO2maybeascribedtoiicsnlee,iitlniinten23-i2i,dthedyesensationefectofRhB.PhotodegradationforcolorlessphenoloccurredatamuchslowerratethanthatforRhB,andthephenoldidnotcompletelydegradewithin700min.Received:February13,2021;Revised:June12,2021;Publishedoneb:June16,2021.Correspondingautho.Email:xuyao@sxicc.ac;el:+86-351-4049859;Fax:+86-351-4040159.TheprojectwassupportedbytheNaturalScienceFoundationofShanxiProvince,China(202101007-3).山西省自然科學(xué)基金(202101007-3)資助工程?EditorialoficeofActaPhysico-ChimicaSinica1544ActaPhys.-Chim.Sin.2021Keyords:iO2;In2O3;Photocatalysis;Modification;Doping1IntroductionNano-structuredsemiconductorphotocatalystshaveattractedextensiveattentiondueto1544ActaPhys.-Chim.Sin.2021Keyords:iO2;In2O3;Photocatalysis;Modification;Doping1IntroductionNano-structuredsemiconductorphotocatalystshaveattractedextensiveattentionduetoitswidepotentialapplicationinair,se,dr-3sefetgsmesattractedmuchattentionduetoitshigheficienc,chemicalsta-,y,d-,deydnenflcsde-le,%)sdsegmaterial,tetraethylorthosilicate(TEOS,99%)asthesiliconsourceandindiumnitrate(In(NO3)3?2O)astheindium,.lsedtru-rification.TheIn-Sico-modifiediO2nanoparticlesweresyn-thesizedviaamicrowave-assistedsolvothermalmethod.Inatypicalprocedure,indiumnitrateg)wasdissolvedintheef4Lcrd2L-drrelectromagneticstirring.ThenmLTEOSwasaddeddrop-eoenhgr0.n8LTwasaddedtothissolutiondropwisewithvigorousstirringfor2homae.ednsndoa0L-ded-dat180°Cfor1hinamicrowavereactor(MDS-8,microwaver0,o.rydomm-perature,theprecipitationwasfilteredandwashedthreetimeshsld-d,dttdt80°Cfor10h.TherestIn-Sico-modifiediO2withdiferentmsedaer,deseds-xgonee.yedrsdt0°Crwatertreatments.4-7Howeve,thepracticalapplicationofiO2tsydydnfdsd.tslnto-tocatalystsindegradationofoganicpollutantsshouldmeetthefollowingconditions:(1)photoabsorptionandgenerationofsd,)endnoe-?reactionsites;(3)formationofhighlyactiveoxidants2r?OH.8Therefore,lagelightharvestingeficiencyandeficientseparationofphotoelectronsandholesareindispensableinphotocatalyticdegradation.Manyefortshavebeenattemptedsenf-enef.ysedteli-,,,,,d,deenfsds.-2eldnO2.eO,-dO-O,d-dO22222etesoee,e-gnenf-e.,noblemetalsaretooexpensivetobewidelyusedpracticall.,md2senn-vestigatedbysomeresearchers.1315Knownasanimportantfunctionalsemiconductorwithhighelectricalconductivityandopticaltransparenc,In2O3hasbeenwidelyexploitedinsolar,,dc7,enhasbeenpaidtotheapplicationofindiummodifiediO2inphotocatalysis.Ontheotherhand,ithasbeenwellestablishedthatthemor-ydef2dnteno-tocatalyticactivit.Smallparticlesbenefitthemigrationofsmkoef2dseeseparationofelectronsandholes.Furthermore,smallerparticleesreatsectgec.ysedthatsynthesisapproach,solvent,dopants,andstartingmaterialssignificantlyaffectedthestructureofiO2-basedphotocat-alyst.6,-0go-3elhsiandP)modificationsreducedtheparticlesizeandenlagethesurfaceareaofiO2.Si-modificationcanalsoinhibitthephasemmeoedeel.oetfr,wsedn2ttlt-iidithilindiimrto-degradationofoganicpollutants.