ᐇ㦂␒ྕ㸸 㸰㸳㹑㸮㸮㸳 2013 ᖺᗘ ᡂᯝබ㛤↓ൾ⏝ᴗ ᡂᯝሗ࿌᭩ ൦እԈᔺȷ્ЈᢅᆉƴƓƚǔᘮэ҄ᙲ׆Ʒᚐଢ ⱥᩥ㢟ྡ Study on poisoning deterioration factor in hydrogen absorption/desorption process ඵᮌఙஓࠊᑠᕝᬛྐࠊሯ⏣༓ᜨࠊỈ㇂๛ኈࠊ ⸨ᮏᚿࠊ㔠⨾ࠊෆᒣ┤ᶞ Shinya YAGI, Satoshi OGAWA, Chie TSUKADA, Tsuyoshi MIZUTANI, Taichi FUJIMOTO, Tomomi KANAI, Naoki UCHIYAMA ྡྂᒇᏛࠊᰴᘧ♫ࢶ࣑ࢸࢵࢡ Nagoya University, Atsumitech 1. ᐃᐇ᪥ 2013 ᖺ 11 ᭶ 29 ᪥ 10 㸫18 30 ศ㸦2 ࢩࣇࢺ㸧 㸪BL6N1 2013 ᖺ 12 ᭶ 10 ᪥ 18 30 ศ – 22 30 ศ (1 ࢩࣇࢺ)㸪BL5S1 2013 ᖺ 12 ᭶ 10 ᪥ 18 30 ศ – 22 30 ศ (1 ࢩࣇࢺ)㸪BL6N1 2014 ᖺ 2 ᭶ 19 ᪥ 10 㸫18 30 ศ㸦2 ࢩࣇࢺ㸧 㸪BL6N1 2014 ᖺ 2 ᭶ 21 ᪥ 10 㸫18 30 ศ㸦2 ࢩࣇࢺ㸧 㸪BL6N1 2014 ᖺ 2 ᭶ 26 ᪥ 14 30 ศ – 22 30 ศ (2 ࢩࣇࢺ) 㸪BL5S1 2014 ᖺ 2 ᭶ 28 ᪥ 10 㸫18 30 ศ㸦2 ࢩࣇࢺ㸧 㸪BL5S2 2. ᴫせ ⌧ᅾࠊࢼࣀ⢏Ꮚ࡛ᵓᡂࡉࢀ࡚࠸ࡿ 3G0J1L ⣔ࢆ୰ᚰỈ⣲྾ⶶᮦᩱࡢ◊✲㛤 Ⓨࢆ᥎㐍ࡋ࡚࠸ࡿࠋࡇࡢᮦᩱࡣࠊ⌧ᅾࠊᐊ ࣭Ẽᅽ࡛Ỉ⣲ࢆ⧞ࡾ㏉ࡋ྾ⶶ࣭ ᨺฟྍ⬟࡞ࣞ࣋ࣝ࠶ࡿࡀࠊẼ୰ᨺ⨨ࡋ࡚࠸ࡿࠊᚎࠎỈ⣲྾ⶶ࣭ᨺฟ ≉ᛶࡀຎࡋ࡚ࡋࡲ࠺ࠋࡑࡢཎᅉࡋ࡚ࡣࠊẼ୰ࡢỈẼࡸ㓟⣲ࠊࡉࡽࡣ 