http://support.spring8.or.jp/Report_JSR/PDF_JSR_31A/2019A1624.pdf

2019A1624BL14B2࢝ࣝ࣎ࣥ㓟ࡢ㧗㑅ᢥⓗ㑏ඖ཯ᛂࢆಁ㐍ࡍࡿྜ㔠ゐ፹ࡢ In situ XAFS ᐃ࡟ࡼࡿᒁᡤᵓ㐀ゎᯒAnalysis of Local Structure of Alloy Catalysts for High Selective Reductionof Carboxylic Acid by In situ XAFS⚟ఫ ㅬ஽ a, ୰㇂ ဴ a, Ỉᇉ ඹ㞝 b, ⣽ᕝ ୕㑻 c, ᮏ㛫 ᚭ⏕ dNoriyuki Fukuzumia, Tetsu Nakatania, Tomoo Mizugakib, Saburo Hosokawac,
Tetsuo Honmadaᰴᘧ఍♫䝎䜲䝉䝹, b ኱㜰኱Ꮫ኱Ꮫ㝔ᇶ♏ᕤᏛ◊✲⛉㻘㻌c ி㒔኱Ꮫ㻘㻌d㻌㻔බ㈈㻕㧗㍤ᗘග⛉Ꮫ◊✲䝉䞁䝍䞊aDaicel Corporation, bOsaka University, cKyoto University, dJASRI Mo-Pd-Fe2O3 ゐ፹ࡣ࢝ࣝ࣎ࣥ㓟ࡢ㑏ඖ࡟ᑐࡋ࡚㧗࠸άᛶࢆ♧ࡍࡇ࡜ࢆ☜ㄆࡋ࡚࠸ࡿࠋ㧗άᛶ࠿ࡘ㧗ᑑ࿨ࡢゐ፹ࢆタィࡍࡿࡓࡵ࡟ࡣヲ⣽࡞ゐ፹ࡢᵓ㐀ゎᯒࡀᚲせ࡛࠶ࡿࠋࡇࢀࡲ࡛ࡢᐇ㦂࠿ࡽᮏゐ፹ࡣ Fe2O3 ࡟ᑐࡍࡿ Pd 㔞࡟ࡼࡗ࡚άᛶࡀኚ໬ࡍࡿ஦ࡀ☜ㄆࡉࢀ࡚࠸ࡿࡀࠊᐇ㝿ࡢ཯ᛂ㞺ᅖẼ࡛࠶ࡿỈ⣲ࠊ㓑㓟ඹᏑ㞺ᅖẼ࡟࠾ࡅࡿゐ፹ࡢᵓ㐀ࡣゎ᫂ࡉࢀ࡚࠸࡞࠸ࠋ௒ᅇỈ⣲ࠊ㓑㓟ඹᏑ㞺ᅖẼୗ࡛ Pd 㔞ࡢ␗࡞ࡿゐ፹ࡢ XAFS ᐃࢆᐇ᪋ࡍࡿࡇ࡜࡛άᛶⅬ࡟㉳ᅉࡍࡿ Fe ࡢ≀ᛶኚ໬ࢆ㏣㊧ࡋࡓࠋ࣮࣮࢟࣡ࢻ㸸 XAFSࠊྜ㔠⢏ᏊࠊỈ⣲໬཯ᛂࠊ㑏ඖ཯ᛂ⫼ᬒ࡜◊✲┠ⓗ㸸▼Ἔ౯᱁ࡢ㧗㦐࡜ᑗ᮶ⓗ࡞ᯤῬࡢᠱᛕ࠿ࡽ⬺▼Ἔࡢືࡁࡀୡ⏺ⓗ࡟㐍ࢇ࡛࠸ࡿࠋ࢚ࢳࣞࣥㄏᑟရࡢ㟂せࡀୡ⏺ⓗ࡟ఙࡧ⥆ࡅࡿ୍᪉࡛ࠊࢼࣇࢧ⏤᮶ࡢ࢚ࢳࣞࣥ〇ရࡀ୺ὶ࡞᪥ᮏ࡛ࡣᏳ౯࡞ኳ↛࢞ࢫ⏤᮶ࡢᾏእ〇ရ࡟ᑐࡍࡿ➇தຊࢆ⥔ᣢࡍࡿࡇ࡜ࡣ㞴ࡋࡃࠊ௒ᚋᅜ㝿➇தຊࡢపୗࡀᠱᛕࡉࢀࡿࠋࡑࡢ཯ᛂᛶࡢ㧗ࡉ࠿ࡽ᭷ᶵྜᡂရࡢᇶᖿཎᩱ࡜ࡋ࡚⏝࠸ࡽࢀࡿ࢔ࢭࢺ࢔ࣝࢹࣄࢻࡶ࢚ࢳࣞࣥㄏ
