环境微界面过程的原位和在线研究方法

29120091ActaScientiaeCircumstantiaeVol.29,No.1Jan.,2009:(No.50621804);(No.40775081)SupportedbytheFundsforCreativeResearchGroupsofChina(No.50621804)andtheNationalNaturalScienceFoundationofChina(No.40775081):(1965),,(),E2mail:[e-mail];3()Biography:HEHong(1965),male,professor(Ph.D.),E2mail:[e-mail];3Correspondingauthor,,.2009.[J].,29(1):11-20HeH,LiuYC,QuJH.2009.Insituandonlineresearchmethodsformicro-interfaceprocessesinenvironment[J].ActaScientiaeCircumstantiae,29(1):11-203,,,100085:2008210217:2008211219:,.,.,,,,.:;;;;2:025322468(2009)01211210:X131:AInsituandonlineresearchmethodsformicro2interfaceprocessesinenvironmentHEHong3,LIUYongchun,QUJiuhuiResearchCenterforEco2EnvironmentalSciences,ChineseAcademyofSciences,Beijing100085Received17October2008;accepted19November2008Abstract:Micro2interfaceprocessesaretheprimaryprocessesforthetransportationandtransformationofpollutantsinenvironment,andarealsothebasisfordevelopingenvironmentalpollutioncontroltechnologies.Itisimportanttodevelopinsituandonlineresearchtechniquesfortheexplorationofthetransferandtransformationofpollutantsonmicro2interface.Onthebasisofthecharacteristicsofmicro2interfaceprocessesinenvironmentandtheinsituresearchmethodsappliedinenvironmentalheterogeneouscatalysis,thechallengeandcountermeasureduringthestudyofmicro2interfaceprocesseswerediscussed.Theapplicationofinfrared,Ramanandmassspectroscopiesinmicro2interfaceprocessesstudybetweensolidandgasphasewerealsodiscussedinthisarticle.Finally,theframeworkofinsituandonlineresearchmethodologyformicro2interfaceprocessesinenvironmentwasproposed.Keywords:micro2interfaceprocesses;insituandonlineresearchtechniques;infraredspectroscopy;Ramanspectroscopy;Knudsencell2massspectroscopy1(Introduction),.,;();.,;,.,.,,.,..,(PAHs)(Perraudinetal.,2007),,29.,..,,.,.,,22,,.,.,,(Pressureandmaterialsgaps)(,2003;Zaera,2002).,,.,;,.,.,..2(Characteristicsofmicro2interfaceprocessesinenvironment)1),.,,NO2SO20.310-90.010.110-9()(Ertl,1999),NO225010-9()(Underwoodetal.,1999);PAHsngm-3gm-3(Changetal.,2006),PAHsngm-3(Schaueretal.,2003);ngm-3(Villeneuveetal.,2000).,,,.,,(Schaueretal.,2003).,,.,,..2).,1,,FeMn(BrownJr,2001).(Ertl,1999),(,2007a).