http://support.spring8.or.jp/Report_JSR/PDF_IAe_ALL/IAe_11A1835.pdf

2011A1835                            BL14B2ࠕ◲㯤ಟ㣭㔠ࠖཬࡧࠕ◲㯤ಟ㣭㔠࡟ᢸᣢࡋࡓ⎔ቃㄪ࿴ᆺ
ࣃࣛࢪ࣒࢘ゐ፹ SAPdࠖࡢᵓ㐀ゎᯒStructural Analysis of Environmentally Benign Palladium Catalyst,
Sulfur-modified Au-supported Pd, SAPd࢔ࣝ࢔࣑ࣥ ࣔࣁ࣐ࣥࢻ a, బ⸨ 㝯ಇ a, ᫍ㇂ ᑦ஽ b, ᮏ㛫 ᚭ⏕ c, ࿘ᮾ ᬛ a, ᭷⃝ ගᘯ a
Mohammad Al-Amina, Takatoshi Satoa, Naoyuki Hoshiyab, Tetsuo Honmac,Satoshi Shutoa, Mitsuhiro Arisawaaa໭ᾏ㐨኱Ꮫ኱Ꮫ㝔⸆Ꮫ◊✲㝔, b㻔ᰴ㻕ࣇࣝࣖ㔠ᒓ, c㻔බ㈈㻕㧗㍤ᗘග⛉Ꮫ◊✲ࢭࣥࢱ࣮ Hokkaido University Faculty of Pharmaceutical Sciences, bFuruya Metal Co. Ltd., cJASRIa⎔ቃㄪ࿴ᆺ Pd ゐ፹ SAPd ࡢ Pd K-edge ࡜ Au L3-edge ࡟ࡘ࠸࡚྾཰➃㏆ഐࡢ XANES ᐃࢆ⾜ࡗࡓࠋPd K-edge ᐇ㦂ࡢ⤖ᯝࠊ໬Ꮫⓗ཯ᛂᛶࡣ㢮ఝࡋ࡚࠸ࡿࡶࡢࡢ Pd ࡸ S ࡢᢸᣢ㔞ࡢ␗࡞ࡿ➨㸯
ୡ௦ SAPd ࡜➨ 2 ୡ௦ SAPd ࡀඹ࡟࡯ࡰྠࡌ Pd ࢆ᭷ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡉࡽ࡟ࠊSAPd ࡢAu L3-edge ᐇ㦂ࡢ⤖ᯝࠊSAPd ᙧᡂ࡟㛵ࢃࡗ࡚࠸ࡿ Au ࡣ⾲㠃ୖࡢ 1ࠥᩘཎᏊᒙ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ࣮࣮࢟࣡ࢻ㸸 ⎔ቃㄪ࿴ᆺゐ፹ࠊXAFS⫼ᬒ࡜◊✲┠ⓗ㸸 ᆅ⌫ ᬮ໬ࢆ⦆࿴ࡍࡿⅭ࡟ࠊ ᐊຠᯝ࢞ࢫࡢ᤼ฟᢚไࢆྍ⬟࡜ࡍࡿ⎔ቃㄪ࿴ᆺ〇㐀ᢏ⾡ࡀồࡵࡽࢀ࡚࠸ࡿࠋኴ㝧㟁ụᮦᩱࠊⰍ⣲ࠊ་⸆ရࡢ〇㐀࡟ Pd ゐ፹ࡣᖜᗈࡃ౑ࢃࢀ࡚࠸ࡿࡀࠊ㧗άᛶ࡛⧞㏉ࡋ౑࠼ࠊ཯ᛂ⣔ෆ࡟₃ὤࡍࡿ Pd 㔞ࡢᑡ࡞࠸ᅛᐃ໬ᢏ⾡ࡣ㛤Ⓨࡉࢀ࡚࠸࡞࠸ࠋ➹⪅ࡣ༙ᑟయᢸᣢᆺ Pd ゐ፹ࡢ㛤Ⓨࢆ⾜࠸ࠊᩘࠎࡢᡂᯝࢆ࠶ࡆ࡚ࡁࡓࡀ࣒࢞ࣜ࢘ࠊࣄ⣲ࡢ᭷ᐖ≀ࢆྵ᭷ࡍࡿࡇ࡜ࡀၥ㢟࡛࠶ࡗࡓ[1]ࠋ᭱㏆ࠊᅗ 1㸬SAPd ࡢ〇㐀᪉ἲࡇࡢၥ㢟ࢆゎỴࡍࡿ Pd ࡢ᪂ࡋ࠸⪏⇕ᛶ
3R㻔ࣜࢹ࣮ࣗࢫࠊ࣮ࣜࣘࢫࠊࣜࢧ࢖ࢡࣝ㻕㔠ⷧ⭷ᅛᐃ໬ゐ፹ࠊ◲㯤ಟ㣭㔠࡟ᢸᣢࡋࡓࣃࣛࢪ࣒࢘
㻔Sulfur-modified Au-supported Pd: SAPdࠊᅗ 1㻕ࡢ㛤Ⓨ࡟ᡂຌࡋࡓ㻔໬Ꮫᕤᴗ᪥ሗࠊᖹᡂ 21 ᖺ 10 ᭶ 23
᪥ࠊグ஦࡜ࡋ࡚ᥖ㍕㻕[2]ࠋᮏ᪂ゐ፹ࡢせࡣ➹⪅ࡀⓎぢࡋࡓ◲㯤ಟ㣭㔠࡛࠶ࡾࠊᚑ᮶ࡢᆒ୍⣔ゐ፹࣭୙ᆒ୍⣔ゐ፹ࡢ㛗ᡤࡢࡳࢆ᥃ࡅྜࢃࡏࡓࠊ඲ࡃ᪂ࡋ࠸ᴫᛕࡢゐ፹࡛࠶ࡿࠋ༶ࡕࠊྛ✀໬Ꮫᐇ㦂ࡢ⤖ᯝࠊSAPd ࡣ◲㯤ಟ㣭㔠ࡀࣃࣛࢪ࣒࢘ࢆᙉᅛ࡟ᅛᐃࡋࡓ୙ᆒ୍⣔ゐ፹࡛࠶ࡾࠊ㕥ᮌ—ᐑᾆ࢝ࢵࣉࣜࣥࢢ࡞࡝ࣃࣛࢪ࣒࢘ࢡࣟࢫ࢝ࢵࣉࣜࣥࢢ཯ᛂ⣔୰࡟㧗άᛶ࡞ᆒ୍⣔ࣃࣛࢪ࣒࢘ࢆᚲせ᭱ᑠ㔞ᨺฟࡍࡿࡇ࡜࡟ࡼࡾࠊඃࢀࡓ⧞㏉ࡋ฼⏝ᛶ㻔ᩘ༑ᅇ௨ୖ㻕࡜ᩥ⊩ྐୖ᭱ᑠ㔞ࡢࣃࣛࢪ࣒࢘₃ὤ㔞㻔཯ᛂ
ᾮ୰ 1 ppm ௨ୗ㻕ࢆවഛࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡲࡓࠊ➹⪅ࡽࡣ㕥ᮌ—ᐑᾆ࢝ࢵࣉࣜࣥࢢ
࡟࠾ࡅࡿ SAPd ࡢ཯ᛂᶵᵓࠊᾮᒙࢥࣥࣅࢼࢺࣜ࢔ࣝࢣ࣑ࢫࢺ࣮ࣜ࡬ࡢᛂ⏝࡟ࡘ࠸࡚ࡶ᫂ࡽ࠿࡟ࡋ
࡚࠸ࡿ[3]ࠋࡑࢀᨾࠊSAPd ࡣ⏘ᴗ⏺࠿ࡽࡶዲホࢆᚓ࡚࠸ࡿࡀࠊ◲㯤ಟ㣭㔠࡜ SAPd ࡢᵓ㐀ࡣᮍゎ࡛᫂࠶ࡾࠊ᭦࡞ࡿ SAPd ࡢⓎᒎ㻔Pd ௨እࡢゐ፹㔠ᒓᐃ╔࡬ࡢᛂ⏝ࠊ᭦࡟㧗άᛶ࡞ SAPd ࡢ๰〇㻕ࡀᅔ㞴࡞≧ἣ࡛࠶ࡗࡓࠋᮏㄢ㢟࡛ࡣ◲㯤ಟ㣭㔠ࢆ㘽໬ྜ≀࡟ᤣ࠼ࠊXAFS ࢆ⏝࠸࡚ SAPd ࡢᵓ㐀ゎᯒ࡟࢔ࣉ࣮ࣟࢳࡍࡿࠋࡲࡓࠊ➹⪅ࡽࡣ⌧ᅾ SAPd ࡢ〇㐀᪉ἲࢆ 2 ✀㻔౽ᐅୖࠊᮏ✏࡛ࡣ➨ 1 ୡ௦ SAPdࠊ➨ 2 ୡ௦ SAPd ࡜࿧ࡪࠋ㻕 ᭷ࡋ࡚࠸ࡿࠋఱࢀࡢ SAPd ࡶ໬Ꮫⓗ཯ᛂᛶࡣྠࡌࡶࡢࡢࠊᢸᣢࡉࢀ࡚࠸