ᑟရࡢ୍ࡘ࡛࠶ࡾࠊᑗ᮶ⓗ࡞࢚ࢳࣞࣥࡢ㧗㦐ࢆᠱᛕࡋࢼࣇࢧ௨እࡢཎᩱ࠿ࡽྜᡂࡍࡿᢏ⾡ࡀồࡵࡽࢀ࡚࠸ࡿࠋ▼Ἔ㈨※ࡢ࡞࠸᪥ᮏ࡟ࡣ௒ᚋࣂ࢖࣐࢜ࢫཎᩱࢆ⏝࠸ࡓ໬Ꮫ〇ရࡢ〇㐀ࡀᮃࡲࢀࡿࡀࠊࣂ࢖࣐࢜ࢫཎᩱࡢㄏᑟရ໬࡟࠾࠸࡚ࡣྵ㓟⣲໬ྜ≀ࡢ㑏ඖᢏ⾡ࡀᴟࡵ࡚㔜せ࡛࠶ࡿࠋ࢔ࢭࢺ࢔ࣝࢹࣄࢻࡣ࢝ࣝ࣎ࣥ㓟ࢆ㑏ඖࡍࡿࡇ࡜࡟ࡼࡾᚓࡽࢀࡿࡀࠊ୙Ᏻᐃ࡞࢔ࣝࢹࣄࢻ࡛㑅ᢥⓗ࡟Ṇࡵࡿ࡜࠸࠺ᢏ⾡ࡣᴟࡵ࡚㞴ࡋ࠸ࠋᡃࠎࡢ◊✲ࢢ࣮ࣝࣉ࡛ࡣࠊࡇࢀࡲ࡛࡟ᅛయゐ፹ࢆ⏝࠸ࡓ㓑㓟ࡢ㧗㑅ᢥⓗỈ⣲໬཯ᛂ࡟ࡼࡿ࢔ࢭࢺ࢔ࣝࢹࣄࢻྜᡂࡢ᳨ウࢆ⾜ࡗ࡚ࡁࡓ[1]ࠋࡇࢀࡲ࡛ࡢ◊✲⤖ᯝ࠿ࡽ Mo-Pd-Fe ゐ፹ࡀᮏ཯ᛂ࡟ᑐࡋ࡚㧗࠸άᛶࢆ♧ࡍࡇ࡜ࢆ☜ㄆࡋ࡚࠸ࡿ[2]ࠋᮏゐ፹ࡣ཯ᛂ୰ Pd 㔞࡟ࡼࡗ࡚ PdFe ྜ㔠ࡢ⏕ᡂ㔞ࡀኚ໬ࡋࠊPdFe ⢏Ꮚࡢ⾲㠃✚࡟࡯ࡰ┦㛵ࡍࡿᙧ࡛཯ᛂᛶࢆไᚚ࡛ࡁࡿࡇ࡜ࡶゎ᫂ࡋ࡚࠸ࡿࠋࡲࡓ཯ᛂ᫬ Fe ࡣ㓟໬๣࡛࠶ࡿ㓑㓟࡟ࡼࡾ㓟໬ࡉࢀࠊ㟁Ꮚࣜࢵࢳ࡞≧ែ࡟࡞ࡾࡸࡍ࠸஦ࡀ⪃࠼ࡽࢀࡿࡀࠊᮏゐ፹࡟࠾࠸࡚ࡣᐇ㝿ࡢ཯ᛂ㞺ᅖẼ࡛࠶ࡿỈ⣲࡜㓑㓟ඹᏑ㞺ᅖẼୗ࡛ࡢᵓ㐀ࡣᮍゎ࡛᫂࠶ࡿࠋᮏᐇ㦂࡛ Pd 㔞ࡢ␗࡞ࡿ Mo ῧຍゐ፹ࢆ XAFS ᐃࡋࠊMoࠊPd ࡀ Fe ࡟ᑐࡋ࡚࡝ࡢࡼ࠺࡟ᙳ㡪ࡋ࡚࠸ࡿ࠿ࢆ☜ㄆࡋࡓࠋάᛶ࡟㉳ᅉࡍࡿ Fe ࡢᵓ㐀ࢆゎ᫂ࡍࡿ஦ࡀฟ᮶ࢀࡤࠊゐ፹タィ࡟཯ᫎࡍࡿࡇ࡜࡛ゐ፹ᑑ࿨ࢆྥୖࡍࡿࡇ࡜ࡀྍ⬟࡜࡞ࡾᕤᴗ໬ࡋࡓ㝿ࡢゐ፹஺᥮㢖ᗘࢆపῶࡍࡿࡇ࡜ࡀᮇᚅ࡛ࡁࡿࠋ
ᐇ㦂㸸 40 wt%Pd-Fe2O3ࠊ80 wt%Pd-Fe2O3 ゐ፹䠄Fe2O3㸸100 wt%࡟ᑐࡋ࡚ Pd㸸40 or 80 wt%䠅ࡣࠊ௵ពࡢ๭ྜ࡛◪㓟ࣃࣛࢪ࣒࢘⁐ᾮ࡜◪㓟㕲ࠊࢡ࢚ࣥ㓟ࢆΰྜࡋࠊ110°௚ ࡛஝⇱ࠊ400°௚ ࡛↝ᡂฎ⌮࡟ࡼࡾㄪ〇ࡋࡓࠋ28 wt%Mo-40 wt%Pd-Fe2O3ࠊ28wt%Mo-80wt%Pd-Fe2O3 ゐ፹䠄Fe2O3㸸100 wt%࡟ᑐࡋ࡚ Pd㸸
