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k XANES XyNg`óÍÞ·éDÜ½S^OXeC^_»¨G}ð L1, K k XANES æèðÍµ½
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1. Í¶ßÉ
X üzûªõ@ªLN^[[VÌêè@ÆµÄFm³êC³Ü´ÜÈªìÅp³êéæ¤ÉÈÁÄvµ¢D±Ìªõ@ÌpÒÍCÀ{Å«éúËõ{Ýâr[CÌÁÉÁ¦ÄCúËõ{ÝâwïåÃÌu
KïâÀKªJÃ³êéÈÇC{ÝCr[CSÒÌ²sÍÆ²¦Íàå«ÈvöÆµÄCÁµ±¯Ä¢éÆvíêéD½Æ¦Î Fig. 1 É X üzûªõ@ÉÖAµ½
uXANESvCuEXAFSvCuXAFSvÌL[[hÅC¶£õð Thomson Reuters ÐñÌwp¶£f[^x[XðpµÄsÁ½ÊðNx²ÆÉÜÆß½D±ÌÊÍ
K¸µàpáÆÍêvµÈ¢ªCU´qíC£CzÊÈÇÌ\¢ÉÖ·éîñð¾é EXAFS ÉÎ

Fig. 1

Remarkable increment of number publications related to
XANES. Number of published articles was counted by a key­
word search with Web of ScienceSM supported by Thomson
Reuters.

µCÎÌ«C´q¿óÔâÎÌ«CzÊÈÇÉq´È
XANES ÌpªßN}µÄ¢éXüª\êÄ¢éD»ÌÈ©Å 3d JÚà®Ì XANES XyNgÍCÈwI/àµC»wóÔªÍðsÁ½¤áðÐî·éDÀ±IÈdv«ÉÁ¦Ä K zû[GlM[ª 4_10 keVÆåCÅªèÂ\ÅéÀ±µâ·¢ÌæÅÇÌRÅLxÈñáªé±ÆÈ

2. vGbWs[NéDXANES páÌÁÉÖµÄÍC±êÜÅ EXAFS ÌÝðÍµÄ¢½¤Òª{èÌ 4dC5d JÚà®ÉÖ·é XANES ÌðàÉæ¾

XANES ð¹p·éæ¤ÉÈÁ½±ÆCðÍÎÛÆÈé³ÁÄCXyNg`óÉÖA·éêÊIÈXüÉÂ¢ÄfÌ»wóÔÉq´Å

3d JÚà®ÌvGbWs[N®ðp¢Äðàµ½

é±Æðpµ½wäIÈpá

é Ti, V, Mn, Fe ¨æÑªÁµ½ÈÇCp@ÌFmªLÜÁÄ«½±Æàvö¢DlÊÌ¨æÑªÊÌzÊÅÅCu »¨Ì XANES XyNgð Fig. 2 É¦·DlÊÌéÆl¦çêCÒ©gàvGbWs[NÌðß¨æÑêÊIÈXüÉÂ¢ÄðàµÄ¢é1_3)DzÊÅé Ti, V, CrC¨æÑ Mn »¨Ì XANES Xy

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NgÉÍs¢vGbWs[NªÏ@³êé±ÆÍL­rC¥«CõwÞ¿ðÍ¶ßÆµ½L¢ªìÅLxÈñmçêÄ¨èCÁÉ Ti4,5)CV6,7)nÅÚ×É¢³êÄ¢áª

éD±ÌvGbWs[NÍ 4, 5, 6 ÆzÊªå«­ÈéàÌÌC3d JÚà®Æär·éÆ_»]¿ÈOÌpÍ­È¢D»±Å{eÅÍ 4dC5d JÚà®ÌéÉ]ÁÄ­xÍáºµC³çÉs[NGlM[àÏ»XANES XyNgðè«IÉðß·é½ßÌl¦ûðð·é±Æ©çG}Þ¿CZ~bNXCöÌC¶¨n¿úËõ Jan. 2012 Vol.25 No.1  3ÖÌdqJÚÅÍÈ¢DdCoÉqJÚÌIð¥ Dl}1
É]¢Cs dq©ç p O¹ÖÌJÚÍeÅ
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éDÂÜèCs_d O¹ÔÅÍ¢©ÈéêÅàJÚ[gÌå«¢dCoÉqJÚÍN±ç¸Cd_p ¬¬O¹ª`¬³êÄ¢éêÉ p ¬ªÖÌdCoÉqJÚÆµÄ°ÈvGbWs[NªmF³êéÌÅéDd_p ¬¬O¹¬¬O¹Ì`¬ÍÎÌ«Éæèxz³êÄ¨èCÈPÉ
Í_QÌwW\ð©é±ÆÅ»ÊÂ\Åé1,2,8)DÜ¸C