ࡿ Pd ࡸ◲㯤ࡢ㔞ࡀ␗࡞ࡗ࡚࠸ࡿࠋᮏㄢ㢟࡛ࡣࡇࢀࡽ Pd ࡢ┦ྠᛶ࡟ࡘ࠸࡚ࡶ᫂ࡽ࠿࡟ࡍࡿࠋᐇ㦂㸸
SAPd ࠾ࡼࡧᶆရࡢ Pd K-edge ࡜ Au L3-edge ࡟࠾ࡅࡿ྾཰➃㏆ഐࡢ X ⥺྾཰ࢫ࣌ࢡࢺࣝ㻔XANES㻕ࡢ ᐃࢆ⏘ᴗ฼⏝ϩࣅ࣮࣒ࣛ࢖ࣥ BL14B2 ࡛ᐇ᪋ࡋࡓࠋศග⤖ᬗ࡟ࡣ Si㻔311㻕ࢆ⏝࠸ࡓࠋPd K-edge࡟࠾ࡅࡿ SAPd ࡢ ᐃࡣࠊ19 ⣲Ꮚ Ge ༙ᑟయ᳨ฟჾࢆ౑⏝ࡋࡓ⺯ගἲ࡟ࡼࡾ⾜ࡗࡓࠋAu L3-edge࡟࠾ࡅࡿ SAPd ࡢ ᐃࡣࠊ㌿᥮㟁Ꮚ཰㔞ἲ࡟ࡼࡾ⾜ࡗࡓࠋᶆရࡣࠊ୧྾཰➃࡜ࡶ࡟㏱㐣ἲ࡟ࡼࡾᐃࢆ⾜ࡗࡓࠋᅗ 2㸬Pd K-edge XANES ࢫ࣌ࢡࢺࣝ
ࡲࡎࠊSAPd ࠾ࡼࡧᶆရࡢ Pd K-edge ࡟ࡘ࠸࡚྾཰➃㏆ഐࡢ XANES ᐃࢆ⾜ࡗࡓࠋ༶ࡕࠊ⏝࠸ࡓヨᩱࡣࠊ➨ 1 ୡ௦ SAPd㻔཯ᛂࡢ౑⏝ࡍࡿ๓ࡢࡶࡢ㻕ࠊ➨ 2 ୡ௦ SAPd㻔཯ᛂ࡟౑⏝ࡍࡿ๓ࡢࡶࡢ㻕ࠊ㕥ᮌ—ᐑᾆ࢝ࢵࣉࣜࣥࢢ࡟ 10 ᅇ౑⏝ࡋࡓ SAPdࠊBuchwald-Hartwig ཯ᛂ࡟ 10 ᅇ౑⏝ࡋࡓ SAPdࠊࣆࣛࢽ࢔ฎ⌮㻔⃰◲㓟࡜㐣㓟໬Ỉ⣲ࡢΰྜᾮฎ⌮㻕ࢆࡏࡎ࡟స〇ࡋࡓ㔠ᇶᯈ࡟ᢸᣢࡋࡓࣃࣛࢪ࣒࡛࢘࠶ࡿࠋࡇࢀࡽࡣ඲࡚ᯈ≧࡛࠶ࡾࠊ⺯ගἲࢆ⏝࠸࡚ ᐃࡋࡓ㻔2.5°ഴࠊᦂື᭷ࠊࢫࣜࢵࢺࢧ࢖ࢬ 5 mm㻕ࠋࡲࡓࠊᶆရ࡜ࡋ࡚ࠊ㔠ᒓࣃࣛࢪ࣒࢘㻔Pdࠊᯈ≧㻕ࠊ㓟໬ࣃࣛࢪ࣒࢘㻔PdOࠊ⢊ᮎ㻕ࠊ◲໬ࣃࣛࢪ࣒࢘㻔PdSࠊ⢊ᮎ㻕ࠊ◲㓟ࣃࣛࢪ࣒࢘㻔PdSO4ࠊ⢊ᮎ㻕ࠊࢸࢺࣛ࢟ࢫࢺࣜࣇ࢙ࢽࣝ࣍ࢫࣇ࢕ࣥࣃࣛࢪ࣒࢘㻔Pd㻔PPh3㻕4ࠊ⢊ᮎ㻕ࢆ᥇⏝ࡋࠊ㏱㐣ἲ࡟ࡼࡾ ᐃࡋࡓ㻔ᅗ 2㻕ࠋ ḟ࡟ࠊSAPd ཬࡧᶆရࡢ Au L3-edge ࡟ࡘ࠸࡚྾཰➃㏆ഐࡢ XANES ᐃࢆ⾜ࡗࡓࠋ༶ࡕࠊ⏝࠸ࡓヨᩱࡣࠊAu on Micaࠊࣆࣛࢽ࢔ฎ⌮῭ Au on Mica㻔➨ 1 ୡ௦㻕ࠊࣆࣛࢽ࢔ฎ⌮῭ Au on Mica㻔➨ 2 ୡ௦㻕࡛࠶ࡿࠋࡇࢀࡽࡣ඲࡚ᯈ≧࡛࠶ࡾࠊ㌿᥮㟁Ꮚ཰㔞ἲ࡟ࡼࡾ ᐃࡋࡓ㻔5°ഴࠊᦂື᭷㻕ࡲࡓࠊᶆရ࡜ࡋ࡚ࠊ㔠ᒓ㔠㻔Auࠊᯈ≧㻕ࠊ㓟໬㔠㻔Au2O3ࠊ⢊ᮎ㻕ࠊሷ໬㔠㻔AuClࠊ⢊ᮎ㻕ࢆ⏝࠸ࠊ㏱㐣ἲ࡟ࡼࡾᐃࡋࡓ㻔ᅗ 3㻕ࠋQuickTimeý Ç²êLí£ÉvÉçÉOÉâÉÄ