(In-iO2)weresynthesizedviathesimilarprocess.Characterizationsofcatalystselesdyar-yf-fraction(XRD,CuKαradiation,40k,100mA,D/max2500.eOlesdyra2h)n.e--r)surfaceareaofthephotocatalystwasmeasuredbynitrogenad-sorptionat77K(ristar3000,Micromeritics).RamanspectrawereobtainedusingaJYHR800spectroscopywithlaserwave-lengthofnm.TheelementalcompositionandsurfacechemicalstateweredeterminedwithanX-rayphotoelectronspectroscopy(XPS,MgKαasradiationsource,PHI5300X,-.egysdhtoable1PhysicalpopertiesandphotocatalyticdataofmodifiediOSamplen/nn/nCrystalsize/nmSurfacearea/(m?g)D/%10k/miniOSi-iO00-00-~30~50100In-iOIS-1IS-2IS-3IS-4P25molarratio.degradationrateofRhBunderUVlightwithin3minwith[catalyst]=1g?L,[RhB]=30mg?L.ReactionrateconstantofRhBdegradationundervisiblelightthatwascalculatedfromthekineticsshowninwithafirst-classreactionassumption.Forcleardispla,thereactionkineticswasnotshowninFig.5.2 ExperimentalPreparationofcatalystsTIANHongetal.:SynthesisofIn-SiCo-ModifiediO2withEnhancedPhotocatalyticActivity1545CseTIANHongetal.:SynthesisofIn-SiCo-ModifiediO2withEnhancedPhotocatalyticActivity1545Cselkt6.e)aedtmenaeo-ri-)gnssensrce,allsalesereecitedat0maelet.-isdiffusereflectancespectrum(DRS)andUisabsorptionspectrumwereobtainedwithU-isspectrophotometer(Shi-madzuU-3150).TheDRSsystemwasequippedwithaninte-gratingsphereandBaSO4asreference.Photodegradationexperimentsoevaluatethephotocatalyticactivityindetail,bothcolorfulRhodamineB(RhB)anduncolorlessphenolwereusedasthedegradationsubstrates.Photodegradationexperimentswerecar-dtrhVdet.eVtsourceuseda300Whighpressuremercurylampwiththemnt5.eeteda0WnpdafrsdoeeVtbelow400nm.TheinitialRhBconcentrationwas30mg?L-1ins.ellns0g?-1inaqueoussolution.ratilttlticti,tltseidoBsnotanf1g?-.nlexperiments,priortoirradiation,thesuspensionwasstirredinkr0noen.en-centrationofRhBatthispoint(C0)wasusedastheinitialvalueforthefurtherkineticstudyofthephotodegradation.Atagivenne,t0Lnsdddoeeg.en)fdBsdge-snofRhBat540nmwavelengthonaShimadzuU-3150spectro-photomete.neefl,tninphenolaqueoussolutionwasalsomaintainedto1g?L-1.Similarl,theconcentrationofunreactedphnolwasmeasuredusingtheU-isabsorptionofphenolat270nmwavelength.Inallthephotodegradationexperiments,(C0-C)/C0wasde-signedasphotodegradationrate.oobtainthereactionrateconstant(k),afirst-classreactionassumptionwasutilized.ocomparethephotocatalyticactivit,commercialiO2(P25,De-,s%ed%)sdsareference.RamanspectraofiO,Si-iO,andIS-2IS-2:In-Sico-modifiediOwithSi:In:imolarratioof0.03:0.02:1displayedfivepeaksofanatasephasewithRamanshiftsat143,,,,d8-1igtoteE,E,B,A,g g 1g1gdElsfO42dhee,geenserdddrrr,gteledr.entsndagreementwiththeXRDresults.oinvestigatethemorphologyandcrystalstructureinmoredetail,TEMimagesweretakenforiO2(Fig.2(a))andIn-Sico-modifiediO2(IS-2)(Fig.2(b)).Obviousl,aftermodification2se,hdtmisenteringintoiO2crystallatticeandinhibitingiO2crystalliza-.mDttn,r-d,enf)nkdornem°o°,gtelem-sernefe.nrso-reticalresearch,24indeedsiliconatomscanenterintothecrystallatticeofiObecausetheradiusofSi4+(42pm)issmallerthan2tf4+8.e-nndkehf2.roDktsdr-,gtmntroel3+3ef2eosrsfn1.onrslkt,elef2leefyei4+hn.)s3+eMefe-.et2sconfirmthedecreasedcrystallizationaftermodification.Thespecificsurfaceareasofsamplesarealsosummarizedinle.llifidiO2eiitedlrscificsrfcearane2e-ndei-zationofanatase.25FurthermorethesurfaceareadecreasedwithincreasingIncontentbecausemoreionswereinducedintothecnddnf2.ChemicalcompositionXPSanalysiswasemployedtoanalyzetheelementalcompo-sdelefe.hnSafipenn.r-,ei2kf2do8Vmel0e,butnochangewasfoundafterIn-modification.Thiscon-dteisdoelef2t3 ResultsanddiscussionCrystalstructureFromtheXRDpatterns(notshownhere),allthepureandmodifiediO2wereofanatasephase.SiorIn-modificationshowednoefectonthecrystallinephaseofiO2,andIn-Sico-d2htmsdephasewell.Howeve,theweaker(101)peakofmodifiediO2thanthatofthepureiO2,indicatedthatmodificationledtotheef.snedyeledme)ktsdne.sD,naedorethecrystalphaseandshowninFig.1.RamanspectraofiO21546ActaPhys.