Oh ÅÍ dCp O¹ª¯¶ÎÌ«ðÆÈéKñ\»ª¶ÝµÈ¢DTd ÅÍ px Cpy Cpz O¹Æ dxy Cdxz Cdyz O¹ª¯¶
T2 É®µÄ¨èCd_p O¹ª`¬µ¤éD±Ìæ¤Év
Fig. 2

Typical K­edge XANES spectra of 3d transition metals with
sixfold or fourfold coordination. TiO6: TiO2 (anatase),
VO6: V2O3; MnO6: MnO, FeO6: a­Fe2O3, CuO6: CuO, TiO4:
K6Ti2O74), VO4: NH4VO3, MnO4: KMnO4, FeO4: FePO4,
CuO4: CuAl2O4 (66.5÷ Td and 33.5÷ Oh).

GbWs[NÌðßÉð§Â¬¬O¹Ì`¬ÍCvZÈ
wIè@ðpµÈ­ÆàeÕÉ»fÂ\ÅéDÈãC

dCoÉqJÚÉîÃ­°ÈvGbWs[NªmF³
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èC©Â d O¹Éó«ªéðªéÆÜÆßé±ÆªÅ«éDÀÛÉÍ®S

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O¹CXANES XyNgÌvGbWs[N`óÉÖ·éÚ×ÈvZ»wI¤à­ÉsÈíêÄ¢éD

3. 4d JÚà®Ì XANES XyNg
4d JÚà®»¨Ì K k XANES XyNgÉÖµÄ
àC2 ßÅðàµ½Ið¥ªKp³êéDuf¨æÑ W  R j E  »  ¨ Ì XANES X y N g  ð Aritani
ç9) CImamura ç10) Ì¶£ ©ç² µ Ä Fig. 4 ÉÜ Æß½Dcñ¾ªÊÌzÊÆlÊÌzÊÌÇ\¢ðL·é
Fig. 3

Dependence of pre­edge peak height of metal­oxygen species
with tetrahedral symmetry on the number of d­electrons.1,2)

uf»¨ÌvGbWs[Nðär·éÆC3d JÚà®ÌÆ¯lÉlÊÌzÊÌÆ«É­xÆÈÁÄ¢é±ÆªmF³êéDÜ½æêzÊª Oh ÎÌ«ÆÝÈÈÇÌ]¿Ép³êÄ«½DvGbWs[NÍlÊÌ

·±ÆªÅ«éWRjEAZ`AZgi[göÌÅzÊÅêÎK¸µà­­Ï@³êéí¯ÅÍÈ¢DÞµÍ d_p ¬ ¬O¹ ª` ¬³ êÈ ­Èé ½ß Év Gb W

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Í¼Ì¤ÒÉæèñ³ê½XyNg©çÇÝæÁÄ

är·é±ÆÉæè¢m¨¿Ì¶ÝóÔÍèÂ\Å¨èCs[N³Ée¿·élXÈvöC½Æ¦ÎúËõèCjIu6)Cuf11)_»¨ðlXÈà®_»¨ã{ÝCr[CCªõ»CXbgÈÇÍl¶µ

ÉS³¹½G}Ì»wíâC^~Ngi¤¶·éúËÄ¢È¢Dµ©µÈªçè«IÈXüÆµÄCs[N­x«¯Ê³fÉæèñ»¿»µ½z¨jÌjIuí12) Èðxz·éàÌÍ³fíÅÍÈ­CS´q d O¹ÌdÇÌðÍÉp³êÄ¢éDFig. 4 ÌlÊÌzÊÅ

qÅ

é±ÆÍ¾ç©ÅéD±ÌÁ¥IÈvGbWs[NÍ 1s O¹©ç 3d O¹

4  úËõ Jan. 2012 Vol.25 No.1

uf»¨ÌufíÍZ¿ÅO¹dqÍ[ÅéèC³Ì 4déDvGbWs[N­xÉÖ·éêðà ¡ 4d, 5d JÚà®Ì XANES XyNgÉæé»wóÔªÍRjAÌ ZrO7 jbgÍ C1 Å

