TPD

2004/4/10(Temperature-programmedDesorption)2004/4/101.R.I.Masel,PrinciplesofAdsorptionandReactiononSolidSurfaces,JohnWiley&Sons,Inc.,1996.2.A.I.Hubbard(Ed),TheHandbookofSurfaceImagingandVisualization,CRCPressInc.,1995.2004/4/10TPDTemperature-programmedDesorptionTPDTPDTPDTPRSTemperatureProgrammedReactionSpectroscopyReaction-limitedDesorptionDesorption-limitedProcess2004/4/10“”“”“”θθνθθ⎥⎦⎤⎢⎣⎡-=-=RTEdtdrn)(exp)()(qqqnqq2004/4/10Fig.10.1Source:Chittenden,Pylant,Schwaner&White,inHubbardTPD2004/4/1010.1TPDTPDTPD1010Torr“”molecules/cm2⋅secTPDTPD2004/4/10TPDvanderWaalsTPD2004/4/10LEED2×2c(2×2)¼½10.22004/4/10Fig.10.2Source:Chittenden,Pylant,Schwaner&White,inHubbard2004/4/10110K/s2004/4/10TPD“”HREELSIRASLEEDXPSSIMS10.3TPDTPD2004/4/10Fig.10.3Source:Chittenden,Pylant,Schwaner&White,inHubbardTPD2004/4/1010.41.0LangmuirTPDStickingCoefficentStickingProbability1.010.5tiA1A2TPD2004/4/10Fig.10.4Source:Chittenden,Pylant,Schwaner&White,inHubbardTPD2004/4/10Fig.10.5Source:Chittenden,Pylant,Schwaner&White,inHubbardTPD2004/4/10nkArrheniusEaνRTPolanyi-Wigner1.0nkdtdrqqq=-=)(⎟⎠⎞⎜⎝⎛-×=RTEkaexpn⎥⎦⎤⎢⎣⎡-=RTEran)(exp)()(qqqnqTPD2004/4/10Polanyi-WignernEaνnEaνlnr(θ)–nlnθ1/TEaνTPDTPD⎥⎦⎤⎢⎣⎡-=-RTEnra)(lnln)(lnqnqqRESlopea-=nln=InterceptTPD2004/4/101962P.A.RedheadTPDTPDTPDRedhead1)β(K/s)tT02)3)4)EatTT×+=b0Redhead2004/4/10Polanyi-WignerTTPDn=1n=2θTPEdν=1013s-1()TPTPDEdTP10.6⎟⎟⎠⎞⎜⎜⎝⎛-⎟⎟⎠⎞⎜⎜⎝⎛=pdPdRTERTEexp12bn⎟⎟⎠⎞⎜⎜⎝⎛-×=⎟⎟⎠⎞⎜⎜⎝⎛PaPaRTERTEexp2202nbq⎥⎦⎤⎢⎣⎡-⎟⎟⎠⎞⎜⎜⎝⎛=64.3ln1bnPPdTRTERedhead2004/4/10Fig.10.6Source:Chittenden,Pylant,Schwaner&White,inHubbardRedhead2004/4/10RedheadTPDEanRedheadTPDνn0RedheadEaν⎟⎟⎠⎞⎜⎜⎝⎛×=-PanPaRTEnRTEexp12qbnRedhead2004/4/10Habenschaden-KüppersRedhead,EaνTPDPolanyi-WignerTEdCOCo(1010)TPD10.7CCl4GaAs(110)TPD10.8LibermanRETddnTddTdrdd-=--)/1(ln)/1()ln()/1()](ln[qqbn2004/4/10Fig.10.7Source:Chittenden,Pylant,Schwaner&White,inHubbard2004/4/10Fig.10.8Source:Chittenden,Pylant,Schwaner&White,inHubbard2004/4/10Polanyi-Wignerθ→0d/dθθνθ→0TPDEaθn=1νθTPDqqnqnqnqbddERTddnRTERTEaPPaPan×-+=⎟⎟⎠⎞⎜⎜⎝⎛××-exp21⎥⎦⎤⎢⎣⎡×+⎟⎟⎠⎞⎜⎜⎝⎛×××⎟⎠⎞⎜⎝⎛≈-qqnqbnddERTRTERTEnaPPaPanexp1212004/4/10Chan-Aris-WeinbergCAW10.9EaνTPDTPDCAW1)⎟⎟⎠⎞⎜⎜⎝⎛++-=2121832.51WTTWRTEPPPd⎟⎟⎠⎞⎜⎜⎝⎛=PdPdRTERTEexp2bnCAW2004/4/102TPDEaνθEaνCORh(111)10.10Ea≈31.6±1kCal/molν=1013.6±0.3s-1CAW10.11Eaνθ0~θ0EaνθEa⎟⎟⎠⎞⎜⎜⎝⎛++-=2121117.31WTTWRTEPPPd()⎟⎟⎠⎞⎜⎜⎝⎛+=PdPPddRTETRRTEEexp2/3202qbnCAW2004/4/10Fig.10.9Source:Chittenden,Pylant,Schwaner&White,inHubbardCAW2004/4/10Fig.10.10Source:Chittenden,Pylant,Schwaner&White,inHubbardCAW2004/4/10Fig.10.11Source:Chittenden,Pylant,Schwaner&White,inHubbardCAW2004/4/10TPDnEaνPolanyi-WignerTPDθ(T)10.5A2Eaν1TEaνCAWEaνθ0θ→0EaνEaνTPD12Eaν310.1213Ag(111)Ea≈15.2±1.5kCal/molν=109.61±1s-1[]RTEnra-=--)](ln[ln)(lnqnqq[]qqln)(lnnr--2004/4/10Fig.10.12Source:Chittenden,Pylant,Schwaner&White,inHubbard2004/4/10TPDAg(111)2CH2CH(a)→C4H4(g)1)Ea≈62.3kCal/molν=109.6s-110.132)RedheadEa≈83kCal/molν=7.24×1012s-110.143)Ea≈41.2kCal/molν=3.40×109s-110.154)CAWEa≈50kCal/molν=6.35×105s-110.16TPD2004/4/10Fig.10.13Source:Chittenden,Pylant,Schwaner&White,inHubbard2004/4/10Fig.10.14Source:Chittenden,Pylant,Schwaner&White,inHubbardRedhead2004/4/10Fig.10.15Source:Chittenden,Pylant,Schwaner&White,inHubbard2004/4/10Fig.10.16Source:Chittenden,Pylant,Schwaner&White,inHubbardCAW2004/4/10n=0Source:R.I.MaselTPD2004/4/10H2OCCl4Au(111)Au(111)R.S.Smithetal.,PRL79(1997)909.25K162K2004/4/10i)15Kii)1)2)3)4)5)2004/4/10R.S.Smith&B.D.KayNature398(1999)788.2004/4/10R.S.Smith&B.D.KayNature398(1999)788.2004/4/10R.S.Smith&B.D.KayNature398(1999)788.2004/4/10K.P.Stevensonetal.,Science283(1999)1505.2004/4/10K.P.Stevensonetal.,Science283(1999)1505.2004/4/10K.P.Stevensonetal.,Science283(1999)1505.