-Chim.Sin.2021TEMimagesof(a)iO,(b)IS-2,and(c)H1546ActaPhys.-Chim.Sin.2021TEMimagesof(a)iO,(b)IS-2,and(c)HTEMimageofIS-2nsd.SafOselenn3.eOssdoost2d2Vrd2,deyfekteVdecreasedafterIn-modificationcomparedwiththeSi-d.est,,,,d8VyedoensniO,n―O―In,i―O―Si,Si―O―Si,andthei―OHgroupsontheef2seeten.)showstheXPSspectraofIn3dforIn-Sico-modifiediO2,thekt9Vdedo.,6n,eindiumcontentof3.67%(x)fromXPSislagerthanthatoforiginaladdition,indicatingthattheindiumadditivemainlydispersedontheparticlesurface.U-isdiffusionreflectivespectra4seee-snaf,ir-d.emf2sfaenw08r-dO,e2absorptionedgeshiftedtowardstheUVregioncomparedwith,eisdoelef2dbroadenedthebandgap.24ForIn-modifiediO,aslightshift2towardsvisiblelightabsorptionwasfoundcomparedtoiO2,29hsthetfgt3net,ensntroelef2dlyeneeinemfn23.23sieydptdpf6Vdtdpf8)dtknneefe6sre-i-dO,eder2XPSspectraofIS-2(a)i2p,(b)O1s,(c)In3d.Theinsertinthefigure(b)showsthedetailedXPSinformationofO1s.U-isabsorptionspectraof(a)iO,(b)Si-iO,(c)In-iO,and(d)IS-2TIANHongetal.:SynthesisofIn-SiCo-ModifiediO2TIANHongetal.:SynthesisofIn-SiCo-ModifiediO2withEnhancedPhotocatalyticActivity1547againfromIn-iO2,showingthatSi-modificationplayedanim-portantroleinadjustingbandstructure.PhotocatalyticactivityeenfBrVtsotoes-e,eyftunderUVlightwasevaluatedbythedegradationratewithin3n,snne.me,2drc.,eid-d2drcyn2dl.et-2ydBn3nrV.ystecc-,gl,e,,.Inthepresentstud,In-Sico-modifiediO2photocatalystheldsmallparticlesizeandhighsurfacearea,whichfavoredthen.leesei-nfdsmkoef2.,-ndnterthatplayedanimportantroleonhighphotocatalyticactivitybyinhibitingtherecombinationofelectronsandholes.AlthoughIn-Sico-modifiediO2photocatalystshowednovisiblelightresponse(seeFig.4),unexpectedl,highvisiblecysdnenfBaqueoussolution.ThevisibledegradationofRhBisshownini.5.rcarisn,tolakexerietserecarriedt,genekdrrett.l5sodnee.nm,tseoeeBtlightorphotocatalysts,indicatingthatvisiblelightandiO2teeren.eIn-Sico-modifiediO2exhibitedhigherphotocatalyticactivitythanP25,whichwasattributedtosmallerparticlesize,lagersurfacearea,andmoreeficientchagetransferoftheIn-Sico-d.oeeyf,dnfBsdtn-2detisshowninFig.6.Afterthesecondrecycle,IS-2lostalittleactivit.showsthephotodecompositionkineticsofphenoloverl5dtsre.ObviouslythedecompositionofphenolundervisiblelightisPhotocatalyticdegradationofRhBwithecycledIS-2undervisiblelightDegradationkineticsofphenoloverdiffeentphotocatalystsundervisiblelighthrntfBye.n0inlnedlyltlyr-2re,t,yt%feel.om.,edfcysestfg:----.s,5doyrenfe-nol.PhotocatalyticmechanismPhotoluminescence(PL)techniquehasbeenwidelyusedtoeeyf,ndei-nefdsd,,0ut0dyelsdysphotocatalystsandfoundthatthepHvaluesofthesolutionandeef2ydenef?.dneehnti-conductors(suchasrutileiO2,ZnO,WO3,CdS,Bi2WO4,andBiOCl,etc.),anewconcep‘?OH-indexwasproposedtocompareactivityofphotocatalysts.Inthepresentwork,PLysodoeetf-i-tinn?Hrti.i.8steLiintraofiO2andmodifiediO2photocatalysts.Thepeakbetweenwavelength420and470nmwasascribedtothetransitionofsmensoeedf.eLyf2sdyri-,gtenfdDegradationkineticsofRhBoverdiffeentphotocatalystsundervisiblelight1548ActaPhys.