Ç™Ç±ÇÃÉsÉNÉ`ÉÉÇ¾å©ÇÈÇžÇ½Ç…ÇÕïKóvÇ-ÇÅBᅗ 3㸬Au L3-edge XANES ࢫ࣌ࢡࢺࣝ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸 ࡲࡎࠊᅗ 2 ࡟♧ࡋࡓ㏻ࡾࠊSAPd ࠾ࡼࡧᶆရࡢ Pd K-edge XANES ࢫ࣌ࢡࢺࣝ࠿ࡽࠊ➨ 1 ୡ௦ SAPdࡶ➨ 2 ୡ௦ SAPd ࡶṤ࡝ྠࡌ Pd ࢆ᭷ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ ࡲࡓࠊ➨ 1 ୡ௦ SAPd ࢆ㕥ᮌ—ᐑᾆ࢝ࢵࣉࣜࣥࢢࠊBuchwald-Hartwig ཯ᛂࡢఱࢀ࡟௜ࡋࡓሙྜ
࡛ࡶࠊ཯ᛂᚋࡢ SAPd ࡣ཯ᛂ๓ࡢ SAPd ࡜Ṥ࡝ྠࡌ Pd ࢆ᭷ࡋ࡚࠸ࡿࡇ࡜ࡶศ࠿ࡗࡓࠋ10 ᅇ⧞ࡾ㏉ࡋ฼⏝ࡋࡓ࡟ࡶ࠿࠿ࢃࡽࡎࠊṤ࡝ኚ໬ࡀ࡞࠸ࡇ࡜ࡣࡇࡢඛࡶ⧞ࡾ㏉ࡋ཯ᛂ࡟౑⏝࡛ࡁࡿ஦ࢆ♧ࡋ࡚࠾ࡾࠊSAPd ࡢ⧞㏉ࡋ฼⏝ᛶࡀ 10 ᅇ⛬ᗘ࡟␃ࡲࡿࡶࡢ࡛࡞࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋ ᭦࡟ࠊ◲㯤ಟ㣭ࡋ࡚࡞࠸㔠ᇶᯈ࡟┤᥋ Pd ࢆᢸᣢࡋࡓሙྜ࡛ࡶୖグ SAPd ࡜ྠᵝࡢࢹ࣮ࢱࡀᚓࡽ
ࢀࡓࠋᮏ Pd ࡣ Pd ࢡࣟࢫ࢝ࢵࣉࣜࣥࢢ࡟⧞ࡾ㏉ࡋ௜ࡍ࡜ࠊᚎࠎ࡟཰⋡ࡀపୗࡋࠊ㏻ᖖࡢ SAPd ࡼࡾࡶゐ፹άᛶ࡟ຎࡿࡶࡢ࡛࠶ࡿࡀࠊSAPd స〇᫬ࡢ◲㯤ಟ㣭ࡢព⩏ࠊSAPd ࡢᵓ㐀ࢆ⪃ᐹࡍࡿୖ࡛㔜せ࡞▱ぢ࡛࠶ࡿࠋ ḟ࡟ࠊᅗ 3 ࡟ SAPd ࠾ࡼࡧᶆရࡢ Au L3-edge XANES ࢫ࣌ࢡࢺࣝࢆ♧ࡋࡓ㏻ࡾࠊSAPd ᙧᡂ࡟㛵ࢃࡗ࡚࠸ࡿ Au ࡣ⾲㠃ୖࡢ 1ࠥᩘཎᏊᒙ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ௒ᚋࡣࡼࡾⷧ࠸㔠ୖ࡟ SAPd ࢆస〇ࡋࡓࢧࣥࣉࣝࢆㄪᩚࡍࡿࡇ࡜ࡀᮃࡲࡋ࠸ࠋ௒ᚋࡢㄢ㢟㸸BL27SU㻔2011B㻕࡟࠾࠸࡚ SAPd ࡢ S K-edge ࠾ࡼࡧ Pd L-edge ࡟ࡘ࠸࡚ XAFS ᐇ㦂ࢆ⾜࠸ࠊ➨ 1
