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úËõ Nov. 2013 Vol.26 No.6  317(C) 2013 The Japanese Society for Synchrotron Radiation Research½êÉéÙÆñÇ·×ÄÌ»wíðÆç¦é±ÆªÅ«é NAP_XPS ðæèã°éBÈ¨C``NAP'' Í ``Near
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Fig. 2 (Color online) Schematics of the NAP_
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318  úËõ Nov. 2013 Vol.26 No.6

[^[r[ðà ¡ åC³ X üõdqªõ@ÉæéG}\ÊÌ»ÌêÏªªoéB
NAP_XPS uÍAJC[bpðnßC¢E
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Fig. 3(Color online) Schematics of the NAP_XPS system deve­
loped at the Photon Factory; reaction cell and dierential
pumping electron energy analyzer. Inset: Conguration ofsample, x­ray window, aperture, shields for dierential
pumping and analyzer entrance. Details are described inRefs. 8, 9).

êé±ÆâCNAP_XAS ÌªèÖg£Å«é±Æª°çêéBÅßÅÍCóÔªð\ðÂdqGlM[ªÍí Æ g Ý  í ¹ ½è13,14) C d X ü ð p ¢é ± Æ É æ ÁÄCæè[¢ê©çÌîñâÅtEÊÌîñðø«o·Ýàsíêæ¤ÆµÄ¢éBÀ±ºÅàúËõ{ÝÅàCNAP_XPS ÍG}ð²×é½ßÉ³­ÄÍÈçÈ¢è@ÌêÂÉ­WµÄ¢­Â\«ªéB

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ÉCAiCU[©gªÂ 2 iÌ·®rCnÆªèÄ«½ªC±±Åæèã°é Pd(100) \ÊÅÍC´^ÉÝ¯½ 2 iÌ·®rCnÆð¹Ä 4 iÌ·®rCn

óºCº·É¨¢ÄCCO ªqÍ(100)\ÊÌ bridge siteµCí¢¦0.5 MLi±±ÅÍ\Ê Pd ê´qwð 1

ð¿C1 mm ÌAp`[JûaÅ 1 Torr öxÌ³ÍÉzºÉu©ê½¿ÌªèªÂ\ÉÈÁÄ¢éBÜ½Cõd

ML ÆµÄ¢éjCi2 2 ~ 2 )R45
Ìüú\¢ðÆé±qÆ¤É·®rCnÉüéKXÌêðTvOµC

ÆªmçêÄ¢éiFig. 4(ajjBîÂðá·ÉââµÄs¿ÊªÍviMSjÅªè·é±ÆÅC¿ßTÌCí­Ææè½­Ì CO ªqªz·éæ¤ÉÈèCæÉÌª³ðj^[·é±ÆªÅ«éB±ÌCÌ½íÉ§xª`¬³êÄ¢­iFig. 4(b), (cjjB³çÉ³Å¶¬íÌª³Ï»©çG}«ðA^CÅmé±Æ

CO ð±üµ½êÉÍC·×ÄÌ\Ê Pd ´qÉ CO ª

úËõ Nov. 2013 Vol.26 No.6  319

Fig. 5

Fig. 4(Color online) CO adsorption phases on Pd(100) with
_2CO (udierent CO coverages; (a) (2 2 ~ 2 )R45
_4CO (u0.67 ML), (c)0.50 ML), (b) (3 2 ~ 2 )R45
_6CO (u0.75 ML), (d) (1~1)_CO (u(4 2 ~ 2 )R45
1 ML). Reproduced from Ref. 15).

(Color online) Ambient­pressure XP spectra obtained under
the presence of gaseous CO up to 0.5 Torr for (a) Pd 3d5/2and (b) C1s regions at room temperature. Labels in thegures (a, b, g and d) show the series obtained at same pres­sure conditions. X­ray energy of 435 eV was used for Pd3d5/2
and C1s. Pd 3d5/2 was deconvoluted into three components``Bulk'' at 334.9 eV (blue line), ``CO(I)'' at 335.5 eV(green line) and ``CO(II)'' at 335.9 eV (orange line).
Reproduced from Ref. 15).

