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CeWFgG}i©®ÔG}jÌ©ÈÄ¶yÑG}½ÌMà® Pd im±qÌóÔÏ»ð XAFS Éæèv |u»ÌêvÏ@µC]^ÌSG}ÆÙÈÁ½Ué¢ð¾ç©Éµ½B_»ºÌ\ÊÅ¢G}«ª¾çêéÆ¢¤_IwjÉîÃ«CMà®ÌãÖ³fÆµÄåÆµÄ Cu ð¢µ½Bà®im±q_SÌÔÌÝìpð§ä·é±ÆÉæèCCu Ì_»Ò³Á«ðMà®ÉßÃ¯é±ÆªÅ«é±Æªª©Á½BÜ½CMà®Éä×Ä«\Ìòé³fÅ é Cu Æ Ni ðg¹½Æ±ëCNO Ò³«\ªüãµ½BNi_Cu àÅÍ Ni ÌDæI_»É
æè Cu \ÊÌÒ³óÔªÛ³êÄ¢é±Æªª©Á½B±ÌlÈÝvwjÉæèJ­³ê½ Cu G}ÍCúiÌÀèIÈðºÅÍ

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çC2002NÉñ³ê½»ÌJjYÍC_»µÍC} É Í Pd, Pt, Rh Ì 3 í Þ Ì M à ® ª g p ³ ê Ä ¢ é

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[^[[VÉæéÛLäÌÁÈÇÉÎ·é½ßÉClXÈMà®gpÊá¸ÌwÍª¥íê±¯Ä¢éB»ÌêáÆµÄÍCG}Ìò»ðµCMà®ª©ÈÄ¶i©ÈCj·é@\ðÂuCeWFgG}vªè C _ C n c H Æ É æ è 2002 N É Pd niLaFe0.95Pd0.05O3 jÉ¨¢ÄÀp»³ê½1,2) Bø±«C2005NÉÍ Rh niCaTi0.95Rh0.05O3 jC2006NÉÍ Pt niCaTi0.95Pt0.05O3 jÌÀp»ªÈ³ê½3)BuCeWFgG}vÍ]^ÌSG}ÆS­ÙÈÁÄ¨èCMà®³fðCIÆµÄyuXJCg_»¨»ÉÅn³¹½àÌÅéBMà®ÆêÌÆÈé_»¨ÌíÞð¤Ü­gÝí¹êÎC©®Ô^]ÉsíêéANZìâGWÌdq§äÉæéroKXÌu_fZxÌh
ç¬i_»Ò³µÍCÏ®jvÆ¢¤©RÈÂ«Ï»ÉµÄCG}ªKØÈ\¢Ï»ðN±·iFig. 1CFig. 2jB
Ò³µÍCºÅÍMà®ªÍoµÄà®im±qð`¬µC_»µÍCºÅÍÂXÌCIÉªð³êÄ_»¨Fig. 1(Color online) Precious metal reversibly moves into and outof the perovskite oxide (the intelligent catalyst) in order tosuppress the growth of the precious­metal particles as it iscycled between reductive and oxidative atmospheres typicallyencountered in exhaust gas of petrol engines. On the otherhand, metal particles dispersed on a solid support (the con­ventional catalyst) are exposed to the heat of exhaust gas so
as to agglomerate and grow in the course of time.

úËõ March 2013 Vol.26 No.2  57(C) 2013 The Japanese Society for Synchrotron Radiation ResearchFig. 2(Color online) Palladium as well as platinum and rhodium
occupies the B­site (6­fold coordination) of the perovskitestructure in an oxidative atmosphere, and segregates out toform small metallic particles in a reductive atmosphere. The
local structure around palladium changes in a completely
reversible manner. The catalyst retains a predominantly
perovskite structure throughout a redox cycle.
Fig. 3~NXð¼ÚÏªµ½àÌÅÍÈ©Á½BG}½Ì\Time dependence of coordination numbers of Pd_O and Pd_Pd shells under the H2 (left) and the O2 (right) atmospheres
C.
for Pd­perovskite (top) and Pd/Al2O3 (bottom) at 300¢âdqóÔðÏ@µC»ÌÁ«ðð·é±ÆªÅ«êÎCXÈéMà®Ìí¸âVµ¢@\ð©o·±ÆªÂ\ÉÈéÍ¸ÅX±ü¼ãÅÍCÇ¿çÌ¿É¨¢Äà Pd_O ÌzéB