éD³û»WRj

AÌ ZrO8 ½ÊÌÉÍ·ÌÙÈéñíÞÌ Zr_O Îª¶ÝµCå¬ñíÞÌ ZrO4 ³lÊÌjbgªgÝí³ÁÄ¢éÆàl¦é±ÆªÅ«éD±Ì\¢ð_QèÌ¬ê}ÉÄÍßéÆ Td Å

é±ÆÍeÕÉmFÅ«éD±±Å Oh CC1CTd ÌwW\ÉÚ·éÆCp O¹Æ

d O¹ª¯¶Kñ\»É®·éàÌÍ Td ÌÝÅéD±ÌÊC³û»WRjAÌvGbWs[N­xªå«­ÈéÆ\z³êCÀXyNgÌXüÆàÎµÄ¢éD
2p dqÅ

êÎ 4d O¹ÖÌdCoÉqJÚÍeÅéD»ê_ÉæéÆªÊÌzÊÆlÊÌzÊÌÆ«C»ê¼êÌ d O¹Í 3F2C2F3 Éªô·éDBare ç14)
Í l X È   u f  »  ¨ Ì Mo L3 k XANES ð ª èµC»Ìñ÷ªXyNgÉmF³êéñ{Ìs[N­x¨æÑGlM[ÌÎIÈÖWªC»ê_Å\z³êé d O¹ªôÆêv·é±ÆðmFµ½D»ÌÊð¥Ü¦CL3 k XANES XyNgæè d O¹ÌªFig. 4

Zr K­edge and Mo K­edge XANES spectra of authentic com­pounds with tetrahedral or octahedral symmetry. Zr K­edge
XANES spectra were reproduced from Imamura et al.10) Mo
K­edge XANES spectra were reproduced from Aritani etal.9)ô¨æÑs[N­xäð]¿·é±ÆÉæéSuf_»¨G}Ì\¢ðÍ15,16)âCS}K_»¨ãÉzµ½ufíÌðÍ©çn

»wI¢ðsÈÁ

½á17) ÈÇªñ³êÄ¢éDpWE¨æÑWE
ÍG}Þ¿ÆµÄsÂÈ¨¿ÅéDµ©µ XANES

XyNgðpµ½¤ÆµÄÍCà®É_»¨Ì¬ä¦ð K k XANES ÉÄèµÄ¢éáªå¼ÅèC»wíÌwäIpÉÖ·épÍÀè³êÄ¢éDÜ½
L3 k XANES XyNgÌzCgC­xª d O¹
ÌóÔ§xÆÎµÄ¢é±Æðpµ½_»óÔÌ¢àsÈíêÄ¢éªCzû[ªî X üÌæÉÊu·é½
ßÉpáÍÀçêÄ¢éD

4. 5d JÚà®
Fig. 5

Zr K­edge XANES spectra of ZrO2 polymorphism and therst derivatives. (Reprinted with permission from Phys.
Rev. B 48, P. Li, I. W. Chen, J. E. Pennerhahn, 10063_
10073, Copyright (1993), by the American PhysicalSociety).

X üzûÀ±ªåCÅÀ{Â\C©ÂúËõ{ÝÅärIeÕÉªèÂ\ÅÅéGlM[ÌæÍ 4_30 keVéDóyÞ³fÆ 5d JÚà®Ì K zû[Í40 keVÈãÌGlM[ÌæÉÊuµCXANES ðpµ½¤Í»ÝÅàå¼ª L zû[ÉÖ·éàÌÅéDÁÉ

L3 k XANES ÅÍ 2p_5d JÚÉÎ·ézCgCÊ¥iFig. 3jðQÆ·éÆC±ÌêÌs[N­xÍ0.7­xª d O¹ÌóÔ§xÉ§ÚÉÎ·é±Æ©çiFig.

©ç 1 öxÉÈéÆ\z³êéªCÀÛÉÍ0.5öxÌ­618)jCÎÛ³fÌ_»]¿ÉL­p³êÄ¢éBÏ»xµ©Ï@³êÈ¢D±Ì´öÉÂ¢ÄÍ 5 ßÉÄðà