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320  úËõ Nov. 2013 Vol.26 No.6

éÌÍ NO »ÌàÌCàµ­Í NOéðà ¡ åC³ X üõdqªõ@ÉæéG}\ÊÌ»ÌêÏªð£zðµ½Ê¶¶½àÌÆl¦çêéB´^óºÅÌ±êÜÅÌÀ±©çÍCPt(111) ÅÍð£zCÌå«³Í 1 nm öxÅèCXebvßTÌæ¤ÈªN±ÁÙÈêÉÇÝ·éí¯ÅÍÈ­C\ÊSÌÉ_çÈ¢Æ³êÄ«½ÌÅC±ü³ª­ÈÁ½±ÆÉæÁÉªzµÄ¢é±ÆªmF³ê½B±Ì±ÆÍCNO ªq

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ÉCNO ðrCµ½ãÌ\Êðªè·éÆ NO hC«ð¦·Â\«ªéB»Ì½ßC»Ìæ¤Èim±qðà NO{O hCà»ÌÜÜcéB·Èí¿C1 Torr Ì¬µCKX¶ÝºÅÌ®ð»ÌêÏª·é¤ª·ñNO ð±üµ½Æ«Ì\ÊÍ³Íð UHV ÉßµÄà³ÌÉsíêÄ¢éB±±ÅÍCñ³ànÌ Core­Shell \óÔÉßçÈ¢ÀèÈzóÔð¦·D¢ðÂ÷±qÉ¨¢Ä­©³ê½\¢]ÚÉÂ¢ÄÐî±Ì±ÆðpµÄCUHV Éßµ½\ÊÌ STM ðÏµÄ¨­BUC Berkeley Ì Gabor Somorjai mçÌ¤@µÄÝéÆCXPS ©çè³êéÆ¨èCNO{O hO[vÍTCYIðIÉ¬µ½15 nm aÌ Rh0.5Pd0.5

Cª NO ÌÉªUµ½ª¾çêéDêÂÌhà±qð XPS Åo[xðÏ¦ÈªçªèµCPd ªcore, Rh ª shell ÆÈÁ½ Core­Shell \¢ðæÁÄ¢é±ÆðmFµ½B³çÉ±Ì±qð0.1 Torr Ì NO µÍCº
Æ NO{CO µÍCºÉu­ÆCKXµÍCÉæÁÄ coreÆ shell Ìà®ªüêÖíé±Æð©oµ½iFig. 7jBNO¾¯ð±üµÄ¢éðÅÍ Rh ª±q\Êð¢ÁÄ¨èC»Ì»wIóÔÍ Rh _»¨ÆÈÁÄ¢éBNO{COÌG}½ðÉ·éÆCCO ÉæéÒ³ªN±èC\ÊÉÍà® Pd Ìª­ÈéB±Ìæ¤È Core­Shell ÌFig. 7
Fig. 6(Color online) (Top) N 1s XPS spectra for NO on Pt(111)under dierent conditions. From bottom to top: After doseof 18 L NO taken under UHV; 1~10|7 Torr NO; 1~10|6
Torr NO; 1~10|5 Torr NO; 1~10|2 Torr NO; 1~10|1
Torr NO; 1 Torr NO; after NO evacuation. (Bottom) Struc­ture model for NO/Pt(111) at 1 Torr. Reproduced from
Ref. 18) with modication.

(Color online) (Top) Gas­induced changes in Rh and Pd
Catomic fractions in the Rh0.5Pd0.5 nanoparticles at 300
under oxidizing conditions (100 mtorr NO or O2) and cata­
lytic conditions (100 mtorr NO and 100 mtorr CO). (Bot­tom) Changes in the fraction of the oxidized Rh (left y axis)
and Pd atoms (right y axis) measured under the same reac­tion conditions as the top part of the gure. Reproduced withpermission from Ref. 19); F. Tao et al. Science 322, 932_934(2008).

úËõ Nov. 2013 Vol.26 No.6  321

üêÖíèÍ±ü·éKXÌíÞÉ¶ÄÂtIÉN±
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éB±Ìæ¤È±Æð²×é½ßÉCP»âim±qðfG}ÆµÄ½KXð±üµCG}ÆµÄ®ì³¹ÈªçG}«ÆG}\ÊóÔð in­situ ÇÕ·é¤ª NAP_XPS ðgÁÄsíêÄ¢éB±±ÅÍC½¿ªsÁ½ Pd P»ðfG}Æ·é CO _»½Ì»ÌêÏ@ÉÂ¢ÄÐî·éBPd Í©®ÔrKXG}Å
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Fig. 8Fig. 8(a)É Pd(111) îÂð300
CÉÛ¿C_fÆ CO ð±üµÈªçCCíÌª³ðj^[µ½Êð¦·BßÉ CO ð 2~10|2 Torr ±üµÄêè¬ÊÉÛ¿C_
fð±üµÄ¢­ÆCPd G}ÉæÁÄ CO Ì_»½ªiÝCCO2 ª¶¬·éB_f³ª 2~10|1 Torr ÉBµ½ÔÌæiajÅÍCÙÆñÇÌ CO ª½µÄ CO2 ÉÈ(Color online) (a) Time evolution of partial pressures of O2,
CO and CO2 under CO oxidation reaction conditions on
Pd(111) measured at the NAP_
XPS system. The time region
denoted by a is corresponding to the most active condition.
(b) O 1s XP spectrum taken at the time region a. (c)Structure model of a surface oxide (Pd5O4). Yellow and redballs indicate oxygen atoms coordinated by three and four
Pd atoms, respectively. Reproduced from Ref. 8) withmodication.

