Pring-8/SACLA฼⏝◊✲ᡂᯝ㞟฼⏝◊✲ᡂᯝSS
Pring-8/SACLA
2015A3622, 2015B3624            Section AB        BL14B1XAFS ᐃ࡟ࡼࡿ㞺ᅖẼኚືୗ࡛ࡢ㈗㔠ᒓ(Rh,Pd)ᢸ
ᢸᣢ≧ែゎᯒ
Analysis of Precious Metals (Rh,Pd) States under Atmosphere Switching
Conditions by EXAFS Measurementᯇᯞ ᝅྖ, ᯇஂ ᝆྖ, ᖹᑿ ဴ኱
Satoshi Matsueda, Yuji Matsuhisa, Tetsuhiro Hiraoᰴᘧ఍♫࢟ࣕࢱ࣮ࣛCATALER CORPORATION⮬ື㌴⏝᤼࢞ࢫί໬ゐ፹ࡢㄢ㢟࡜ࡋ࡚ࠊ㈗㔠ᒓจ㞟ᢚไ࡟ࡼࡿᛶ⬟ྥୖཬࡧ㈗㔠ᒓ౑⏝㔞పῶࡀせồࡉࢀ࡚࠸ࡿࠋ⌧ᅾ◊✲୰ࡢ᪂つ Rh ᢸᣢἲゐ፹ ௨ୗࠊ᪂つἲ ࡣࠊᚑ᮶ Rh ᢸᣢἲゐ፹ ௨ୗࠊᚑ᮶ἲ ࡟ᑐࡋࠊRh จ㞟ࡢᢚไ࡜ࡼࡾప ࠿ࡽࡢάᛶྥୖຠᯝࢆぢฟࡋࡓࠋ௒ᅇࠊࡇࡢせᅉࢆ᥈ࡿࡓࡵࠊEXAFS ࡟ࡼࡿ Rh ≧ែゎᯒࢆ⾜ࡗࡓ⤖ᯝࠊ᪂つἲ࡛ࡣ㑏ඖ㞺ᅖẼୗ࡟࠾࠸࡚ప ࠿ࡽ㏿ࡸ࠿࡟ Rh-O ࡀ Rh-Rh ࡟ኚ໬ࡍࡿ஦ࡀ☜ㄆࡉࢀࡓࠋ୍᪉ࠊຎ໬ᢚไ࡛ࡣࠊ
㓟໬㞺ᅖẼ୰࡟⏕ᡂࡍࡿࠕRh-O-Ndࠖࡢᙳ㡪ࡀ኱ࡁ࠸஦ࡀ᥎ᐃࡉࢀࡓࠋࡲࡓࠊXANES ࡢ⤖ᯝ࡛ࡣࠊᚑ᮶ἲࡢ Rh ྾཰➃࡟ᑐࡋ࡚㧗࢚ࢿࣝࢠ࣮ഃ࡟ࢩࣇࢺࡋ࡚࠸ࡿࡇ࡜࠿ࡽࠊ᪂つᢸᣢ᪉ἲࢆ㐺ᛂࡍࡿ
஦࡛ Nd2O3 ࡢ෌㓄ศࡀಁ㐍ࡉࢀࠊRh ࡟ᑐࡋ࡚ Nd2O3 ࡢ᥋ゐ㢖ᗘࡀ㐺ᗘ࡟㧗ࡲࡾຎ໬ᢚไ࡜ప άᛶࡀ㧗࠸࡛ࣞ࣋ࣝ୧❧ࡋࡓࡶࡢ࡜᥎ᐹࡋࡓࠋ
