葡萄糖基水热炭构建Co―N...苯催化加氢反应性能（英文）_杨雨.pdf

Cite this:NewCarbonMaterials,2023,38(3):555-565DOI:10.1016/S1872-5805(23)60723-1Synthesis of CoNC catalysts from a glucose hydrochar andtheir efficient hydrogenation of nitrobenzeneYANGYu,BUYu,LONGXing-lin,ZHOUZhi-kang,WANGJing,CAIJin-jun*（School of Chemical Engineering,Xiangtan University,Xiangtan 411105,China）Abstract：Alow-cost,greencatalystfornitrobenzene(NB)hydrogenationisneededforanilineproduction.Wereporttheprepar-ationofhighly-dispersedCoparticlessupportedonN-dopedcarbonsbythehydrothermaltreatmentofglucose,followedbythepyro-lysisofamixtureofurea,glucosehydrocharandcobaltnitrateinone-pot.Theeffectofthepyrolysistemperatureonthemicrostruc-tureofthecatalystswasstudied.ResultsindicatedthattheactivityforNBhydrogenationwashighlyaffectedbythesurfacearea,Co-loadinglevelandCo-Nxcoordinationinthecatalysts.CoNCG-800pyrolyzedat800Cwith10%Cointheprecursorhadex-traordinaryactivityforNBhydrogenation,achievingfullconversionand99%anilineselectivityinisopropanolat100Cand1MPaH2pressurefor2.5h.NBconversionandanilineselectivityoverthecatalystsremainedalmostunchangedaftersixrecycles,duetothestrongcoordinationbetweentheN-andCo-species.ThereactionsystemshowednotonlyahighNBactivitybutalsoagreenanddurablecatalyticprocess,witheasyoperation,easyseparationandcatalystreusability.Key words:Biomassglucose；Hydrothermal；Co-N-Ccatalysts；Nitrobenzenehydrogenation1IntroductionReduction or hydrogenation of nitrobenzene(NB)are 2 main strategies to produce anilines13whichisoneofimportantintermediatesforchemicalsi.e.pesticide,dyeandpigment.Inparticular,NBhy-drogenationover these catalysts is a widely de-velopedstrategy,andalmost70%ofanilinesarepro-ducedbythismethod4.Forinstance,sucrose-basedCoNCcatalystshadhighactivityinNBconver-sionusingformicacidasaH2donor5,whichcanbemagnetically recovered with high recyclability fromtheeffectofuniformlyN-speciesandCoparticlesonthesurface.AscomparedtostoichiometricreductionwithchemicalH2,hydrogenationusingH2gasiseco-friendly and cost-effective for NB conversion intoanilines6,in which a key issue is to find catalystswithhighactivityandselectivityundermildcondi-tion.Heterogeneouscatalysts using carbons as sub-stratehavebeenreportedforhydrogenationi.e.noble-metals,non-noblemetalsandmetal-freecarbons,us-ingH2asareductant.NoblemetalssuchasPd,PtorRu as active centers have good catalytic perfor-mances79.Pd-loadedcarbontubesownedhighactiv-itywithTOFvalueof66900h1andanilineselectiv-ity of 99%for NB hydrogenation10.Vanyorek etal.11reportedcarbonblackanchoredPd-PtcatalystsusingNiOorFe2O3aspromoter,showinglittlediffer-enceinactivityandselectivityatawidetemperaturerangeand2MPaH2,whileactivationenergyofcata-lystswaslowof7.6kJ/mol.Pd,N-dopedcarbonfoamalsousedinNBhydrogenation12,andNBconversionwith 99.1%aniline yield and 99.8%selectivityreachedregardlessoftemperature.CarbontubeswithP,N-speciesandB-Nco-dopedgrapheneswerealsoreportedasthemetal-freecatalystsfornitroarenehy-drogenation1315,while the comparable activity wasonlyobservedaspressureover3MPaandreactiontimeupto15h.As comparison,non-noble metal-based carbonsi.e.MNC(MFe,CoorNi)alsohadamazingactivities and low costs,16 and great progress hasachievedeveniftheiractivityisstillslightlyinferiorto that noble metal-based carbons1721.CoNCcatalysts as pyrolyzed by hybrids of melamine,Co(NO3)2andpolyacrylonitrilehadgoodactivityinnitroarene reduction22,and the catalyst with fluffyReceived date：2022-11-30；Revised date：2023-01-29Corresponding author：CAIJin-jun,Associatedprofessor.E-mail:Author introduction：YANGYu,Masterstudent.E-mail:第38卷第3期新型炭材料（中英文）Vol.38No.32023年6月NEWCARBONMATERIALSJun.2023mesoporesandrichN-speciesshowedbothafullcon-versionandanilineselectivityat120Cand1MPaH2.Recently,numerousmethodshavebeenreportedtoprepareMNCcatalyst,especiallyforpyrolys-isofzeoliteimidazolateframework(ZIFs)2325,be-causetheyoftenhaveadvantagesofhighsurfacearea,hierarchical pores,high N content from imidazole,andeasilysubstitutionofmetalsfromdifferentmetalsalts.Forinstance,Co-Nco-dopedcarbonswerede-rivedbyZIF-67pyrolysisandthesizemodulatedbycontent of imidazole3,exhibiting a full conversionandanilineselectivityover99%at1MPaH2.NBhy-drogenationdidnotoccurafteretchingtoremoveCo-species3,indicatingthesynergisticeffectbetweenCoandN-species.Liuandco-workersreportedthedesignofhollowCoSxanchoredonN-dopedcarbonsbyZIF-67pyrolysisandNH3etching26,andS-defectincata-lysts was positive to achieve high activity for nitrocompoundshydrogenationat100Cand1.6MPaH2.ItisadmittedthatN-speciesareusefultoadjustelec-tronicof carbon atom and uniformly stabilize ul-trafinemetals,boostingactivityofM-Nxcoordination.However,ZIFsproductionrequiredlongtimeandpro-hibitivecostinthelinkersandpyrolysisalsolargelyreducedyield,limitingtheirpracticaluseinmasspro-duction.ItisnecessarytoseekagreenandscalablemethodtocreateCoNCcatalystsforthebetteruseofhydrogenationreaction.Herein,wereportedafacilemethodtoincorpor-ateCo-speciesintoN-dopedcarbonsthroughhydro-thermal treatment of glucose biomass,followed bypyrolysisofhybridofhydrochar,Co(N