³fíªvWFNguEMà®ðÚw·im±q©ÈÊÍ¸­µCPd_Pd ª»êÄ­éB±êÍCPd ª`¬G}ÌVK­@vi½¬19N©ç23NxjÍC©ÈÄ_»óÔ©çÒ³³êÄà®im±qð`¬·é±Æð¦¶»ÛÆG}½ÌJjYðð¾·é±ÆÉæèCåµÄ¢éByuXJCg_»¨ÅÍÒ³KX±ü¼ã 2_ÉàÉÌMà®í¸iMà®gpÊ[jÌwjð¾böxÅ\¢Ï»ª®¹µÄ¨èC±Ì½¬xÍ·xËé±ÆðÚIÆµÄÀ{³ê½B±±ÅÍC´qÍ@\C¶µÈ¢½ßC{À±ðºÅÍCÌzßöª¥¬ÉÈ Ck»»wHÆò Cåãåw CMD (Com­_CncHÆòÁÄ¢é±Æªª©Á½B»ÌãÍ Pd_Pd ÌzÊÍê

putational Materials Design) O[vÌYw¯AgÉæèÅ

èCÀ{³ê½¤¬ÊÌêðÐî·éBèCPd im±qÌTCYªêèÅé±Æð¦µÄ¢éB»êÉÎµÄCA~iSG}ÅÍÒ³KX±ü 3 bÈ~ÅàXÉzÊªÁµÄ¨èCA~i2. Mà®im±qÌ©ÈÄ¶Ì»ÌêÏ@ãÌ Pd im±qÌTCYªåµ±¯Ä¢é±Æªª©
éBêûC_»KXiO2(50÷)/Hej±üãÌyuXJ©ÈÄ¶@\Ì®I®Ìð¾ÍCG}ÌgpÂ«ðlCg_»¨ãÌ Pd im±qÍ¬â©Éªð³êÄ_fª¶µ½Vµ¢G}ÝvÌLÍÈm©ÆÈéBG}Ì®ìÊÌÌSÉÚ®·éB»êÉÎµÄCA~iSG}Ì»\¢ÆdqóÔðÏ@·é½ßÉÍCúËõðp¢ÅÍ Pd im±qÌ_»ÍåÏx¢Ìªª©éB_»KX½ XAFS ðªè·éÌªÅKÅ±üã 1 b­ç¢ÅzÊÌ¬¢¸­ª©çêéªC±éBSPring­8 Ì´qÍ@\êpr[C BL14B1 ÉÍCGlM[ªU^êÍúÌ\Ê_»ð¦´µÄ¨èC»ÌãCXÉ_»õwnðL·éª XAFS ªèuiªU^ XAFSjª±qàÉisµÄs­lqðÏ@µÄ¢éÆl¦çêðÝuµÄ¨èC1 ~bÌÔªð\ÅMà®ÌóÔðéBu»ÌêÏ@vÅ«é4)BµÍCKXðØÖ¦Èªç·Mà®im±qÌ¶¬ÁÅÉ¨¢ÄÍC_»Ò³Ï®

ÅÏ@µ½Æ±ëCMà®ÌÅnÉÍoÍñíÉ¬ÅÀµÍCºÅÌ_»¨»\¢ÌÀè«Ì]¿âCPd ´qpãÌ_»Ò³µÍCÏ®É\ªÇ]µÄ¢é±Æªª©

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Á½5) BFig. 3 ÉÍµÍCKXØÖãÌCeWFg×jÌðªdvÅG} LaFe0.9Pd0.1O3 iXAFS ªèpÉ Pd ZxðÁµÄLaFe0.95Pd0.05O3 ÉÂ¢Äæê´vZÉæè_f¹¶¢éjÆA~iSG}Ì\¢ÌÔÏ»ð¦·BÒ³¬GlM[ð]¿µ½Æ±ëCPd ÌüèÌ 6 ÂÌ_f

KXiH2(50÷)/Hej±üOÅÍCÇ¿çÌ¿à Pd_O´qi2.09 eVjÍSÌüèÌ_f´qi3.02_3.08 eVjÌÝªÏª³êÄ¨èC¿ª_»óÔÉ