ª¾ÄÅ

·éD

Ö·é¤à­Å

_»WRjE½`Ì Zr_K k XANES XyNgÌé½ßÉßNÅÍªªèÉæé®I®É
é D 2s d q Ì z û Åé L1 kXANES ÍCIð¥Éæè d O¹ÖÌJÚª§À³êéDärÍ»¡[¢DFig. 5 É Liu ç13)Éæèªè³ê½»]ÁÄ´qÌÇ\¢C»wóÔÉæéXyNg`óÌnÌÙÈé ZrO2 Ì XANES XyNg¨æÑ»Ìê±Ï»ðó¯â·¢±Æðpµ½wäIÈ]¿ª½­síÖð¦·D±ÌXyNgððß·é½ßÉÜ¸C³ÜêÄ¢éD{ßÅÍC»wóÔªÍÉpµ½gsbNX´ÜÈ»ÌWRjE´qðSÆµ½_f½ÊÉµÚÁÄðàðsÈ¤DÌðÈPÉf»µC»Ì_Qðl¦éDzIÈ§û
»WRjAÌ ZrO8 jbgÍ OhCPÎ»CÎû»W

Fig. 7 ÍlXÈ^OXe»¨Ì L1 k XANES X
yN gðÀ ±ºnu Éæèªèµ ½àÌÅéDúËõ Jan. 2012 Vol.25 No.1  5

Fig. 6

Dependence of number of 5d electron on white line intensityof L3­edge XANES spectra for 5d metals. (Reprinted withpermission from J. Sinfelt, and G. Meitzner18). Acc. Chem.
Res. 26, 1, Ý 1993 American Chemical Society.)Fig. 8W L3­edge XANES spectra of tungsten compounds with Td,
distorted Oh and Oh symmetry and the second derivatives.
(a) Ba2NiWO6, (b) Cr2WO6, (c) (NH4)10W12O41¥5H2O,(d) WO3, (e) H3PW12O40¥13H2O, (f) Sc2W3O12, and(g) Na2WO4. (Reprinted with permission from Yamazoe,
et al.23). J. Phys. Chem. C 112, 6869, Ý 2008 American
Chemical Society.)»¨G}Ì]¿19_22)ÈÇÉp³êÄ¢éD
ßN³ËCcçÌ¤O[vÍClXÈ^OXe»¨¨æÑS^OXe_»¨G}Ì L1 CL3 k
XANES XyNgðªèµCvZÈwIè@ðgÝí¹é±ÆÅCÇ\¢Æ d O¹ÌªôÉÖ·énIÈ¤ðsÁÄ¢é23,24)DFig. 8 Í Yamazoe çÉæèñ³
ê½lXÈÎÌ«ðL·é^OXe»¨Ì W L3 k
XANES XyNgÌzCgC¨æÑ»Ìñ÷ª
XyNgÅ

é23) Dê© 1 {ÌzCgCÌæ¤É©¦éwe|_â Na2WO4 ÅàCñ÷ªXyN
Fig. 7W L1­edge XANES spectra of tungsten compounds with Td,
distorted Oh and Oh symmetry.

g©çÍñ{Ìs[NªdôµÄ¢é±Æªí©éDªôµ½s[NÌGlM[¤ÆáGlM[¤Ìs[N­xäÍC³ªÊÌ^ÅÍ¨æ» 3F2C³lÊÌ^ÅÍ
2F3 Å

12105 eV tßÉ

Á½DÜ½³lÊÌ^ÌªôÍ¬³©Á½D

Ú·éÆ^OXeüèÌ_f½Ê

± ê ç Ì  Ê Í Mo L3 XANES Ì  Ê14) Æ Þ  µ Ä ¨é Na2WO4É2H2O ÅÍ¾ÄÈvGbWs[

èCf\¢ÉÎ·éÊq»wvZÊÆàêvµ½D

NªmF³êéÌÉÎµCOh ÌÎÌ«ð¦· Sr2CaWO6,

Ü½s[NªôÆ L1 k XANES XyNgÉÏ@³ê

Ba2NiWO6 ÅÍ­ÕxÅévGbWs[N­xÌÔÉÖª

Ìª Td ÅéDÜ½cñ¾ Oh Åéé±Æð©oµC

p^OXe_AjECWO3 ÅÍV_[d_p ¬¬O¹Ì p O¹ÌÉæèà¾Å«é±ÆðØs[NªmF³êéD±ÌvGbWs[NÍ 2s O¹Ìµ½DÈãæè¢mG}¿ÌÇ\¢ªèÂ\ÅdqÉæé 5d_6p ¬¬O¹Ì p ¬ªÖÌdCoÉqJÆ_µCNH3 Ìõ_»½ð£i·é`^jAS_èC¬¬O¹ª`¬³êÈ¢ Oh»^OXeG}Ì^OXeíÌ\¢ªSÊÁÎÌ«Ì»¨ÅÍ 3dC4d nÌêÆ¯lÉ¬³¢DêÉº¢ Td ©çcñ¾ Oh ÖÏ»·éÏJðñµ½D±ÊIÉXs_O¹Ýìpªå«¢ 5d JÚà®ÈÇÌÌ»ÛÍ¼Ì 4dC5d JÚà®ÅÚÉA®³êéàÌÅ