40 or 80 wt%䠅ࡣ๓グࡢ 40 or 80 wt%Pd-Fe2O3 ゐ፹࡟ᑐࡋ࡚࢖࢜ࣥ஺᥮Ỉ࡛⁐ゎࡉࡏࡓ୐ࣔࣜࣈࢹࣥ㓟භ࢔ࣥࣔࢽ࣒࢘㺃ᅄỈ࿴≀ࢆ௵ពࡢ๭ྜ࡛ຍ࠼ࠊ110°௚ ࡛஝⇱ࠊ400°௚ ࡛↝ᡂฎ⌮ࡋㄪ〇ࡋࡓࠋXAFS ᐃࡣࠊSPring-8 ࡢ⏘ᴗ฼⏝ࣅ࣮࣒ࣛ࢖ࣥ BL14B2 ࡟࡚ᐇ᪋ࡋ Mo . ➃࡟ࡣ Si䠄311䠅㠃ࢆ䠉㻞㻠䠉౑⏝ࡋࡓࠋXAFS ᐃ⏝ࡢ᳨యࡣࠊ཯ᛂ๓ࡢྛゐ፹⢊ࢆ┤ᚄ 7 mm ࡢࢹ࢕ࢫࢡ≧࡟ᡂᆺࡋ Fe. Ẇ
ࡢ㏱㐣ἲ Quick XAFS ᐃࢆᐇ᪋ࡋࡓࠋFe ࡢࣜࣇ࢓ࣞࣥࢫ໬ྜ≀࡟ࡘ࠸࡚ࡣ Fe foil䠄Fe䠅ࠊ㓟໬㕲䠄Į-Fe2O3ࠊFe3O4䠅ࢆ⏝࠸ࡓࠋ㓑㓟౪⤥ࡣ ᐃࢭࣝࡢ๓࡟タ⨨ࡋ࡚࠸ࡿ௵ពࡢ ᗘ࡛ಖ ࡋࡓ㓑㓟ࣂࣈ࣮ࣛ࡟ᑐࡋ࡚࢟ࣕࣜ࢔࢞ࢫࢆὶධࡉࡏࡿࡇ࡜࡛㓑㓟࡜ゐ፹ࢆ཯ᛂࡉࡏࡓࠋࢹ࣮ࢱゎᯒࡣ Athenaver.0.9.25 ࢆ౑⏝ࡋࡓࠋ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸
ྛゐ፹ࡢ Fe . Ẇ㏱㐣ἲ XANES ᐃࡢ⤖ᯝࢆᅗ 1 ࡟♧ࡍࠋ⾲ 1 ࡣྛ᮲௳࡟࠾ࡅࡿࢫ࣌ࢡࢺࣝ࡟ᑐࡋ࡚ Į-Fe2O3ࠊFe3O4ࠊFe䠄metal䠅ࡢΰྜࢫ࣌ࢡࢺ࡛࣐ࣝࢵࢳࣥࢢࡋࡓ᫬ࡢࢫ࣌ࢡࢺࣝࡢ๭ྜࢆ♧ࡋ࡚࠸ࡿࠋᅗ 1ࠊ⾲ 1 ࡟♧ࡍࡼ࠺࡟ H2 㞺ᅖẼୗࠊ300°௚ࠊ1hr ಖᣢࡍࡿࡇ࡜࡛ Fe ࡣ 0 ౯ࡲ࡛㑏ඖࡍࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋࡑࡢᚋࠊ㓑㓟䠄AC䠅ࢆ H2/AC=15 ࡢẚ⋡࡛ὶධࡉࡏࡓ࡜ࡇࢁⱝᖸ㓟໬ࡀ㐍⾜ࡍࡿࡶࡢࡢ࡯࡜ࢇ࡝ኚ໬ࡣࡳࡽࢀ࡞࠿ࡗࡓࠋḟ࡟ࠊࡼࡾ㓑㓟ࡢᙳ㡪ࢆ☜ㄆࡍࡿࡓࡵ࡟ H2 ࢆ He ࡟ษࡾ᭰࠼ࡓ࡜ࡇࢁࠊFe䠄metal䠅ࡢ୍㒊ࡣ㓑㓟⏤᮶ࡢ㓟⣲࡛ Fe3O4 ࡲ࡛㓟໬ࡉࢀ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋ
 ⾲ 1 ࡟♧ࡍࡼ࠺࡟ Fe2O3 ࡟ᑐࡍࡿ Pd 㔞ࡀ␗࡞ࡿ࡜ H2/ACࠊHe/AC 㞺ᅖẼୗ࡟࠾ࡅࡿ Fe ࡜ Fe3O4