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q O(1) Ì¹¶¬ãÍCO(2ji2.34 eVjÆ O(3ji2.51ªèÉæéiqU®Ìñ²a«â_f×ª´öÆµÄeVjÌ_f¹¶¬GlM[ªC¼ÌSÌüèÌ_fl¦çêéBÜ½CPdO ÅÌzÊÍ 4 Å´qÉä×Ä¬³­]¿³ê½B·Èí¿CPd Ìüè©

58  úËõ March 2013 Vol.26 No.2éBÒ³Kðà ¡ EMà®ðÚwµ½©®ÔG}Ì¤ç_fª²¯Äs«â·¢ªCâÍèSÌüèÌ»\¢ÍÀèÅ

é±Æª_IÉØ¾³ê½B±ÌlÉC_f¹ªiñ¾ÛÌ»\¢Ï»ðl@·é±ÆªÂ\ÆÈÁ½BrCKXÉ_fZxÌ\ªÉé_»µÍCºÅÍCPd Í_fªÊÌÌSÉÅnµ½óÔªÀèÅéBêûC_fZxªs«µÄ¢éÒ³µÍCºÅÍCfàµ­ÍY»fKXªCÉ¶ÝµCÒ³ÜÆµÄ­­±ÆªmçêÄ¢éB±êçfâY»

fKXª_»¨»Ì_f´qÆ½·éÛÉ­¶·éRÄGlM[âÍoµÄ«½ Pd ´qªW·éÛÉ­¶·éÃWGlM[ðl¶·éÆCãqÌ_f¹¶¬Gl

Fig. 4M[ðâ¤±ÆªÅ«CPd ÌÍoÆim±q¶¬Ì½ßÌ½ð£i·é±Æªª©Á½B·Èí¿CroKXµÍCºÅÌG}½ðl¶·é±ÆÉæèCà®im±qÌÅnÉÍovZXªXCb`·é±ÆªðÅ«½B

3. Mà®im±qÌ CO/NO G}½ãqÌ O2 KXÆ H2 KXðp¢½_»Ò³µÍCÆ¯

Variations of XAFS parameters of Pd_
Pd shell of (a) Pd/
Al2O3 and (b) Pd/LaFeO3, during CO/NO successive
dosing at 400C, where E. shift, CN, s2 and R are energy
shift of the Pd K­edge, coordination number, Debye­Waller
factor and interatomic distance of the Pd_
Pd bonding,respectively.

» Ì½ßÉ Ïv«ªå «¢±ÆCA ~iS G}
iPd/Al2O3jÍY»¨â_»Ì¬·ÉÁÅªµ­N±é½ßC«Í¢ªÏv«ÉRµ¢±Æªª©Á½BlÉCCO KXÆ NO KXðp¢ÄàMà®ÌÅnÉÍoÍN±éªC±±ÅÍCÒ³ðsÁÄêU¶¬µ½
Pd im±qÌ CO/NO G}½ºÅÌÇ\¢ÆdqóÔÌÔÏ»ÉÂ¢ÄÐî·é7) B±±ÅÒ³KXÍ CO(9÷)/HeC_»KXÍ NO(9÷)/He ðp¢Ä¢éB4. Mà®©çJÚà®G}Ö
{vWFNgÅÍMà®ÉÖíérL^XÈ³fÆµÄCÀ±yÑ_IÈÂ\«à¢µCCu, Ni, Co, FeFig. 4(a)ÉÍärÌ½ßÉCÜ¸A~iÉ 4 wt÷ÅSÌJÚà®Ì©ç Cu ðIñ¾BXÉCà®ÌÅnÉCÌÊð¦·B
³ê½ Pd ÷±qiPd/Al2O3 jÌ400