éé Nb, Mo Re, Ta É

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à¯lÌAv[`ªÂ\Åé±Æð¦µÄ¢é24)D

NiWO6 ÌXyNgÅs[NªÉßÄ¬³¢±Æ©çCÚµ¤évGbWs[NÍ d_p ¬¬O¹Ì p ¬ªÖÌdCoÉqJÚÅ
®Å

5. XyNgªð\éÆl¦çêéD¼Ì 4d JÚàé Ta â Re É¨¢Äà_f½ÊÌªlÊÌzÊÅ

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6  úËõ Jan. 2012 Vol.25 No.1

O ß Ì Fig. 4 É ¦ µ ½ Æ ¨ è l Ê Ì z Ê Å

é Na2

MoO4 Ì Mo K k XANES ÉÏ@³êévGbWs[

ðà ¡ 4d, 5d JÚà®Ì XANES XyNgÉæé»wóÔªÍ

Fig. 10Similarity of spectral features between Mo K­edge XANES
for Na2MoO4 and W L1­edge XANES for Na2WO4 due totheir natural width of the core level.

Ì©RÍK¸µàÎµÈ¢DZr æè´qÔÌ¬³¢³fÅÍ K kæèzû[GlM[Ìá¢ L1 kÌ©RÌûªå«­C´qÔ30©ç74ÜÅÍÏ»Í¬³¢DFig. 10 ÉCSà®üÓÌÇ\¢ªÞµÄ¢é
Na2MoO4ÉnH2O Ì Mo K k Æ Na2WO4ÉnH2O Ì W L1 k
XANES XyNgð¦·D±Ìzû[Ìàk©RÍ
4.52C5.61 eV Æß¢½ßCXyNgÌÝèûª¯öx
Fig. 9Natural width for K, L1 and L3 levels plotted as a function of(a) atomic number, and (b) absorption edge energy. The
natural level widths are taken from Krause & Oliver25).

ÆÈéD±Ìæ¤Él¦éÆXyNg`óªÉßÄÞµÄ¢é±ÆªðÅ«éD
dCoÉqJÚÌIð¥ÌÏ_©çC{¿IÉÍ L1 k
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ÉXyNgªå«­ÝéDÁ¦Ä Pb2{ ÅÍ 5d 10 ÅN­xÍ0.5öxÅÈÇõwnÌá¢Éæée¿ÈÇªl¦çêéªC{¿I

è L3 k XANES ÅÍ 2p_5d JÚªN±çÈ¢D±Ìæ¤ÈâèÆµÄCÀÛÉñ^ªå«¢ÌÍàkxÌ©RÈ ð  ª d È Á ½ Pb n Ì l É C L1 Å Í È ­ L3 kÅéDFig. 9 Í Krause Æ Oliver25) ªvZµ½ K, L1,

XANES ª»wóÔªÍÉp³êéê26,27)à

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ZrO2)28)iWOx_µ¢Æ¼è·êÎC©Rªå«¯êÎzûs[N©gªHinoCArata çÉæèJ­³ê½C^OXe_ðLªé½ßÉ³Íá­ÈéDïÌIÉÍâ^\¢ðL_»WRjEÉSã1073 K ÅÄ¬µÄ¾éÅÌ

42Mo ÅÍ»ê¼ê0.94, 4.52 eV ÅéDd O¹dqª·é MnO, FeO, CoO, NiO Ì K k XANES ÌXyNg

G}ÍCêÊIÉÍ100÷°_æè­¢_Ì¶ÝºÅis`óÍCåÉdCldÉJÚÉNöµC©Â d dqÉ·é n_u^ðC\u^Öº·Å]··éiÙ«»Ë¶·é¬³ÈvGbWs[Nð¢ÄñíÉæ­Ä½ð£i·éÅÌ´­_«ð¦µCSÊ15dÊ÷öéDMn_Ni ÅÍ´qÔªßxÌ«ªÅà¢29) D»Ì¢_­xÉÁ¦Ä²»¨¢é±ÆÍümÌÀÅ