ÁÄ¨èCñíÉ«ª¢óÔÉÈéªC±ÌÆ« O
1s XPS ðªèµ½àÌª Fig. 8(b)ÅéB±üµ½_f

ÏªðsÁ½Êð Fig. 9(b)É¦µÄ¢éB«Ìá¢Æ CO ÌKXÌs[NÉÁ¦C¶¬µ½ CO2 KXÌs[A, B ÌðÅÍCC 1s XPS ©ç\ÊÉ CO ªqªzµ

Nª©çêéBPd \ÊÌ_fíÆµÄÍCO(IjCO(II)Ä¢élqªª©éBPd 3d5/2 Å©Äà CO ÌÝðz³

Æ¼t¯½ñÂÌ¬ªªÏª³êéB±êçÌs[NÍC¹½iFig. 4jÆ¯lÌGlM[ÊuÉñÂÌs[Pd Ì_»ÉÖ·é XPS, STM, DFT vZÈÇÉæé¤NªÏª³êéB·xª¢ B ÌðÅÍ\ÊÌ CO z

É î Ã ­ Æ C Fig. 8 ( c ) É ¦ · æ ¤ È P w Ì \ Ê _ » ¨ªá±aÉÈÁÄ¢élqàª©éB±Ìæ¤ÉC

iPd5O4jÌ_fíÉA®³êéB±Ì_fíÉÍ Pd zÊ

190CÈºÅÍCPd \ÊÍ CO ªqÉ¢íêÄ¨èCO2ÌÙÈé 2 íÞÌ_féªC±Ì¤¿C½·éÌÍzÊªá¢ 3 zÊÌ_fÅ

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CO2 ¶¬Í­ÉisµÄ¢éÌÅC±ÌðÅÍ\Êé±Æª¦´³ê½8)B¯ l Ì À ± ð Pd ( 100 ) Ê É Î µ Ä à s Á ½

20) B Pd

Ézµ½ CO ªqÌ½ÏØÝÔªZ¢½ßÉXyNg(100) \ÊÉ_fÆ CO ðêè³i P(O2)2~10|1 Torr,ÆµÄ©¦È¢Æl¦çêéBPd 3d5/2 ð©éÆCbulk

P(CO)2~10|2 TorrjÅ±üµC\Ê·xðã°Èªs[NÌáGlM[¤É 1 ÂCGlM[¤É 2 ÂçÏªµ½Êð Fig. 9 É¦·BFig. 9(a)Í NAP_XPS ÌVµ¢s[NªÏª³ê½B±êÜÅÌ Pd Ì_»Ì¤uÌ¿ÊªÍvÅªèµ½ CO2 ¶¬¬xÌ·xË¶«Å © ç C ± Ì   «  Ì \ Ê É Í Fig. 10 É ¦ · æ ¤ ÈCÓèÜÅÍG}«ªá­s«ÅéBº·©ç170

Ìüú\¢ðÂ\Ê_»¨ªoÄ¢i 5 ~ 5 )R27

CÅ}É«ªüãµC»ÌãÉâ©É¸
éªC190­µÄ¢­lqªª©éBA, B, C, D Ì·xðÅ XPS

322  úËõ Nov. 2013 Vol.26 No.6éÆªµ½B\Ê_»¨Í Pd(111) ãÅ`¬³ê½àÌà»¤ÅéªCêÊIÈoN_»¨ÆÍÙÈèCàðà ¡ åC³ X üõdqªõ@ÉæéG}\ÊÌ»ÌêÏªFig. 11
Fig. 9(Color online) (a) Temperature dependence of MS intensityof CO2 under exposure to 2~10|1 Torr of O2 and 2~10|2
Torr of CO. The CO2 background contribution from theresidual gas was subtracted. Each label (A, B, C, and D)
indicates temperature where XP spectra were measured. (b,c) XP spectra recorded at Pd 3d5/2 region and C1s region,
respectively, which indicate a drastic change in surface chem­
ical state at around 190C. XP spectra denoted by ``E'' weretaken at 370C under P(O2)2~10|1 Torr, after stopping
the CO gas dose. Reproduced from Ref. 20).