-Chim.Sin.2021lighttogeneratephotoelectronsandholes.Therefore,diferentn1548ActaPhys.-Chim.Sin.2021lighttogeneratephotoelectronsandholes.Therefore,diferentnmte.goe2csdbetdex-citedtogeneratephotoelectrons.Ifthephotoelectronswereseparatedfromdye+?andinjectedintotheconductionbandofiO2,teecsitinsldeaciee.iss-calledye-nmnedoneeg-radationofRhB,similartotheotherreport.33Theelectronspro-dyeneydy2-d-?ne2eomenl2.g-?g2dnernf.Inthisprocess,theexistenceofIn2O3oniO2surfaceplaysanimportantroleintransferringelectronsbecauseIn2O3possesseddttygelytid.sedaenesd.e-nmnoedyehrdenflrelightbecausephenolcannotabsorbvisiblelightandsensitizephotocatalyst.WhatevervisibleorUVphotodegradation,lagesurfaceaready-ndoehcactivit.AlthoughIn-modificationreducedslightlythesurfaceady-,edeasenoughtoeficientlyadsorbreactant.PLspectraof(a)iO,(b)In-iO,and(c)IS-2ssd3eeesf-d2ettsdnsredsdseoeeneenegylevelsoftheirconductivebandandvalenceband.12In,-ndoreytdesdtenfe4eLtyedyeydefmodifiediO2.showstheillustrationoftheefectofIn-nneydef.e3possessesclosebutmorenegativeconductivebandandvalencedn,edseyormedf3otf2eeo-eseyormeedf2otf.sedsdserichintheconductivebandofiO2andvanlencebandofIn2O3.Consequentlytherecombinationofelectronsandholesisefec-tivelydecreased.Thismechanismcanexplainthegreatlyen-dVc,rBr.esdsdh-d2dOo4 Conclusions-i-de2sedviaamicrowave-assistedsolvothermalmethodwithin1h.TheobtainedphotocatalystwithgoodcrystallinityandlagesurfaceareacoulddecomposetheRhBefectivelyunderbothUVande.-ndyeeafO.-nydnnOrnOt2232-?producesuperoxideanion(O2)andhydroxylradical(?OH),denfdsd,respectivel.ithSi-modification,thehigherbandgapenegye2rglfed,whichwasthemaindrivingforceofdecomposingoganicmol-ecules.21rI-i-ifidi2teitdyisileaswellasprovidedfastelectrontransferattheInO/iOinter-23 2face.Refeences(1)Cheng,B.;Le,.;u,J.G.J.Hazad.Mate.2021,177(1-3),971.doi:Liu,X.;Fang,Z.;Zhang,X.;Zhang,.;ei,X.;Geng,B.Cryst.GowthDes.2021,9(1),197.doi:Song,L.;Zhang,S.;Chen,B.Catal.Commun.2021,10(12),1565.doi:ang,G.;Jiang,Z.;Shi,H.;Xiao,.;an,Z.J.Mate.Chem.2021,20(25),5301.doi:Zhao,.R.;Zeng,.J.;Xi,H..;u,X.X.ActaPhys.-Chim.Sin.2021,30(4),761.[趙偉榮,曾婉昀,奚海萍,余纖纖.物理化學(xué)學(xué)報(bào),2021,30(4),761.]doi:WHXB202102132Liu,M.;Piao,L.;Zhao,L.;Ju,S.;an,Z.;He,.;Zhou,C.;ang,.Chem.Commun.2021,46(10),1664.doi:b924172h(2)(3)(4)(5)CarriermigrationbetweeniOandInOonthesurfaceofIn-modifiediOCB:conductionband;VB:valenceband;BG:bandgap;SHE:standardhydrogenelectrode(6)TIANHongetal.:SynthesisofIn-SiCo-ModifiediO2withEnhancedPhotocatalyticActivity1549(7)Hidalgo,M.C.;Aguila,M.;TIANHongetal.:SynthesisofIn-SiCo-ModifiediO2withEnhancedPhotocatalyticActivity1549(7)Hidalgo,M.C.;Aguila,M.;Maicu,M.;Navío,J.A.;Colón,G.Catal.oda.2007,129(1-2),50.doi:Kudo,A.;Miseki,.Chem.Soc.Re.2021,38(1),253.doi:He,Z.;Xie,L.;Song,S.;ang,C.;u,J.;Hong,.;Liu,Q.;Chen,J.;Xu,X.J.Mol.Catal.A:Chem.2021,319(1-2),78.doi:Liu,M.;ou,.;Lei,Z.;Zhou,G.;ang,J.;u,G.;Ma,G.;Luan,G.;akata,.;Hara,M.;Domen,K.;Li,C.Chem.Commun.2004,2192.Rodríguez-González,.;Zanella,R.;delAngel,G.;Gómez,R.J.Mol.Catal.A:Chem.2021,281(1-2),93.doi:u,J.;Xiong,J.;Cheng,B.;Liu,S.