࣮࣮࢟࣡ࢻ㸸 XANESࠊEXAFSࠊRh ≧ែゎᯒࠊ㞺ᅖẼኚືୗࠊRh ᢸᣢἲ⫼ᬒ࡜◊✲┠ⓗ㸸⮬ື㌴⏝᤼࢞ࢫί໬ゐ፹ࡢ㛤Ⓨ࡟࠶ࡓࡾࠊάᛶ✀࡛࠶ࡿ㈗㔠ᒓࡢ᣺ࡿ⯙࠸ࢆ⌮ゎࡍࡿࡇ࡜ࡣᴟࡵ࡚㔜せ࡜⪃࠼ࡿࠋᙜヱゐ፹ࡣ✀ࠎࡢ⎔ቃୗࠊ౛࠼ࡤ⮬ື㌴ጞື᫬ࡢᐊ ࠿ࡽ㧗㏿㉮⾜᫬ࡢ1000Υ࡟⮳ࡿ㧗 ᮲௳ࡸຍ㏿᫬ࡢ㑏ඖ㞺ᅖẼ࠿ࡽῶ㏿᫬ࡢ⇞ᩱ࢝ࢵࢺ᫬ࡢ㓟໬㞺ᅖẼ᮲௳࡞࡝ࠊྛ⎔ቃୗ࡛ࡢ㈗㔠ᒓ≧ែࢆᢕᥱࡍࡿ஦ࡀᚲせ࡛࠶ࡿࠋ㈗㔠ᒓࡣࡇࡢࡼ࠺࡞౑⏝⎔ቃୗ࡛จ㞟ࡋࠊάᛶ⾲㠃✚ࡢῶᑡ࡟ࡼࡿᛶ⬟పୗࢆᘬࡁ㉳ࡇࡍၥ㢟ࡀ࠶ࡾࠊ㈗㔠ᒓจ㞟ᢚไ᪉ἲࡣከᒱ࡟Ώࡾ᪥ࠎ◊✲ࡉࢀ࡚࠸ࡿ[1]ࠋୖ㏙ࡢ◊✲ᑐ㇟ࡢ୍ࡘ࡜ࡋ࡚㈗㔠ᒓࡢᢸᣢἲࡀ࠶ࡿࠋ㈗㔠ᒓࡢᢸᣢἲࢆኚ࠼ࡿ࡜㈗㔠ᒓࡢ≧ែࡶኚ໬ࡍࡿ஦ࡀ୍⯡ⓗ࡟▱ࡽࢀ࡚࠾ࡾࠊᢸᣢἲ࡜㈗㔠ᒓ≧ែཬࡧྛ⎔ቃୗࡢ≧ែࢆ㛵㐃࡙ࡅ࡚ᩚ⌮࡛ࡁࢀࡤࠊ㈗㔠ᒓจ㞟ᢚไ࡟ࡼࡿ㧗ᛶ⬟ゐ፹ࢆᑟฟ࡛ࡁࠊ㈗㔠ᒓ౑⏝㔞పῶ࡟㈉⊩࡛ࡁࡿ࡜⪃࠼ࡿࠋ⌧ᅾ◊✲୰ࡢ᪂つ Rh ᢸᣢἲゐ፹ࡣࠊᚑ᮶ Rh ᢸᣢἲゐ፹࡟ᑐࡋࠊ౑⏝⎔ቃࢆᶍᨃࡋࡓฎ⌮ᚋ
㸦1000Υ10 ᫬㛫ࠊ㓟໬㸭㑏ඖ㞺ᅖẼኚືୗ㸧࡟࠾࠸࡚ Rh จ㞟ࡀᢚไࡉࢀ࡚࠸ࡿ஦ࢆ STEM-EDS
ほᐹࡸ XRD ࡢ Rh ⤖ᬗᏊᚄ࡛☜ㄆࡋࡓ Fig. 1-a,bࠊFig. 2 ࠋࡲࡓࠊప ࠿ࡽࡢάᛶྥୖࢆࣔࢹࣝ࢞ࢫ ᗘ≉ᛶ࡟࡚☜ㄆࡋࡓ Fig. 3)ࠋ
௒ᅇࠊRh จ㞟ᢚไ࡜ప ࠿ࡽࡢ㏿ࡸ࠿࡞ί໬άᛶࡀᚓࡽࢀࡿせᅉࢆ᥈ࡿࡓࡵࠊゐ፹ࡀ᫹ࡉࢀࡿ
㞺ᅖẼ࡛ࡢ Rh-ᢸయ⢊ᮎ࡟࠾ࡅࡿ⏺㠃⤖ྜ≧ែࡸ Rh ≧ែࢆ in-situ XAFS ᐃ࡟ࡼࡗ࡚ㄪᰝࡋࡓࠋ