(BrownJr,2001).,(Al2AbadlehandGrassian,2003).,.,.,,(OCS)(Heetal.,2005;Liuetal.,2006;2007b;2008a),.,,,,.,,.3),.,,(BrownJr,2001).,.,,1,211:1(BrownJr,2001)Fig.1Schematicdiagramofthecomponentsandstructureofmicro2interfaceinenvironment(BrownJr,2001),.,(CO2);,(Baltrusaitisetal.,2007).,,.4).22,,.,,(SO2)(NOx)(Al2O3),2(Maetal.,2008).,NOxAl2O3(1230cm-1)2NOxSO2Al2O3(a.NO2,b.NO2SO2)(Maetal.,2008)Fig.2SynergisticeffectfortheheterogeneousreactionofNO2andSO2onAl2O3(a.NO2alone,b.NO2andSO2)3129,SO2Al2O3S(IV);SO2NOx,N2O4(1733cm-1),S(IV)S(VI)(SO2-4,1176cm-1).,OCS,NOxSO2CO2OCSMgO.,.,.,,;,.,,.3(insituandonlineresearchmethodsformicro2interfaceprocessesinenvironment)3.1,.,,,,.,,;,,(Sakaietal.,2007).1).,,.(Transmission)(ATR)(RAS)(DRIFTS).2,23(a.(Grassian,2002),b.(,2003),c.(DolamicandBrgi,2006))Fig.3Schematicdiagramofinsituinfraredreactorsuitableforstudyingthemicro2interfaceprocessinenvironment(a.transmissioninfraredreactor,b.DRIFTSreactor,c.ATR)2.3.3aGrassian(2002).1/2,,;411:,,.,,(Soot),.3b,,(,2003).3c.GeZnSe,(1m),,22(DolamicandBrgi,2006).,,2,ATR.,;,,(AubinandAbbatt,2006;Ravishankara,1997).,GrassianHNO3NOxSO2CO2Soot(Baltrusaitisetal.,2007;Grassian,2002;Underwoodetal.,1999;Usheretal.,2002),(NO-3)(NO-2)(SO2-4)(CO2-3)(HCO-3).HNO3CaCO3,(H2CO3)(Al2HosneyandGranssian,2004).,,.Hung(2005)NO3,(ONO2)(NO2)(O2NO2).,.,2.,Dolamic(2006)ATRTiO2(4).4a4TiO2(a.10-4molLTiO2,bc.UV7min20min,df.)(DolamicandBrgi,2006)Fig.4SeriesofATR2IRspectraofmalonicacidonTiO2(Spectrum(a)wasrecordedinthedarkwhileasolutionofmalonicacid(10-4molL)wasflowingovertheTiO2film.Spectra(b)and(c)wererecordedwhileilluminatingtheTiO2filmandsimultaneouslyflowingmalonicacidsolution(10-4molL)at7and20min,respectively.Spectra(d)(f)weresubsequentlyrecordedinthedarkwhileflowingpurewaterovertheTiO2film),10-4molL-1TiO2;bc7min20min,,1708169014211275cm-1(2);df,,.Parikh(2008)ATRAs(III)As(V),As.OCS(Heetal.,2005;Liuetal.,2006;Liuetal.,2007b),5129(HSCO-2)CO2-3HCO-3SO2-4SO2-3.5OCSMgO.,OCS:OCSHSCO-2;HSCO-2HSO-3CO2,H2OH2SCO2;SO2-4(Heetal.,2005;Liuetal.,2006;Liuetal.,2007b).OCS,2.5OCSMgO(Liuetal.,2007b)Fig.5insituinfraredspectrafortheheterogeneousreactionofOCSonMgO2).,,;,;,,SiO2Al2O3,1000cm-1,.,SiO2Al2O3.,;,1m,(,2005).,.,NOx,.(2005)NO2NaCl,NaClNO-3(vs,1067cm-1),NO-3(,723cm-1)NaNO3.,,,,.,,OyamaZhang(1996)C2H5OHMoO3/SiO2,6984cm-1MoO.,28922872cm-1MoOMoMoOCH3CH2OCH2.,MoO,984cm-1(960cm-1).373K473K,MoOCH3CH2O;,MoO,.MoOMoCH3CH2O523K.,MoOMo,MoO.,,.,.,,.,,,(,2003;Zaera,2002).,,,611:.,(Pierceetal.,1990)(Noda,1993);,.,.,,(,2003).,.6C2H5OHMoO3/SiO2(Oyamaetal.,1996)Fig.6CatalyticoxidationofC2H5OHonMoO3/SiO23.2.,,;,,.,.,,.,.,2(KnudsenCell2Massspectrometer)(FenterandRossi,1996;GebelandFinlayson2Pitts,2001;Grassian,2002).72,3,,2.,,,.;,,-.OCS2Al2O3MgOH2SCO2(8),7129OCS(Liuetal.,2008a;2008b).72Fig.7SchematicdiagramofKnudsencell2massspectroscopysystemOCS,.,..,Hiden2HPR200.020.03mm,76Torr.OCSMg