­C©Rà1.16C1.44Æ0.3 eV µ©áíÈ¢ÌÅügæÑæèµ¢ªeÕ©ÂåÌe¿ÍÚ§½È¢Dµ©µüúðÜ½¢¾³fÔÅÍÝÈç¸C¡øÊÉæè­_«ª­»·éwpIÏ_©

©RÌ·ªå«­CXyNgªÝéøÊª°ÉÏªçàÚÌ¢G}QÅ

³êéÌÅ

é30_32) DS³ê½^OX

eíÌ\¢ÉÂ¢ÄCmC[CNX^[CweéDKCL3 kÌ©RÍ´qÔÉÎµÄP²ÉÁ·éÌÉÎµCL1 kÅÍ´qÔË¶«Í¡GÅ

H«ªá¢ÈÇÌÀpI_ÌéDFig. 9(b)©ç¾ç©ÈÆ¨èCzû[GlM[Æàkx

|_ClÊÌzÊÌWIL\íÈÇ³Ü´ÜÈfªñÄ³êÄ¢éªC»ÝÅàêµ½©ðÍ¾çêÄ¢È¢D

úËõ Jan. 2012 Vol.25 No.1  7

Fig. 12 Proposed model structure of WOx­ZrO2 catalysts.

Fig. 11W L1­edge XANES spectra of WOx­ZrO2 solid acid catalysts
in a dried and hydrated state.

{nÉÎ·é XAFS ðÍáàñ³êÄ¢éªCW
RjE»¨ÉK¸¬ü·éntjEÌ L2 zû[Ì½ß É W L3 k EXAFS Ì pÍ k 12 Å|1 É §À ³ê

Fig. 13

La L1­edge XANES spectra of 14 wt÷ LaOx/Al2O3 catalyst
sample and reference compounds. The catalyst sample wascalcined at 773 K, and stored under exposure to the air.

Fig. 14

La K­edge XANES spectra of LaOx/Al2O3 catalyst samples
calcined at 1273 K. Calcined samples were stored without
exposure to the air.

Ä¢½DäXÍ¼Ìzû[Éæé§ÀÌ³¢ W K k
XAFS ðªèµCÎÌ«Éq´È L1 k XANES ðâIÉp·é ±ÆÉæè Vµ¢\¢ fðñ ÄµÄ¢é28)DFig. 11 É_»^OXeSÊÌÙÈéG}ð
a¨æÑ£óÔÅªèµ½ W L1 k XANES XyNg
ð¦µ½DÜ¸a¿ÌvGbWs[N­xÍÇÌSÊÅà¯xèC©Â WO3 æèí¸©Éå«¢D£ãÌs[N­xÍa¿æèå«­CáSÊÉÈéÙÇC­xÁÌöxÍå«©Á½D±±ÅCVJSÌãâ[ICg}gNXÉªUóÔÅÅè»³ê½ VO4, TiO4 íÍC£óÔÅÍ XANES XyNg
És¢vGbWs[NªÏ@³êéÌÉÎµCa·

éÆvGbWs[N­xªºªé±ÆÍümÅ

éD»±ÅC{nÌ^OXeíÉà¯lÌ»ÛªN±èCaóÔÅÍÇ§ WO4 íÍªqÌzÉæèZzÊíÉ

Ï»·éÆl¦½D³çÉ WOx NX^[â WO3 »
qÈÇ{ZzÊÅé^OXeíÍCaµÄà»ÌÇ\¢Íe¿ðó¯È¢Æ¼è·é±ÆÅC

a_£ÔG}âRÄG}ÈÇ·ºÅp·éêÍ»]ßöÅÌs[N­xÏ»ÆQÆ¿ÌXyNg©çGÚC\ÊÏáºiV^OjÉº¤«\ò»Ì}§ª}Ì^OXeíÌlzÊí/ZzÊíÌðZodvÈÛèÅ

µ½DÚ× ÍÈª·é ªC±Ì Êð« ±ÊC

³ê½A~iSÌªÀp»³êÄ¢éDV^O}

XANES/EXAFS, XRD ðÍC³çÉñ³n_»¨ÌóÔ

§@\ÉÖµÄÍ\wÉ`¬³êé LaAlO3 yuXJC}ðîÉ WOx _ZrO2 G}Ì\¢fðèµ½iFig.