ÍoÌ_I]¿ÆµÄæê´MÍwÉæéû@àJ­ßÉ CO ª±ü³êéÆCPd ©ç CO ªqÖdqÌÚµÄ¨èC_»¨Æà®yÑªð¶¬¨ÌOh|e®ªN±èCñ0.07 Å àÌ Pd_Pd ´qÔ£Ìc£ªÏVðär·é±ÆÉæèC·xÆ_fª³ÌÖÆµµ½êÌ CO ªÄÅnÉÍoð]¿Å«éû@ðm§µ½B»ÌÊCyð£·é±ÆÉæèCPd ÌY»¨ª`¬³êÄ¢é½ß

uXJCg_»¨nÉ¨¢Ä Cu ÌÅnÉÍoªÇDÉ@³êéB±êÍCPd \ÊÉªqzÆl¦é±ÆªÅ«éB»êÉº¢zÊà¸­·é½ßCÀ»·énð©oµ½BÆ±ëªcOÈªçC»ÌÜÜÅ

Pd im±qÌ÷×»ª¯ÉN±ÁÄ¢é±Æª¦´³

Í Cu ÉæéG}«ÍMà®Éä×Ä\ªÈ«\ÌàÌêéBø«±«CKXð NO ÉØÖ¦éÆCNO ÍpW

Í¾çêÄ¢È¢BEÌ\ÊÖÌzÆ¤ÉCim±qÌc£Í¬â©Éð©®ÔG}ÅÅà¢ïÅCl¶µÈ¯êÎÈçÈ¢ÌÍ³êCCO ª³êÄpWEÌà®\ÊªêUINO Ò³«\ÅoµÄ©ç\Êª_»³êéBXÉø«±«CKXð COª¢Æ³êÄ¢é Rh Æär·éÆCCu Ì«Í©ÈÉØÖ¦éÆCCO ªqªµÄ©ç_»Ìèá¢B±Ì·ÙÌ´öð¢·é½ßCRh Æ Cu Ì\ªnÜèCâªÄ CO ªqÉ¢íêÄCÈã¯lÌÏÊ´qÌdqóÔ§xðärµ½àÌð Fig. 5 É¦·BéöxzéBMà®ÌÅà NO ªqÌÒ³«»ðJèÔ·BêûCFig. 4(b)ÉÍyuXJCg_»¨

Rh \Ê´qÌ d O¹ÌGlM[ÊªtF~Êß\ÊÉÍoµ½ Pd im±qiPd/LaFeO3jÌÊð¦·

TÉiFig. 4(a)Æ Fig. 4(b)Ìe²Í¯¶XP[ÅèCNO ªqÌð£zÌÛÉdqÌöóªsíê

é±ÆÉâ·¢ÌÉÎµiFig. 5(ajjCCu \Ê´qÌ d O¹ÌGlÓjB»ÌUé¢ÍA~iSG}Æå«­ÙÈèCM[ÊÍtF~Êæè[¢½ßÉdqÌöóªsPd_Pd ´qÔ£ÌÏ»Í­È­Æà0.005 Å É½ÈíêÉ­¢iFig. 5(bjjB»±ÅCCu ð_»¨iCu2OjµÄ¢é CO ªqª³ê½ãCNO ª

Æ·é±ÆÅCCu ´qÌdqª·é O ´qÉø«ñÉæéñíÉÀèÈ_»wª`¬³êé±¹çêC»ÌÊC[©Á½ d O¹ÌGlM[Êð¢B\ÊÉzqÌð£zÆªª©éBPd im±q\îÂÔÌÝìpÌá¢Éæø«ã°éæ¤É\Ê\¢ðfUCµ½iFig. 5(cjjBèCPd im±qÌUé¢ÆG}½ÖÌñ^ÌdûÉ

XÉC_»ºÌÅ\ÊÌ O ´qð·é±ÆÅCå¢Éá¢ª

é±Æð¼ÚÏ@·é±ÆÉ¬÷µ½BCeWFgG}iPd/LaFeO3 jÍÀèÈ¢\Ê_Èà® Cu \Êæèà NO ªqÌð£zª£i³êé±Æð©oµ½8,9)BúËõ March 2013 Vol.26 No.2  59

Fig. 5Fig. 6(Color online) NOx conversion performance of Cu dis­persed on alumina was evaluated at 500C (A/F14.5). The
alumina was doped with Ba, Ce and La. Doping of Ce andLa is useful to maintain higher conversion eciency evenafter the engine aging at 1000
C for 5 hours.

Fig. 7

Time dependence of energy shift of the Cu K­edge for the Cu
nano­particles dispersed on (a) Ce­doped alumina and (b)non­doped alumina, during CO/NO successive dosing at400
C.