(Color online) O1s XP spectra taken under CO oxidation
reaction conditions: at point C, where the reaction rate is the
maximum (bottom), and at point D, where the reaction rate
decreases a little (top). (b) Side view of a model structure
for the ( 5 ~ 5 )R27surface oxide on Pd(100). Largeand small balls indicate Pd and O atoms, respectively. Notethat a broad feature at a higher binding energy (black solidline) is attributed to Pd 3p3/2 photoelectrons from thesubstrate. Reproduced from Ref. 20).

hCb`\¢ðÁÄ¨èCPdO oN_»¨ªêwªÍÏµÄ¢éÆÝé±ÆàÅ«éB±Ì_»¨ÌÌPd ÉÍ_fª 2 zÊµ½àÌÆ 4 zÊµ½àÌÌ 2 ÂÌ»wIÂ«ªÙÈé Pd ªéBDFT Éæé CLS ÌvZ©çCGlM[¤Ì 2 ÂÌs[Nª±êç 2 íÞÌ
Pd RÅ

é±ÆªmF³ê½BÜ½CáGlM[¤Ì ¬ ª Í _ » ¨ Æ à ® î Â Ì « E É ¶ Ý · é Pd ( 2ndlayer) RÅé±Æàí©Á½BO 1s xÌs[NàÜßÄC«ÉÏª³ê½·×ÄÌs[Nªi 5\Ê_»¨ÉA®³êé±ÆðmFµ½B~ 5 )R27
á±«Ì¿½ D ÌÉÍ«Ì¢ C ÌÉä×ÄCPd 3d5/2, O 1s XPS ÆàÉÏ»ª»êéBFig. 11 É CÆ D ÌÉªèµ½ O 1s XPS XyNgð¦µ½B±±ÅCáGlM[¤Ì¬ªÍ\Ê_»¨Ì\Ê¤ÉIoµ½_fCGlM[¤Ì¬ªÍà¤ÉÊu·é_f©
çÌMÉA®³êéB®SÈ\Ê_»¨ÅFig. 10(Color online) The overview (a), and the unit cell from top(b) and side view (c) of the ( 5 ~ 5 )R27surface oxide
on Pd(100). The gray and red balls indicate the Pd and O
atoms, respectively. The labels indicated on surface Pd
atoms ``2f'' and ``4f'' show the coordination number of O
atoms. The labels attached to O atoms ``Up'' and ``Down''
show the relative height of the O atom with respect to the
topmost Pd layer. Reproduced from Ref. 20).

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Pd 3d5/2 XPS XyNgiFig. 9(b)DjÉVµ¢¬ªª»
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Pd(100) \ÊÉ`¬³êé\Ê_»¨Í O_Metal_O ÌTÄ¢é±Æð¦´µÄ¢éB
NAP_XPS ðp¢Ä CO _»½ð»ÌêÏª·é±ÆúËõ Nov. 2013 Vol.26 No.6  323

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úËõ Nov. 2013 Vol.26 No.6  325

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In­situ observation of catalytic surfaces withnear ambient pressure x­ray photoelectron
spectroscopy
Hiroshi KONDOH

School of Science and Technology, Keio University
3_14_1 Hiyoshi, Kohoku­Ku, Yokohama 223_
8522

Ryo TOYOSHIMA

School of Science and Technology, Keio University
3_14_1 Hiyoshi, Kohoku­Ku, Yokohama 223_8522

Abstract

The near­ambient­pressure x­ray photoelectron spectroscopy (NAP_XPS) using synchrotron radi­
ation sources enables us to observe the chemical state at surfaces of a material under thepresence of gas(es) at a near ambient pressure, which has been hardly conducted with the con­ventional XPS technique. The core­level­shift calculations based on the density functional theory
can assist to discuss about adsorption structures and catalytically active surfaces under NAP con­ditions in detail by comparison with the observed CLSs of spectra. In this review article, we in­troduce the development and the current status of this technique and describe atomic andmolecular processes at catalytic surfaces observed by this technique with presenting some exam­
ples of the application studies and nally give comments on the future direction of this technique.

326  úËõ Nov. 2013 Vol.26 No.6