http://support.spring8.or.jp/Report_JSR/PDF_IAe_ALL/IAe_11B1952.pdf

2011B1952                           BL14B2ࠕ◲㯤ಟ㣭㔠࡟ᢸᣢࡋࡓ⎔ቃㄪ࿴ᆺࣃࣛࢪ࣒࢘ゐ፹ SAPdࠖࡢ཯ᛂάᛶ✀ゎᯒ
Structural Analysis of Actual Active Species of Environmentally Benign
Palladium Catalyst, Sulfur-modified Au-supported Pd, SAPd࢔ࣝ࢔࣑ࣥ ࣔࣁ࣐ࣥࢻ a, బ⸨ 㝯ಇ a, ᪂஭ ⪽ྐ b, ᮏ㛫 ᚭ⏕ c, ࿘ᮾ ᬛ a, ᭷⃝ ගᘯ a
Mohammad Al-Amina, Takatoshi Satoa, Satoshi Araib, 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཯ᛂάᛶ✀ࢆゎᯒࡍࡿⅭࠊSAPd ࢆ⏝࠸࡚㕥ᮌíᐑᾆ࢝ࢵࣉࣜࣥࢢཬ
ࡧ Buchwald-Hartwig ཯ᛂࢆ⾜ࡗࡓ࡜ࡁ࡟⏕ᡂࡍࡿ཯ᛂ⢒⏕ᡂ≀ࡢ Pd K-edge ࡟ࡘ࠸࡚྾཰➃㏆ഐ
ࡢ XANES ᐃࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ୧⏕ᡂ≀ࡀ࡯ࡰྠࡌ Pd ࢆ᭷ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡉࡽ
࡟ࠊࡇࡢ Pd ✀ࡣࠕ཯ᛂ๓ࡢ SAPdࠖཬࡧࠕ཯ᛂᚋࡢ SAPdࠖ࡜ྠࡌ Pd 㔠ᒓᚤ⢏Ꮚ࡛࠶ࡿ஦ࡀศ࠿
ࡾࠊSAPd ࡀ࣮ࣜࣜࢫ&࢟ࣕࢵࢳᶵᵓࢆ᭷ࡍࡿ஦ࡀ XAFS ᐇ㦂࠿ࡽࡶ♧၀ࡉࢀࡓࠋ࣮࣮࢟࣡ࢻ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Ⓨᅗ 1㸬SAPd ࡢ〇㐀᪉ἲࠊ㕥ᮌ㸫ᐑᾆ࢝ࢵࣉࣜࣥࢢࢆ⾜࠸ࠊᩘࠎࡢᡂᯝࢆ࠶ࡆ࡚ࡁࡓࡀࠊ࣒࢞ࣜ࢘ࠊࣄ⣲ࡢ᭷ᐖ≀ࢆྵ᭷ࡍࡿࡇ
࡜ࡀၥ㢟࡛࠶ࡗࡓ[1]ࠋ᭱㏆ࠊࡇࡢၥ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᥃ࡅ
ྜࢃࡏࡓࠊ඲ࡃ᪂ࡋ࠸ᴫᛕࡢゐ፹࡛࠶ࡿࠋ༶ࡕࠊྛ✀໬Ꮫᐇ㦂ࡢ⤖ᯝࠊSAPd ࡣ◲㯤ಟ㣭㔠ࡀࣃࣛࢪ࣒࢘ࢆᙉᅛ࡟ᅛᐃࡋࡓ୙ᆒ୍⣔ゐ፹࡛࠶ࡾࠊ㕥ᮌíᐑᾆ࢝ࢵࣉࣜࣥࢢ࡞࡝ࣃࣛࢪ࣒࢘ࢡࣟࢫ࢝ࢵࣉࣜࣥࢢ཯ᛂ⣔୰࡟㧗άᛶ࡞ᆒ୍⣔ࣃࣛࢪ࣒࢘ࢆᚲせ᭱ᑠ㔞ᨺฟࡍࡿࡇ࡜࡟ࡼࡾࠊඃࢀࡓ⧞㏉ࡋ฼⏝ᛶ㻔ᩘ༑ᅇ௨ୖ㻕࡜ᩥ⊩ྐୖ᭱ᑠ㔞ࡢࣃࣛࢪ࣒࢘₃ὤ㔞㻔཯ᛂᾮ୰ 1 ppm ௨ୗ㻕ࢆවഛࡋ࡚࠸ࡿࡇ
࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡲࡓࠊ➹⪅ࡽࡣ㕥ᮌ̾ᐑᾆ࢝ࢵࣉࣜࣥࢢ࡟࠾ࡅࡿ SAPd ࡢ཯ᛂᶵᵓࠊᾮᒙࢥࣥࣅࢼࢺࣜ࢔ࣝࢣ࣑ࢫ
ࢺ࣮ࣜ࡬ࡢᛂ⏝࡟ࡘ࠸࡚ࡶ᫂ࡽ࠿࡟ࡋ࡚
࠸ࡿ [3]ࠋSAPd ࢆ⏝࠸ࢀࡤࠊⅣ⣲í❅⣲⤖ྜᙧᡂ཯ᛂ࡛࠶ࡿ Buchwald-Hartwig ཯ᛂࡶࣜ࢞ࣥࢻࣇ࣮࡛ࣜ㐍⾜ࡍࡿ㻔ୡ⏺ึࡢ౛ࠊᅗ 2㻕[4]ࠋࡑࢀᨾࠊSAPd ࡣ⏘ᴗ⏺
࠿ࡽࡶዲホࢆᚓ࡚࠸ࡿࡀࠊSAPd ࡢᵓ㐀ᅗ 2㸬SAPd ࢆ⏝࠸ࡓ Buchwald-Hartwig ཯ᛂཬࡧ཯ᛂάᛶ✀࡟ࡘ࠸࡚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 SAPd ࢆ㘽໬ྜ≀࡟ᤣ࠼ࠊXAFS ࢆ⏝࠸࡚ SAPd ࡢ཯ᛂάᛶ✀ゎᯒ࡟࢔ࣉ࣮ࣟࢳࡍࡿࠋᐇ㦂㸸 ᅗ 3㸬㕥ᮌíᐑᾆ࢝ࢵࣉࣜࣥࢢ⢒⏕ᡂ≀ᅗ 4㸬Buchwald-Hartwig ཯ᛂ⢒⏕ᡂ≀

ࠕSAPd ࢆ⏝࠸࡚సᡂࡋࡓ㕥ᮌíᐑᾆ࢝ࢵࣉࣜࣥࢢ⢒⏕ᡂ≀⣙ 2 g㻔Pd ྵ᭷㔞㸻0.45 ppmࠊᅗ 3㻕ࠖ࡜ࠕSAPd ࢆ⏝࠸࡚సᡂࡋࡓ Buchwald-Hartwig ཯ᛂ⢒⏕ᡂ≀⣙ 2 g㻔Pdྵ᭷㔞㸻2.75 ppmࠊᅗ 4㻕ࠖࢆ≉〇࣍ࣝࢲ࣮㻔ᅗ 5㻕࡟㟼⨨ࡋࠊࡇࢀࡽࡢ Pd K-edge ࡟࠾ࡅࡿ྾཰➃㏆ഐࡢ X ⥺྾཰ࢫ࣌ࢡ ࢺ ࣝ 㻔XANES㻕 ࡢ ᐃ ࢆ ⏘ ᴗ ฼ ⏝ ϩ ࣅ ࣮ ࣒ ࣛ ࢖ ࣥ
BL14B2 ࡛ᐇ᪋ࡋࡓࠋศග⤖ᬗ࡟ࡣ Si㻔311㻕ࢆ⏝࠸ࡓࠋPdK-edge ࡟࠾ࡅࡿ SAPd ࡢ ᐃࡣࠊ19 ⣲Ꮚ Ge ༙ᑟయ᳨ฟჾࢆ౑⏝ࡋࡓ⺯ගἲ࡟ࡼࡾ⾜ࡗࡓ㻔2.5°ഴࠊᦂື᭷ࠊࢫࣜ
ࢵࢺࢧ࢖ࢬ 5 mm㻕ࠋ
ᅗ 5㸬≉〇ヨᩱ࣍ࣝࢲ࣮⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸 Pd K-edge ᐇ㦂ࡢ⤖ᯝࠊ㕥ᮌíᐑᾆ࢝ࢵࣉࣜࣥࢢࠊBuchwald-Hartwig ཯ᛂࡢఱࢀ࡟௜ࡋࡓ⢒ᡂ⏕≀ࡶṤ࡝ྠࡌ Pd ࢆ᭷ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓ㻔ᅗ 6㻕ࠋᅗ 6㸬Pd ࢡࣟࢫ࢝ࢵࣉࣜࣥࢢ⢒⏕ᡂ≀ཬࡧ SAPd ࡢ Pd K-edge XANES ࢫ࣌ࢡࢺࣝSAPd before: ཯ᛂ࡟௜ࡍ๓ࡢ SAPd