(Color online) Local density of states (LDOS) of (a) the dorbital of surface Rh atoms of Rh(111), (b) the d orbital ofsurface Cu atoms of Cu(111), and (c) the dz2 orbital ofsurface Cu atoms of Cu(111) compared with that of Cu­
terminated Cu2O(111).

ÀÂ«µÍCÅ Cu ðgp·éÛÉÍK¸_fª¶Ý·é½ßCCu Ì\wªÍ»ÀIÉÍ_»³êÄ¢éÆl¦çêéB]ÁÄCãqÌ_IÈwjÍC_»ºÌ\Êðü¿·é±ÆÆðßÅ«C»ÀIÈMà®ãÖG}ÌÝ
P à®±q\vwjÆl¦çêéB»±ÅCÈºÌæ¤Éò¢éB]ÁÄCà®im±qÌ\w¾¯ÅÍÈ­±qSÌQ à»Éæé_»Ò³Á«Ì§äSÌÔÝìpÌ§äòÅäÁ­èÆ_»Ò³vZXðN±·ÙÇ«ÉÈéÈÇÌG}«üãôð¢µ½BÆ¢¤ÖªPòà®±q\SÌÔÝìpÌ§äCe, La, Ba ÈÇðYÁµ½A~iãÉ Cu ðS·é

é±Æªª©Á½B»êÍCMà®im±qÌÁ«ÌêðÄ»µÄ¨èCJÚà®³fÉæéG}J­wjÆµÄ»¡[¢m©ÅéBà»Éæé_»Ò³Á«Ì§ä±ÆÉæèCCu im±q\ÊÌ§äðs¤±ÆðÝ½BQ
ò

Fig. 6 ÉúiÆÀGWÏvãi1000
CC5 ÔjÌ

«_Åé Cu ÆC»Ì¼ÌJÚà®iNi, Fe, Co,500
CÉ¨¯é NO ò»¦ð¦·BCe â La ðYÁµ½Mnjðà»·é±ÆÉæèCCu Ì«\ÊÌü¿ð¿ÍÏvãà¢«ðLµÄ¢é±Æªª©éB»ê¼Úwµ½B±±ÅÍCMg_Al Xsl_»¨ÉªU³¹êÌ¿Ì CO/NO µÍCÏ®ºÅÌ Cu ÌdqóÔÌ

½ Ni_Cu G}ÉÂ¢Äq×éBX üñÜÉæèCNi_Cuu»ÌêÏ@vðªU^ XAFS ÉæèsÁ½BFig. 7 Í Cuim±qÍÏêÈàð`¬µÄ¢é±ÆðmFµÄ¢éBK zû[ÌGbWVtgÊÌÔÏ»ð¦µÄ¢éBz

Fig. 8 ÉÍ Ni_Cu àG}Æ Cu A~iG}Ì NO_50÷

û[Í Cu Ì K vdqª©ðð©êÄãN³êéGlò»¦B·xð¦·iá¢ÙÇÇ¢jBNi_Cu àG}M[ð¦µÄ¨èCCu ªà®óÔÈÌ©_»óÔÈÌÍOÆµÄ_»ðµÄàC«ðáº³¹é±Æ©Æ¢Á½¿Ï»ðmé±ÆªÅ«éi_»Ìx¢ªCÍÈ©Á½BÊíÌ Cu G}ÆärµÄò»·xª100å«¢ÙÇGbWÊuªGlM[¤É¸êéjBYÁàáºµÄ¢éÌÍÁMÉl·éBÜ½CHC Ì_»½Ü³µÌ Cu Í¾ç©É_»vZXªOaµÄ¨èCÀÌ I ð « à ü ã · é ± Æ à ª © Á ½10) B Fig. 9 É Í CèÈ_»ª`¬³ê½ãÍC»êÈãÌ_»½ªiÜ400CÉÄ NOi1÷jÅ_»ðsÁ½ÛÌ Ni yÈ¢±Æð¦µÄ¢éBÜ½CÒ³vZXàñíÉZÑ Cu Ì K z û [ É ¨ ¯ é Ê í ^ õ w n É Ä æ ¾ µ ½