gwªÏM«üãðS¤àâCLa2O3 wª\ÊGlM[

12jD±ÌfÉæéÆ WOx_ZrO2 G}Ì^OXe

ðº°éàÈÇªñÄ³êÄ¢éDèC»ÌÎôÆµÄ­ÊÌ^ªYÁíÍCWO4 íCW_Zr_O ÅnÌiZrO2 Í³û»jC

Fig. 13 É^»¨ð 5 mol÷ LaOx/Al2O3iLa2O3

WOx NX^[©ç\¬³êéD³çÉ³û» ZrO2 \ÊÆµÄ14 wt÷ 773 K Ä¬ãÉåCÅÛ¶jÌ La L1 k

ãÉ WOx NX^[ª¶Ý·éÆÅÌ­_G}ÆµÄ@

XANES XyNgð¦·D\·é±ÆCvGbWs[N­xÏ»ðS¤ WO4 íÅÍC6270_6310 eV É©¯ÄXyNgÔÌáª¯

ÍCÅÌ´­_«­»ÉÖ^µÈ¢±Æª@³ê½D

Ê³êCwäIÈpªÂ\Å6.2

Å LaOx/Al2O3 ÌXyNgð¬ñæ@ÉæèðÍµ½^YÁ_»A~jEG}33,34)A~iÍHÆG}É¨¯éSÌÆµÄL­p³êÄ
¢éDg_Al2O3 ©gÍT^IÈ Lewis _G}Å_G}ÆµÄÌpà­ÅèCÅÌéDA~inG}ð©®

8  úËõ Jan. 2012 Vol.25 No.1í¹Ä¦µ½÷ªXyNg
é±Æª¦³êÄ¢éDÊCA~iãÌ^íÍ La2O3 CLa(OH)3 CLa2
(CO3 )3 ª»ê¼ê35C22C43÷¬ÝµÄ¢é±Æªí©
Á½ DFig. 14 ÍCLa YÁÊ ª1.6_36 wt÷Å

é LaOx /ðà ¡ 4d, 5d JÚà®Ì XANES XyNgÉæé»wóÔªÍ

Fig. 15

Results of convolution analysis for La K­edge XANES spec­
tra of LaOx/Al2O3 with isolated La species and LaAlO3.
The evaluated fraction of LaAlO3 in LaOx/Al2O3 calcinedat 1273 K corresponds to that of aggregated La species infresh sample.

Fig. 16Eect of monochromator crystal on spectral resolution of
Ru K­edge XANES for RuO2.

7. ¨íèÉ
Al2O3 ð 1273 K Å Ä ¬ µ ½  ¿ Ì La K k XANES X yNgÅéDYÁÊª7.5 wt÷ÜÅÍXyNgÍÙÚ{ðàÅÍ 4C5d JÚà® XANES XyNgð¼o¯êÅéÌÉÎµC»êÈãÅÍA±IÉ LaAlO3 Éß±IÈ»wóÔªÍÉp·é½ßCXyNg`óÉÖ¢`ÖÆÏ»µ½D1.6_7.5 wt÷ LaOx /Al2O3 ÅÍC873,·éêÊIÈXüðCÁÉ 4d JÚà® K kÆ 5d JÚà

1073, 1273 K ÅÄ¬µ½¿Ì XANES/EXAFS XyN® L1 XANES ÉÂ¢ÄðàµCÒ©gªðÍðsÈÁ

g`óÍ¯¶ÅèCEXAFS ðÍ©çÍ La ´qªªUóÔÅ¶Ý·é±Æª¦³êÄ¢éD»êÈãÌZx

½áðÇLµ½DXANES XyNgpÉÖ·éLp«ÍàÍâà¾ÍsvÅ

éD½­Ì¤ÒªÚÉµÄ¢½

ÅÍC1073 K Ä¬ãÌ XANES/EXAFS XyNg`óÅªÏ»µCLaAlO3 »qÌ¶¬ª XRD p^[ãÉmÛª©¦³êÄ¢éÅ

F³ê½DFig. 14 É¦µ½eXyNgªÇ§óÔi1.6

k XANES æ è d O ¹ ª ô ð  ¢ µ ½ Yamazoe ç Ì ¤wt÷ LaOx /Al2O3 jÆ LaAlO3 Ìñ¬ªÌÝ©ç\¬³ê23) ÍC¡v¦Î»ê_ÉæèeÕÉ\ª³êéà

