氮掺杂炭综述

Nitrogen-containingporouscarbons:synthesisandapplicationWenzhongShen*andWeibinFan*Nitrogen-containingporouscarbonmaterialsareubiquitouswithawiderangeoftechnologicallyimportantapplications,includingseparationscience,heterogeneouscatalystsupports,waterpurification,electrochemistry,aswellasthedevelopingareasofenergygenerationandstorageapplications.Todate,avarietyofapproacheshasbeendevelopedandappliedtointroducenitrogenintothecarbonmatrix.Itisimportantandnecessarytodesignandcontrolahierarchicalporousstructureandthesurfacechemicalgroupsofnitrogen-containingporouscarbonsfortheirapplications.Inthiswork,wesummarizeandcomparerecentlyreportedroutesforthepreparationofnitrogen-containingporouscarbonmaterialsandtheeffectofnitrogengroupsonitsapplicationsinadsorption,electrochemistry,catalysis/catalystsupportsandhydrogenstorageproperties.1IntroductionRecently,muchattentionhasbeenpaidtothepreparationofporouscarbonmaterialsforbothpracticalandfundamentalinterests.Theyareextensivelyusedaselectrodematerialsforbatteries,fuelcells,andsupercapacitors,assorbentsforsepa-rationprocessesandgasstorage,andassupportsformanyimportantcatalysts.1–3Accordingtotheporediameter,porouscarbonmaterialscanbeclassiedasmicroporous(diameter2nm),mesoporous(2nmdiameter50nm),and/ormac-roporous(diameter50nm)carbons.Conventionalporouscarbonmaterialsaresynthesizedbypyrolysisandphysicalorchemicalactivationoforganicprecursorsatelevatedtemperatures.4Inaddition,hard-templateandso-templateapproachesarealsowidelyutilizedtoobtainorderedporouscarbons.5Thepropertiesofporouscarbonmaterialsdependtoalargeextentnotonlyontherawmaterialandtheirsurfacestructureandporositybutalsoontheheteroatomsbuiltintotheirstructures.Themostimportantandwidelyintroducedhetero-atomsareoxygenandnitrogenontheporouscarbonsurface.Theacidiccharacterofporouscarbonssurfacesiscloselyrelatedtotheiroxygen-containingsurfacegroups,6,7whichareDrWenzhongShenobtainedhisPh.DdegreefromtheInstituteofCoalChemistry(ICC),ChineseAcademyofSciences(CAS),in2003.NowheisanassociateprofessorofICC.Hisresearchactivityisthesynthesisofporouscarbonmaterials,especiallyinthecontrolofporestructureanddesignofsurfaceproperties.DrWeibinFanacquiredhisPh.DdegreeintheICCofCASin1998.From1999to2001,heconductedapostdoctoralfellowshipintheCatholicUniversityofLeuvenofBelgiumundertheguidanceofProfs.RobertA.SchoonheydtandBertM.Weckhuysen.Aerthat,hemovedtoJapanandjoinedProf.TakashiTatsumi’sgroup.ThisismadepossiblebytheJapanSocietyforPromotionofScience(JSPS)andtheJapanAgencyofScienceandTechnology(JST).Attheendof2007,hereturnedtoICCandgotafullprofessorposition.Hisresearchinterestsfocusonthesynthesis,character-izationandapplicationofporousmaterials.StateKeyLaboratoryofCoalConversion,InstituteofCoalChemistry,ChineseAcademyofSciences,Taiyuan,Shanxi,P.R.China.E-mail:[e-mail];[e-mail];Fax:[phone];Tel:[phone]Citethis:J.Mater.Chem.A,2013,1,999Received22ndAugust2012Accepted23rdAugust2012DOI:10.1039/c2ta00028hªTheRoyalSocietyofChemistry2013J.Mater.Chem.A,2013,1,999–1013|999JournalofMaterialsChemistryAFEATUREARTICLEPublishedon02October2012.DownloadedbyShandongUniversityofTechnologyon01/04/201409:26:47.ViewArticleOnlineViewJournal|ViewIssuemainlypresentontheoutersurfaceorattheedgeofthebasalplaneandcontributetothechemicalnatureofthecarbon.Incontrast,thebasicityofporouscarbonisassociatedwith:(i)resonating-electronsofcarbonaromaticringsthatattractprotons,and(ii)basicsurfacefunctionalitiesthatarecapableofbindingwithprotons.8–11Nitrogenfunctionalitiesgenerallyprovidebasicproperties,whichcanenhancetheinteractionsbetweenthecarbonsurfaceandacidmolecules,suchasdipole–dipole,hydrogenbonding,covalentbonding,andsoon.12Thepossiblestructuresofthenitrogenfunctionalitiesincludeamides,imides,lactames,pyrrolicandpyridinicgroups,13,14asshowninFig.1.Originally,interestinnitrogen-richcarbonaceousmaterialshasbeenmainlyfocusedontheiruseasadsorbentsinindustryandinenvironmentalprotection.16–19Inthisaspect,nitrogen-containingporouscarbonswithhighsurfaceareaarerecentlyreceivingagreatdealofattentionduetotheirspecicstructuresanduniqueproperties.20–22Forexample,theyshowenhancedadsorptioncapacityofanions,resultingfromapositivelychargedcarbonsurface,andimprovedthermalstabilitybyincorporatingheteroatomswhentheyareusedascatalyticsupports.23Sincenitrogen-richcarbonaceousmaterialswerefoundtoexhibitanincreasingcapacityforacidgases,24–26thistypeofmaterialhasbeenwidelyinvestigatedandutilizedforthereductionofoxygeninfuelcellsandsupercapacitors27–32andthepreparationofhighlyselectivegas-separationmembranes.33Theschemeforthesynthesisandapplicationsofnitrogen-containingporouscarbonsisshowninFig.2.Thisreviewaimstogiveabriefintroductiontotheeldandthefuturepossibilitiesofnitrogen-containingporouscarbonsbysummarizingrecentresearchprogressonthepreparation,characterizationandapplicationsofnitrogen-containingporouscarbonmaterials.2SynthesisNitrogen-containingfunctionalgroupscanbeintroducedthrougheitherreactionwithnitrogen