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多酸催化析氢

Hydrogen-EvolutionReactionHotPaper

InternationalEdition:DOI:10.1002/anie.201505691GermanEdition:DOI:

多酸催化析氢

10.1002/ange.201505691

PorousMolybdenum-BasedHybridCatalystsforHighlyEfficient

HydrogenEvolution

Yu-JiaTang,Min-RuiGao,Chun-HuiLiu,Shun-LiLi,Hai-LongJiang,Ya-QianLan,*MinHan,andShu-HongYu*

Abstract:WehavesynthesizedaporousMo-basedcompositeobtainedfromapolyoxometalate-basedmetal–organicframe-workandgrapheneoxide(POMOFs/GO)usingasimpleone-potmethod.TheMoOfromthePOMOFs/GO2@PC-RGOhybridmaterialderivedcompositeispreparedatarelativelylowcarbonizationtemperature,whichpresentsasuperioractivityforthehydrogen-evolutionreaction(HER)inacidicmediaowingtothesynergisticeffectsamonghighlydispersiveMoO2particles,phosphorus-dopedporouscarbon,andRGOsubstrates.MoOpotentialcloseto2@PC-RGOexhibitsaverypositiveonsetthatof20%Pt/C,lowTafelslopeof41mVdecÀ1,highexchangecurrentdensityof4.8 10À4AcmÀ2,andremarkablelong-termcyclestability.Itisoneofthebesthigh-performancecatalystsamongthereportednonpreciousmetalcatalystsforHERtodate.

Hydrogen(H),asarenewableenergy,hastriggered2

andenvironment-friendly

broadattentiontoreplacethefossilfuelsbecauseoftheincreasinglyseriousenergycrisisandenviron-mentalcontamination.[1]ProducingHofwaterbythehydrogen-evolution2fromelectrocatalyticsplittingreaction(HER)hasbecomearesearchfocusbecauseofthehighefficiencyofenergyconversion.[2]Ptgroupmetalsarethestate-of-the-artcatalyststogenerateH2withhighcurrentdensityatlowoverpotential(h)inacidicmedia.However,thescarcity,highcosts,andtheinstabilityofPtlimitsthewidespreadapplica-tionfortheHER.[3]Recently,non-nobleelectrocatalystshavebeenwidelystudied,suchastransition-metalsulfides,[4]carbides,[5]phosphides,[6]andnitrides,[7]whichshowthepromisingfuturewhenPt-basedcatalystswillbereplaced.

Molybdenumdioxide(MoOhasahighmetallic-like2)isanunusualtransition-metaloxidethatelectricalconductiv-ityandhighstability,whichhasreceivedmuchattention

[*]Dr.Y.-J.Tang,[+]Dr.C.-H.Liu,Prof.S.-L.Li,http://www.wenkuxiazai.comn,Prof.SchoolM.NanjingofHan

NormalChemistryUniversity,andMaterialsNanjingScience

210023(P.R.China)E-mail:yqlan@http://www.wenkuxiazai.com

Dr.DivisionM.-R.ofGao,[+]NanomaterialsProf.H.-L.andJiang,Chemistry,Prof.S.-H.HefeiYu

NationalLaboratoryforofPhysicalSciencesatMicroscale,CollaborativeInnovationCenterUniversitySuzhou,ofNanoScienceScienceandandTechnologyTechnology,ofChinaDepartmentofChemistry,HefeiE-mail:230026shyu@http://www.wenkuxiazai.com

(P.R.China)[+]Theseauthorscontributedequallytothiswork.

2015Wiley-VCHVerlagGmbH&Co.recently.[8]Besides,theMoedgeandOedgearebothactivesitesofMoO2whichisthekeyfactorthatrendersMoOaHERcatalyst.However,MoO22hasbeenreportedrarelyasHERelectrocatalystsbecauseMoO2islimitedbyanaggre-gationphenomenonandfewexposedactivesites.[9]Toavoidtheaggregationofnanoparticles,substratessuchasporouscarbonandgraphenehavebeenintroducedintometal-basedcatalystsformultiplecatalyticreactions.Onthisbasis,ifthenumberofexposedactivesiteswasincreased,wecouldpreparestableandhighlydispersiveMoO2/CorMoOcatalystsfortheHER.Mostrecently,metal-freedoped2/GOcarbonmaterialshaveshownrelativelyhighelectrocatalyticactivitiesfortheHER.[10]Thesematerialshavelong-termdurabilityandabundantexposedactivesitessincetheheteroatom(N,P,S)iscovalentlyboundwithinthecarbonframework.Assuch,thecombinationofMoO2andheter-oatom-dopedcarbonmaterialsnotonlypreventstheaggre-gationofMoO2,butalsoincreasestheaccessiblenumberofactivesites.Especially,phosphorus-dopedmaterialsdisplayanexcellentcatalyticperformancebecausephosphorushaslone-pairelectronsin3porbitalsandvacant3dorbitals,andcanaccommodate11]thesurfacechargestateandinducelocalchargedensity.[7c,Therefore,itisaverysignificantsubjecttoprepareeffectiveHERcatalystsincombinationwithMoOandP-dopedcarbonsubstrates.

2Polyoxometalate(POM)-basedmetal–organicframe-works(MOFs)havebeensynthesizedinquantitybyresearch-ers,whichcontainPOMunitsandmetal–organicfragmentsformingtheintriguingstructuresandshowpotentialapplica-tionsincatalysis.[12]Recently,novelclassesofporouscarbonmaterials,metaloxidesandtheirnanocompositesderivedfromMOFshavebeenreportedaselectrocatalystsfortheoxygen-reductionreaction(ORR)orelectrodematerialsforLi-ionbatteriesandsupercapacitors.[13]OurgroupnotonlyfocusesonthestudyofPOMOFscrystals,[14]butalsohasreportedheteroatom-dopedmetal-freecarbonmaterialsusingMOFsastemplatesforelectrocatalysts.[15]Todate,onlyLou sgroupchosesPOMOFsasprecursorstopreparenanostructuredMoCxfortheHER.[5b]Hence,wepredictthatPOMOFscanbecarbonizedtoobtainchemicallydopedporouscarbon-coatednanosizedtransition-metal(Mo,W,Vfrompolyoxometalate)oxidesorcarbides.Thisideaintegra-testhenon-noblemetalmaterialswithheteroatom-dopedcarbonmaterialstactfully.

Inthiswork,wefirstlysynthesizedthePOMOFs/GOcompositeusingH3PMooxide12O40·nH(GO)2O(PMoasprecursors12),Cu(OAc)byasimple2·H2O,Hone-pot3BTC,andgraphenemethod(OAc=acetatandHcompositescombine3BTC=1,3,5-benzene-tricarboxylicacid).Thetheadvantages

Weinheim

Angew.Chem.Int.Ed.2015,54,12928–12932

KGaA,

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