SM product: 㕥ᮌíᐑᾆ࢝ࢵࣉࣜࣥࢢ⢒⏕ᡂ≀
SAPd SM after: 㕥ᮌíᐑᾆ࢝ࢵࣉࣜࣥࢢ࡟௜ࡋࡓᚋࡢ SAPd
BH product: Buchwald-Hartwig ཯ᛂ⢒⏕ᡂ≀
SAPd BH after: Buchwald-Hartwig ཯ᛂ࡟௜ࡋࡓᚋࡢ SAPd ࡲࡓࠊࡇࢀࡽࡢࢫ࣌ࢡࢺࣝࢆ๓ᅇ 2011A1835 ㄢ㢟࡛ ᐃࡋࡓࠕ཯ᛂ࡟௜ࡍ๓ࡢ SAPdࠖཬࡧࠕ཯
ᛂ࡟௜ࡋࡓᚋࡢ SAPdࠖࡢࢫ࣌ࢡࢺࣝ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊ඲࡚Ṥ࡝ྠ୍࡛࠶ࡿ஦ࡀศ࠿ࡗࡓࠋࡇࡢ
ࡇ࡜ࡣࠊSAPd ࡟ᢸᣢࡉࢀࡓ Pd ✀㻔Pd 㔠ᒓᚤ⢏Ꮚ㻕ࡀ཯ᛂ⣔୰࡛ࡶࠊ཯ᛂᚋ࡛ࡶኚࢃࡽ࡞࠸ࡇ࡜ࢆព࿡ࡋ࡚࠾ࡾࠊ௚ࡢᐇ㦂࠿ࡽ♧၀ࡉࢀ࡚࠸ࡿ SAPd ࡢ࣮ࣜࣜࢫ&࢟ࣕࢵࢳᶵᵓࢆᣦ♧ࡍࡿࢹ࣮ࢱ࣮࡜ゝ࠼ࡿ㻔ᅗ 2㻕ࠋ௒ᚋࡢㄢ㢟㸸 Pd ప₃ὤᛶࡣ SAPd ࡢඃࢀࡓ≉ᚩ࡛ࡣ࠶ࡿࡀࠊ
⏕ᡂ≀୰ࡢ Pd ྵ᭷㔞ࡀㅽᑡ࡛࠶ࡿⅭ㻔0.45 ppm ࡜2.75 ppm㻕ࠊ௒ᅇ ᐃࡋࡓࢹ࣮ࢱ࣮ࡣ S/N ẚࡀᝏ࠸࡜࠸࠺ၥ㢟Ⅼࢆ᭷ࡋ࡚࠸ࡿࠋㄅୖⓎ⾲ࡍࡿⅭ࡟ࡣࠊ᭦࡟࣐ࢩࣥࢱ࢖࣒ࢱ࢖࣒ࢆ☜ಖࡋࢹ࣮ࢱ࣮ࢆྲྀࡾ┤ࡍᚲせࡀ࠶ࡿࠋཧ⪃ᩥ⊩㸸
[1] M. Arisawa, M. Hamada, I. Takamiya, M. Shimoda, S. Tsukamoto, Y. Arakawa, A. Nishida, Adv. Synth.
Cat., 348, 1063,㻌㻔2006㻕. N. Hoshiya, N. Isomura, M. Shimoda, H. Yoshikawa, Y. Yamashita, K. Iizuka, S.
Tsukamoto, S. Shuto, M. Arisawa, ChemCatChem, 1, 279,㻌㻔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,㻌㻔2010㻕.
[3] N. Hoshiya, S. Shuto, M. Arisawa, Adv. Synth. Cat., 353, 743,㻌㻔2011㻕.
[4] M. Al-Amin, T. Honma, N. Hoshiya, S. Shuto, M. Arisawa, Adv. Synth. Cat., 354, 1061-1068,㻌㻔2012㻕.