ë¤XyNgÉàCÀÛÉÍ½­ÌÌn»Â\È»ë¤D½Æ¦Î 5d JÚà®Ì L3

èCÜ½î X üÌæÌ Mo L3 k XANES Å¾mÈéÆµÄðÍðsÈ¢CLaAlO3 Ìðß½ÊðÌÅ

Fig. 15 É¦·DªUóÔÅA~iãÉÅè»³ê½

Xüªñ³êÄ¢½Éà©©íç¸C²­ÅßÜÅï^íÍ­È­Æà1273 K ÜÅÍ\¢Ï»µÈ¢DµIÈc_ªsÈíêÄ¢È©Á½DXANES Í L1 kÅ]©µZxÅYÁ³êÃWóÔÅ¶Ý·éÆl¦çêé¿· éàÌÅé ÆÌÅèÏOÉ Á¦CL3 kÅÍ EX­^íÍ LaAlO3 ð`¬µC»Ì¡_»¨`¬ªis

AFS SÌðÍªåÆµÄsÈíêÄ¢½½ßÉC¶Á·élª¨æ» 5 wt÷C1 La­atom/nm2 Å­èÆ­ßCär¢³êé±Æª­È©Á½ÌÅÍÈ¢é±Æª©ÆvíêéDÜ½óyÞ_»¨Ì L3 k XANES ÅÍC¾ç©ÆÈÁ½D
La YÁÉæéV^O}§øÊÍCÒðÜß½

ñ÷ªXyNgªªô·é¨¿Æ»¤ÅÍÈ¢¨¿ªéæ¤ÉYÁÊ0.5 mol÷i0.4 La­atom/

é±Æªñ³êÄ¢½36_38) ªC¡êà¥Ýñ¾

­Ìñáªnm2E1.6 wt÷jöxÅ·ÅÉOaµÄ¢éDV^¢ÍsÈíêÄ¢È©Á½DO}§øÊªOaµÄ¢éáSÊÌæÅÍ LaAlO3 Í`e³fÉÂ¢ÄÍ[­¤³êÄ¢Äà³fíð´¦é¬µÄ¨ç¸C·Åà\¢Ï»ªN±çÈ¢Ç§

XANES XyNgÌïIÈc_ÉÂ¢ÄÍÜ¾Ü¾s^íªV^O}§Ì®ÆÈÁÄ¢é±ÆÍ¾ç©ÅéDäXÍ XAFS ðÍÉÁ¦C\Ê_î«Ì¢CXRDC\ªÅèC¢·×«ÛèÍ½­c³êÄ¢éD\¢ùmÌ»¨ÌXyNgðÂÂµC¶Á­èÏ@/¢·öC¤¶ºÅÌV^OÀ±ÉæèC

é±ÆÉæèÌn»Â\©Â»wóÔªÍÉLøÈVµ¢g_Al2O3 \ÊãÌ­¢ Lewis __ª^CIÉæè

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 ÒÐî R{F¿åwåw@\VIÉA[cÉAh
ÉTCGX¤¿åwÈwy³ö
êåFG}»wCÂ«¨»wmªðn
1999Nsåwåw@Hw¤Èm
ÛöC¹C1999Nú{wpU»ïÁÊ¤õC2002NÈwZpU»Æc¤õC2002NHÆåw¹»w¤èC2006NsåwHw¤ÈèC2009Næè»EBðà ¡ 4d, 5d JÚà®Ì XANES XyNgÉæé»wóÔªÍ

XANES Spectra of 4d and 5d Transition Metals
for Empirical Chemical State Analysis
Takashi YAMAMOTO

Department of Mathematical and Material Science,
The University of Tokushima,
1_1 Minamijosanjima­cho, Tokushima 770_8502, Japan

Abstract

Features of XANES spectra of 4d and 5d transition metals were reviewed on the basis of the coor­dination number, the point group and natural level width of the core level, and were compared with those for
3d transition metals. The intense pre­edge peaks are assigned to electric dipole transition of 1s or 2s electron
to p­component in d­p hybridized orbital, the formation of which could be predictable with the character ta­
bles. The spectral features of XANES including pre­edge peaks were broadened due to the natural width of thecore level. The similar level of the natural width give resemble broadening eect independent of the absorption
edge, resulting that spectral features of Mo K­edge XANES spectrum of Na2MoO4 closely resembles to W L1­edge XANES spectrum of Na2WO4. The XANES analysis for LaOx/Al2O3 and WOx_ZrO2 catalysts were rev­
iewed.

úËõ Jan. 2012 Vol.25 No.1  11