Fig. 1-a STEM-EDS(Conventional) Fig. 1-b STEM-EDS(Developed)䠉㻞㻟㻝䠉Pring-8/SACLA฼⏝◊✲ᡂᯝ㞟฼⏝◊✲ᡂᯝSS
Pring-8/SACLA

Section ABFig. 2 Rh crystallite diameter calculated from XRD

Fig. 3 50% purification temperatureᐇ㦂㸸ᐃヨᩱࡣࠊᚑ᮶ཬࡧ᪂つᢸᣢἲ࡛ㄪ〇ࡋࡓ Rh ᢸᣢ⢊ᮎ 2 ✀ࠋ௙ᵝࡣࠊRh㸦0.5wt㸧㸭CeZrNd⣔」ྜ㓟໬≀ࠋㄪ〇᪉ἲཬࡧ ᐃ᪉ἲ㸸
1. ◪㓟 Rh ⁐ᾮ࡜ CeZrNd ⣔」ྜ㓟໬≀⢊ᮎࢆΰྜᚋࠊ኱Ẽ୰ 500Υ࡛ 1 ᫬㛫⇕ฎ⌮ࢆ⾜࠸ࠊRhᢸᣢ⢊ᮎ㸦ᚑ᮶ἲ㸧ࢆᚓࡓࠋࡲࡓࠊࢩࣗ࢘㓟➼ࡢ᭷ᶵ࢝ࣝ࣎ࣥ㓟ࢆῧຍࡋࠊ⢊ᮎ࠿ࡽ㓟⁐ゎࡋࡓNd ࢖࢜ࣥ࡜ࡢ࢝ࣝ࣎ࣥ㓟 Nd ሷ⤖ᬗ⏕ᡂࢆ᪋ࡋࡓࡇ࡜௨እࡣࠊ๓グ࡜ྠᵝࡢ᪉ἲ࡟࡚ࠊRh ᢸᣢ⢊ᮎ(᪂つἲ)ࢆᚓࡓࠋຍ࠼࡚ᚑ᮶ἲ࡜ྠᵝࡢ᪉ἲ࡛ࠊCeO2ࠊZrO2 ཬࡧ Nd2O3 ࡟ࡑࢀࡒࢀ Rh ᢸᣢࡋࡓཧ↷ࢆㄪ〇ࡋࡓࠋ
2. ୖグヨᩱ࡟ࡘ࠸࡚ in-situ ࡛ࡢᐃࡀྍ⬟࡞ᐃࢭࣝࢆ⏝࠸࡚ࠊゐ፹ㄪ〇ᚋཬࡧ㑏ඖ๓ฎ⌮120Υࠊ150Υࠊ300Υ5 ศࠊ5H295He ୰ࡢ Rh ࡢ K ྾཰➃ XAFSᐃ㸦㏱㐣ἲ㸧ࢆ BL14B1࡟࡚⾜ࡗࡓࠋ๓ฎ⌮ཬࡧ ᐃࣇ࣮ࣟࢆ Fig. 4 ࡟♧ࡍࠋ㺙㺻㺪㺽㺷ྲྀ᭰㺔㺼㺛PLQヨ㦂᮲௳ᐃձ኱Ẽ+HFFᗘ

57᫬㛫
PLQᐃղ๓ฎ⌮ձ++HFFΥ

++HFF+HFF

57ЍΥ๓ฎ⌮ղЍΥᐃճ

+HFF๓ฎ⌮ճ++HFFЍΥΥᐃմ ᚋฎ⌮+HFFΥЍΥ



Fig. 4 Preprocessing and measurement flowࡲࡓࠊゐ፹ㄪ〇ᚋࡢ Rh ࡢ K ྾཰➃ XANESᐃ㸦㏱㐣ἲ㸧ࢆ BL14B1 ࡟࡚⾜ࡗࡓࠋ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸ᚑ᮶ἲཬࡧ᪂つἲࡢືᚄศᕸ㛵ᩘࢆ Fig. 5-a,b ࡟♧ࡍࠋ䠉㻞㻟㻞䠉