ୡ௦ SAPdࠊ➨ 2 ୡ௦ SAPdࠊ཯ᛂ౑⏝ᚋࡢ SAPd ࡢᵓ㐀ゎᯒࢆ㐙⾜ࡍࡿࠋ᭦࡟ࠊSAPd ࢆ⏝࠸ࡓPd ࢡࣟࢫ࢝ࢵࣉࣜࣥࢢ࡟ࡼࡾᚓࡽࢀࡿ⏕ᡂ≀୰࠶ࡿ࠸ࡣ཯ᛂ⁐ᾮ୰ࡢ Pd ࢆゎᯒࡋࠊ཯ᛂάᛶ✀ࢆゎ᫂ࡍࡿࠋཧ⪃ᩥ⊩㸸
[1] M. Arisawa, M. Hamada, I. Takamiya, M. Shimoda, S. Tsukamoto, Y. Arakawa, A. Nishida, Adv. Synth.
Cat., 348, 1063, 㻔2006㻕. N. Hoshiya, N. Isomura, M. Shimoda, H. Yoshikawa, Y. Yamashita, K. Iizuka, S.
Tsukamoto, S. Shuto, M. Arisawa, ChemCatChem, 1, 279, 㻔2009㻕. M. Shimoda, T. Konishi, K. Tateishi,T. Toujyou, S. Tsukamoto, N. Nishiwaki, M. Arisawa, N. Hoshiya, S. Shuto, N. Isomura, H. Yokota, Y.
Furukawa, K. Iizuka, T. Ogiwara, Y. Isozaki, Y. Yamashita, H. Yoshikawa, S. Ueda, K. Kobayashi, J.
Appl. Chem., 108, 024309, 㻔2010㻕㻚
[2] N. Hoshiya, M. Shimoda, H. Yoshikawa, Y. Yamashita, S. Shuto, M. Arisawa, J. Am. Chem. Soc., 132,7270, 㻔2010㻕.
[3] N. Hoshiya, S. Shuto, M. Arisawa, Adv. Synth. Cat., 353, 743, 㻔2011㻕.