ÔÅ®¹·é±Æªª©éB»êÉÎµÄCCe ðYÁµXAFS XyNgÏ»ð¦·BNi, Cu ¤Éà®©ç_»½¿Í_»Ò³vZXÍäÁ­èÆisµOaµÉ­¨ÖÆÏ»µÄs­ªCCu Æä×Ä Ni Ìûª¬­_»¢BXÉC±ÌGbWVtgÍ Cu im±qSÌÌ½ÏÊ

³êé±Æªð³êéB0_25bÅ Ni Í_»ªiÞðÏ@µÄ¢é½ßCGbWVtgÊªå«­ÈéÆ¢¤ªCCu É¨¢ÄÍÅà¿Éq´Æ¾íêÄ¢é8980±ÆÍC_»ÌúÝª¦Ä¢éÆ¢¤±ÆðÓ¡µÄeV tßÌ¨\¢Ìs[NÉÍÏ»ªÈ¢B·Èí¿CNi60  úËõ March 2013 Vol.26 No.2

ðà ¡ EMà®ðÚwµ½©®ÔG}Ì¤Fig. 8(Color online) Light­o performance of Ni_Cu alloy andCu catalysts was evaluated after reducing, oxidizing, andre­reducing treatments. The Ni_Cu alloy catalyst began NOdecomposition at low temperature even after the oxidizing
treatment.

Fig. 10Fig. 9

XANES spectra of Ni_Cu alloy observed in the initial 25 sec.
oxidizing treatment at (a) the Ni K­edge and (b) the Cu K­edge.

(Color online) Conversion eciency of NOx, CO, and totalhydrocarbon (THC) in the sweep test for (a) the Cu
catalyst developed in this project and (b) the Pt catalyst as areference. The red rectangular represents a working region
where the conversion eciency for the three kinds of harm­
ful gas is above 80÷.

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ÒÐî¼¨ÛYú{´qÍ¤J­@\Êqr[p¤åÊqr[½§äÉðÍZp¤jbg O[v[_[E­mail: yasuonspring8.or.jpêåFX ü»w
mªðn
1989NÖ¼w@åwåw@w¤È¨wêUmÛöC¹CwmB1989_
1997NªRåwwèB1997N_ú{´qÍ¤Ö¼¤å^úËõJ­p¤B2007N 8 æè»EB62  úËõ March 2013 Vol.26 No.2¼ºå÷

ú{´qÍ¤J­@\Êqr[p¤åÊqr[½§äÉðÍZp¤jbg ¤å²E­mail: daijuspring8.or.jpêåFX üzûªõmªðn
2004Nåwåw@wn¤ÈmÛöC¹Cmiw)B2004Nú{wpU»ïÁÊ¤õiPDjB2005N_ú{´qÍ¤Ö¼¤úËõÈw¤Z^[B2012N 7 æè»EBðà ¡ EMà®ðÚwµ½©®ÔG}Ì¤Precious­metal­free automotive catalyst in theElements Science and Technology ProjectYasuo NISHIHATA

Japan Atomic Energy Agency, Quantum Beam Science Directorate, Reaction
Dynamics Research Division,
1_1_1 Kouto, Sayo­cho, Sayo­gun, Hyogo 679_5148, JapanDaiju MATSUMURA

Japan Atomic Energy Agency, Quantum Beam Science Directorate, Reaction
Dynamics Research Division,
1_1_1 Kouto, Sayo­cho, Sayo­gun, Hyogo 679_5148, JapanAbstractSelf­regeneration of the intelligent catalyst as an automotive catalyst was observed by in­situ
XAFS. Palladium nano­particles in catalytic reaction were also observed to elucidate the dier­ence in activity between the intelligent catalyst and the conventional one. Copper has been inves­tigated as a candidate to replace precious metals since the rst­principle theory predicts an active
copper surface for NO dissociation. The redox property of Cu turned into a similar property of
precious metals by managing the interaction between Cu particles and a substrate. The conver­sion eciency of Ni_Cu alloy particles increased than each element alone. The Ni was oxidized
faster than the Cu so as to maintain a metallic surface of Cu. These properties of Cu were incorpo­
rated into new design of a Cu catalyst, which has achieved high catalytic activity with the regular
operation of engine in the beginning.

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