Pring-8/SACLA฼⏝◊✲ᡂᯝ㞟฼⏝◊✲ᡂᯝ
SSPring-8/SACLA

Section AB

 Fig. 5-a Fourier transformed Rh K-edge   Fig. 5-b Fourier transformed Rh K-edge
EXAFS(Conventional)            
EXAFS(Developed)ㄪ〇ᚋࡢ㓄఩ᵓ㐀ࡣࠊ㓟໬ Rh㸦Rh-O-Rh㸧࡛࠶ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋ㑏ඖฎ⌮ᚋࡢ㓄఩ᵓ㐀࡟࠾࠸࡚ࠊ᪂つἲࡣ 120Υ࠿ࡽ Rh ࣓ࢱࣝ㸦Rh-Rh㸧ࡢ⏕ᡂࢆ☜ㄆ࡛ࡁࡓࠋ୍᪉ࠊᚑ᮶ἲ࡛ࡣ 150Υ
ࡲ࡛ Rh ࣓ࢱࣝࡣ☜ㄆࡉࢀࡎࠊ300Υ࡛ Rh ࣓ࢱࣝࡢ⏕ᡂࡀ☜ㄆ࡛ࡁࡓࠋࡇࢀࡽࡢࡇ࡜࠿ࡽࠊ᪂つἲࡣ㑏ඖ㞺ᅖẼୗ࡛㏿ࡸ࠿࡟ Rh-O ࡀ Rh-Rh ࡟ኚ໬ࡍࡿ஦ࡀศ࠿ࡗࡓࠋ
ࡲࡓࠊᚑ᮶ἲ࡛ࡣ 150Υ㑏ඖฎ⌮ᚋ࡟ࠊ⣙ 3.0ύ఩⨨࡟➨஧㏆᥋ࣆ࣮ࢡࡀ☜ㄆࡉࢀࡓࠋࡇࡢࣆ࣮
ࢡࡣ Rh-O-Rh ࡜ࡣ␗࡞ࡾࠊRh-O-X㸦CeZrNd ⣔」ྜ㓟໬≀ᡂศ㸧࡜᥎ᐃࡉࢀࡿࠋ࡜ࡇࢁ࡛ࠊᐊ
᫬࡟ Rh-O-X ࡟⏤᮶ࡍࡿࣆ࣮ࢡࡀほᐹࡉࢀ࡞࠿ࡗࡓࡢࡣࠊX ⥺ࡢ྾཰ࡀᙉ࠸ᮏᮦᩱ⣔࡛ࡣ➨஧㏆᥋ࣆ࣮ࢡࡢヲ⣽࡞ EXAFS ゎᯒࡀᅔ㞴࡛࠶ࡗࡓࡓࡵ࡜ண᝿ࡉࢀࡿࡀࠊࡑࡢ୍᪉ࠊ㐺ᗘ࡞㑏ඖฎ⌮࡟ࡼࡾ Rh-O-X ࡀ Rh-ᢸయ௜㏆ࡢ⤖ྜ࡜ࡋ࡚ほᐹࡉࢀࡓࡇ࡜࠿ࡽࠊᚑ᮶ἲ࣭᪂つἲ࠸ࡎࢀࡢࢧࣥࣉࣝ࡟࠾࠸࡚ࡶࠊึᮇ ᐊ ࡟࠾࠸࡚ࡣࡇࡢ⤖ྜࡣ⏕ᡂࡋ࡚࠸ࡿ࡜᥎ᐃࡉࢀࡿࠋࡇࡢࡇ࡜ࡣࠊ⪏ஂᚋࡢ SEM-EDX ほᐹ࡟࡚ Nd ௜㏆࠿ࡽከࡃࡢ Rh ⢏Ꮚࡀほᐹ㸦)LJ㸧ࡉࢀࡓ஦ࡸ㐣ཤࡢ▱ぢ[1]࡜ࡶ୍⮴ࡋ࡚࠸ࡿ஦࠿ࡽࠊࡇࡢ Rh-O-Nd ⤖ྜࡀࠊຎ໬ᢚไຠᯝ࡟ᐤ୚ࡋ࡚࠸ࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋ࡞࠾ࠊ᪂つἲ࡛ࡣ Rh-O-Xࡀほᐹࡉࢀ࡞࠿ࡗࡓࡀࠊࡇࢀࡣ㑏ඖ๓ฎ⌮ 120Υ࡛᪤࡟ Rh-Rh ࡟ኚ໬ࡋࡓⅭ࡛࠶ࡾࠊࡼࡾప ࡛ࡣᏑᅾࡍࡿྍ⬟ᛶࡀ࠶ࡿ࡜⪃࠼ࡿࠋ

