Thermal radiative catalysis：Selective dehydrogenation of ethane to ethylene by vibrationally excited carbon dioxide.docx

Artic1eTherma1radiativecata1ysis：Se1ectivedehydrogenationofethanetoethy1enebyvibrationa11yexcitedcarbondioxide夕CepressXueDing,ZeshuZhang,JunchuanSun,.,GeoffreyA.Ozin,ZhigangZou,1uWangzhixin.hu(Z.H.)g.ozinutoronto,ca(G.A.0.)zouzhigangg>(Z.Z.)1wdng(1.W.)High1ightsUti1izationoftheneg1ectedtherma1radiationtoenab1etherma1radiativecata1ysisThetherma1radiativecata1ysisnatura11yintegrates1ightandheatNoinstabi1ityandperiodicityissuesforusingtherma1radiationEmittedtherma1radiationcou1denhancetheethy1eneyie1dandse1ectivityThero1eoftherma1radiationininteractingwithreactantmo1ecu1eswithinthetraditiona1therma1cata1yticprocesshasbeenneg1ectedforcenturies.Thee1ectromagneticradiationemittedbythereactorheatingmodu1escanse1ective1yexcitethevibrationa1modesofthereactantsandthuspromotetheine1asticco11isionbetweenthecata1ystandthereactantmo1ecu1es.Inthiswork,CO2isconsideredthegaseouscata1ysttofaci1itatetherma1radiativecata1yticethanedehydrogenation,resu1tinginanenhancementinethy1eneproductionby120%whi1emaintainingthese1ectivityata1most100%.Artic1eDingeta1.,Jou1e7,1-17October18r20232023E1sevierInc.https:/doi.org/10.1016/jjou1e.2023.08.010Therma1radiativecata1ysis：Se1ectivedehydrogenationofethanetoethy1enebyvibrationa11yexcitedcarbondioxideXueDingz142ZeshuZhangz142JunchuanSun/42Joe1Y.Y.1oh/DongxuJi/Jinghui1u/Chengyuan1iu,31ongZhao,3,4Wenxuan1iu,'5JunhuaZhao,*San1iTang，？MahdiSafari,2Ha1tingCaiz8WenguangTu,1NazirP.Kheraniz2,9ZhixinHu°,*GeoffreyA.Ozi7,*ZhigangZouz1,n,*and1uWang1,n,*AMessSUMMARYTheinteractionbetweentherma1radiationandreactantmo1ecu1esinaconventiona1therma1cata1yticreactorhasbeenover1ookedasanenergysource.Thee1ectromagnetictherma1radiationfromtheheatingmodu1escanexciteinfraredvibrationa1modesofreactantmo1ecu1es,faci1itatingine1asticco11isionsthatse1ective1yenhancereactionpathways.Herein,carbondioxideenab1estherma1radiativecata1yticethanedehydrogenationandisfoundtoboosttheproductionofethy1eneby120%withase1ectivityofabout100%.INTRODUCTIONSincethediscoveryoftraditiona1thermocata1ysisinthefirstdecadeofthe19IhcenturybyGott1iebKirchhoff,therma1excitationfromdirectheatconductionhasbeenconsideredthedominantdrivingforceintheovera11cata1yticprocess,whereastheconsequente1ectromagneticenergy(therma1radiation)thatarisesduetoemissionfromthereactor'sheater;wa11s,orfromthecata1ystbedhasusua11ybeenneg1ected.1Photoe1ectrocata1ysisandphototherma1cata1ysisrepresentanewerainthehistoryofcata1ysisinwhichasecondenergysource,e1ectromagneticenergy,isinvo1vedinthecata1yticprocess.Harnessingthee1ectromagneticenergieswithinawe11-integratedsystemhasshownpromisingprogressandhasprovedtobeadvantageousinreactorengineeringandcata1yticperformance.5-11However,owingtothenon-continuityofsun1ightandthe1ackofacheap,intense,andconstant1ightingsource,thepractica1deve1opmentofthemajorityof“1ight-invo1ved”cata1ytictechno1ogieshasbeenhindered,especia11yin1arge-sca1echemica1production.Therefore,itwou1dbeofhightechno1ogica1importanceandscientificinterestifphotocata1ysiscou1dbeconductedwiththerma1radiation.Iftherma11ydrivencata1yticreactionsareconductedathightemperatures,thecorrespondinge1ectromagnetictherma1radiationassociatedwiththereactorcavitymayp1ayaro1einparticu1arreactions.BasedonP1anck,s1aw,theb1ackbodyradiationemittedattemperaturesbetween500Cand1,OCismain1y1ocatedintheIRregionbetween1,000and10,000nmwiththeb1ackbodyemissiveoutputpowerproportiona1tothe41hpoweroftheabso1utetemperatureaccordingtotheStefanBoItzmann1aw,EquationI.12P=e$s$A$T4(Equation1)Jou1eArtic1eCONTEXT&SCA1EHigh-temperaturethermocata1ysisp1ayedamajorro1eintheindustryoffinechemica1production.Thetemperatureinthermocata1ysisusua11yrepresentsava1uetowardmo1ecu1aractivation,whereasthecorrespondingtherma1radiationhasbeenneg1ectedforcenturies.BasedonP1anck,s1aw,theb1ackbodyradiationemittedattemperaturesbetween500Cand1,000Cismain1y1ocatedintheinfrared(IR)region,whichcou1dbeeffective1yabsorbedbya1argegroupofmo1ecu1esandintermediates.Thus,itwou1dbeofhighimportanceandscientificinteresttostudythero1eoftherma1radiationinHightemperaturereactions.Inthiswork,ethanedehydrogenationhasbeenchosenasthearchetypereactioninaspecia11ydesignedtherma1radiativereactortodemonstratetherma1radiativecata1ysis.Thecarbondioxideactsastheenergymediatorandthecata1yst,whichcou1denab1eanewinitiatestepandthusfaci1itatetheproductionofethy1ene.Whereeistheemissivityofthemateria1,sistheStefan-Bo1tzmannconstantorStefan,sconstant,Aisthesurfaceareaoftheb1ackbody,andTistheb1ackbody'sJou1e7,1-17,October18,20232023E1sevier1nc.-thermodynamictemperature.Ethanedehydrogenationtoethy1enewasusedasanarchetypeRESU1TSTheethy1eneandhydrogenproductionfromethanedehydrogenationwascata1yzedbygreenhousegasmo1ecu1eswiththerma1radiationathightemperatures(500C-600C).TheA2O3-basedceramicheatingmodu1eswereusedasthenon-contactheatingsource.BasedonP1anck,s1aw,theheatingmodu1eswi11emittherma1radiationmain1y1ocatedinthenear-infraredtomid-in