ࡢ๭ྜࡀ␗࡞ࡿࠋ㐣ཤࡢᐇ㦂࠿ࡽ Pd ࡜᥋ࡋ࡚࠸࡞࠸ Fe ࡣࡍࡄ࡟άᛶࢆኻ࠸ࠊMo ࡀ Pd ࡜᥋ࡋ࡚࠸࡞࠸ Fe ࡟ᑐࡋ࡚㟁Ꮚࢆ౪୚ࡍࡿ஦࡛άᛶⅬ࡜ࡋ࡚ᶵ⬟ࡋ࡚࠸ࡿ࡜⪃࠼࡚࠸ࡿࠋ௒ᅇࡢᐇ㦂࡛Pd ࡜᥋ࡋ࡚࠸࡞࠸ Fe ࡟ᑐࡍࡿ Mo 㔞ࡀከ࠸ 28 wt%Mo-80 wt%Pd-Fe2O3 ࡣࡼࡾ Mo ࡀຠ⋡ⓗ࡟ᶵ⬟ࡋ࡚࠸ࡿ஦ࢆ☜ㄆ࡛ࡁࡓࠋ

ᅗ 1㸬Fe .-edge XANES ࢫ࣌ࢡࢺࣝ 28 wt%Mo-40 wt%Pd-Fe2O3㻔ᕥ㻕ࠊ28 wt%Mo-80 wt%Pd-Fe2O3㻔ྑ㻕ᅗ 2㸬Fe .-edge XANES ࢫ࣌ࢡࢺࣝ 28 wt%Mo-40 wt%Pd-Fe2O3 ࡜ 28 wt%Mo-80 wt%Pd-Fe2O3 ࡢẚ㍑⾲ 1㸬ྛ

᮲௳
Air ᐊ
H2 300°௚
H2/AC 300°௚
He/AC 300°௚
H2 300°௚ᗘ࡟࠾ࡅࡿ Fe ࡢ໬Ꮫ≧ែྛ໬Ꮫ≧ែࡢ๭ྜ
28wt%Mo-40wt%Pd- Fe2O3
28wt%Mo-80wt%Pd-Fe2O3
Fe3O4Fe(metal)
Fe2O3
Fe3O4Fe(metal)
Fe2O3
75%
25%
80%
20%
100%
3%
97%
3%
97%
16%
84%
33%
67%
41%
59%
15%
85%
14%
86%

䠉㻞㻡䠉

௒ᚋࡢㄢ㢟㸸 ௒ᅇ Pd 㔞ࡢ␗࡞ࡿ஧✀ࡢゐ፹ࢆᐇ㝿ࡢ཯ᛂ᮲௳࡛࠶ࡿỈ⣲࡜㓑㓟ඹᏑୗ࡛ XAFS ᐃࢆᐇ᪋ࡋࡓࡀ Fe ࡢ≀ᛶ࡟㐪࠸ࡣࡳࡽࢀ࡞࠿ࡗࡓࠋPd 㔞࡟ࡼࡿάᛶࡢ㐪࠸ࡣ Pd ࡢᵓ㐀ኚ໬ࡀ㛵ಀࡋ࡚࠸ࡿ࡜᥎ ࡋ࡚࠾ࡾࠊ௒ᚋ Pd ഃࡢ ᐃࢆᐇ᪋ࡍࡿࡇ࡜࡛ゐ፹ᵓ㐀ࢆゎ᫂ࡍࡿணᐃ࡛࠶ࡿࠋཧ⪃ᩥ⊩㸸
[1] ≉㛤 2017-047377䠄P2017-47377A䠅[2] ≉㛤 2016-150331䠄P2015-30642䠅

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