Fig. 6 SEM-EDX(Developed after aging)ḟ࡟ࠊᚑ᮶ἲཬࡧ᪂つἲࡢ XANES ࢫ࣌ࢡࢺࣝࢆ Fig. 7 ࡟♧ࡍࠋᚑ᮶ἲ᪂つἲRh/Nd2O3
Rh2O3

Fig. 7 Rh K-edge XANESᚑ᮶ἲࡢ Rh ࡢࢫ࣌ࢡࢺࣝࡣ Rh2O3 ࡟㏆࠸ᙧ≧ࢆ♧ࡍࡀࠊ᪂つἲࡢ Rh ࡢࢫ࣌ࢡࢺࣝࡣ Nd2O3

䠉㻞㻟㻟䠉

Pring-8/SACLA฼⏝◊✲ᡂᯝ㞟฼⏝◊✲ᡂᯝ
SS
Pring-8/SACLA

Section AB

࡟ Rh ࢆᢸᣢࡋࡓᙧ≧࡟㏆࠸஦ࡀ☜ㄆ࡛ࡁࡓࠋ㏻ᖖ Rh ࡜ Nd2O3 ࡢᙉ࠸┦஫స⏝ࡣࠊప ࠿ࡽࡢ࣓ࢱࣝ໬ಁ㐍࡟ᑐࡋ࡚㜼ᐖせᅉ࡜࡞ࡿࡀࠊ᪂つᢸᣢἲࢆ㐺ᛂࡍࡿ஦࡛ࠊRh ࡟ᑐࡋ࡚ࡢ Nd ࡢ᥋ゐ㢖ᗘࢆ㧗ࡵࡘࡘࡶࠊRh ୍⢏Ꮚ࡟ᑐࡋ࡚ࠊ㐺ษ࡞㔞[2]ࡢ Nd ࡀᢸయ࠿ࡽ෌㓄⨨ࡉࢀࡓࡓࡵࠊప ࠿ࡽࡢ࣓ࢱࣝ໬࡟ᑐࡋ࡚ࡶ㜼ᐖࡉࢀࡎࠊRh ⢏ᡂ㛗ᢚไ࡟ຠᯝࢆࡋࡓࡶࡢ࡜⪃࠼ࡽࢀࡿࠋ௒ᚋࡢㄢ㢟㸸㧗 㞺ᅖẼኚືࡢ㐣Ώࢆᶍᨃࡋࡓ᮲௳ୗ࡛ࡢ XAFSドཬࡧ Pd ⣔࡛ࡢ᳨ウࢆ⾜࠺ࠋᐃࢆ㏻ࡋ࡚ࠊRh จ㞟ᢚไ࣓࢝ࢽࢬ࣒ࡢ᳨ཧ⪃ᩥ⊩㸸[1] N. Nagai , ゐ፹ 52(2), 149, (2010)[2] T. Tanabe , ゐ፹ 52(6), 465-467, (2010)(Received: August 23, 2018; Early edition: April 10, 2019,
Accepted: July 16, 2019; Published: August 29, 2019䠉㻞㻟㻠䠉