62[㐣㓟◲㯤ࡼࡿ⿕ẘࡀ⪃࠼ࡽࢀࡿࡀࠊࡑࡢຎ࣓࢝ࢽࢬ࣒ࡘ࠸࡚ࡣ᫂ ࡽ࡛ࡣ࡞࠸ࠋᮏ◊✲ㄢ㢟ࡣࠊࡇࡢⅬࢫ࣏ࢵࢺࣛࢺࢆ࠶࡚ࡿࠋ%/1 ࡛ࡣࠊ ᭱⾲㠃ᅛ╔ࡉࢀ࡚࠸ࡿ 3G ࢼࣀ⢏Ꮚࡢ㓟⣲ࠊỈẼࠊ62[ ࡘ࠸࡚ 3G/HGJH;$)6 ࢆࠊ+Hࣃࢫࢆ⏝࠸࡚ࠕࡑࡢሙ㞺ᅖẼ ;$)6 ศᯒࠖࢆ⾜࠺ࠋࡲࡓ %/6 ࡛ࡣࠊẼ㠀ᭀ㟢᮲௳ୗ࡛స〇ࡋࡓࢼࣀ⢏Ꮚヨᩱࡘ࠸࡚ࠊLQVLWX ⎔ቃ ୗ࡛Ỉ⣲࢞ࢫࢆᭀ㟢ࡋࠊỈ⣲྾ⶶ࣭ᨺฟ㐣⛬࠾ࡅࡿ 1L ࡢᏛ≧ែኚࡘ࠸ ࡚ㄪࡿࠋ 㸬⫼ᬒ◊✲┠ⓗ 0J࣐ࢢࢿࢩ࣒࢘⣔ᮦᩱ㝈ࡗ࡚ࡣࠊᖖ ࣭ᖖᅽ᮲௳ୗ࡛Ỉ⣲ࢆ྾ⶶ࣭ᨺฟ ࡍࡿᮦᩱࡣሗ࿌ࡀࢇ↓࠸࠸࠺⌧≧࡛࠶ࡿࠋᡃࠎࡣࠊ3G0J1L ⣔ࢆ୰ᚰ Ỉ⣲྾ⶶᮦᩱࡢ◊✲㛤Ⓨࢆ᥎㐍ࡋ࡚࠸ࡿࠋࡇࡢᮦᩱࡣࠊ⌧ᅾࠊᐊ ࣭Ẽᅽ࡛ Ỉ⣲ࢆ⧞ࡾ㏉ࡋ྾ⶶ࣭ᨺฟྍ⬟࡞ࣞ࣋ࣝ࠶ࡿࠋࡉࡽ࡞ࡿ㧗ᛶ⬟ࡋ࡚ࠊ྾ ⶶ࣭ᨺฟࡢᛂ㛫ࢆ▷ࡃࡍࡿࡓࡵࠊࡇࡢᮦᩱࢆ͇ࢼࣀ⢏Ꮚ͇࡛ᵓᡂࡍࡿࡇ ࢆᥦࡋ࡚ࡁࡓࠋࡇࢀࡼࡾࠊỈ⣲ࡢゎ㞳ᛂࡸᣑᩓ㏿ᗘࢆࡁࡃᨵၿ࡛ࡁ ࡿࡇࡸࠊ⏝ᮦᩱࢆᖜῶࡽࡍࡇࡀ࡛ࡁࡿࠋ ࡋࡋࠊࡇࢀࡲ࡛ࡢ◊✲࡛ࡣࠊ㠀ᖖΎί࡞⾲㠃ࢆᣢࡘ≧ែ࡛ࢼࣀ⢏Ꮚࢆస 〇ࡋ࡚࠸ࡿࡓࡵࠊẼ୰ࡢ㓟⣲ࡸỈẼࡢ྾╔ࡼࡗ࡚ࠊỈ⣲྾ⶶ࣭ᨺฟ≉ᛶ ࡀຎࡋ࡚ࡋࡲ࠺ࡇࡀ᫂ࡽ࡞ࡗ࡚࠸ࡿࠋᮏ◊✲ㄢ㢟࡛ࡣࠊ㌾ ; ⥺ࡽ◳ ; ⥺ࢆ⏝࠸ࡓ ;$)6 ศᯒࡼࡗ࡚ࠊ ຎせᅉࢆ᫂ࡽࡍࡿࡇࢆ┠ⓗࡍࡿࠋ ࡲࡓࠊ ᑗ᮶ⓗỈ⣲྾ⶶỈ⣲࢞ࢫࡢ₃ࢀࢆ᳨▱ࡋࡸࡍࡃࡍࡿࡇࢆᛕ㢌࠾ࡃᚲ せࡶ࠶ࡿࡇࡽࠊỈ⣲࢞ࢫ୰͇⮯͇ࡋ࡚◲㯤ཎᏊࢆྵࡴ᭷ᶵศᏊ࡛ ࠶ࡿ◲ࢪ࣓ࢳࣝ㸦'LPHWK\O6XOILGH㸸'06ࢆῧຍࡋࡓሙྜࢆᐃࡋࠊ'06 3G ࢼࣀ⢏Ꮚࡢ྾╔ᛂࡘ࠸࡚ࡶ᫂ࡽࡍࡿࠋ 㸬ᐇ㦂ෆᐜ XAFS ᐃࡣࠊ2 ࡘࡢࣅ࣮࣒࡚ࣛࣥᐇࡋࡓࠋࡲࡎࠊBL5S1 ࡛ࡣࠊNi K ྾➃ XAFSࠊࡑࡋ࡚ BL6N1 ࡛ࡣ Pd L3 ྾➃ XAFS ᐃࢆᐇࡋࡓࠋ ࡑࢀࡒࢀࡢࣅ࣮࣒࡛ࣛࣥࡣࠊ⏝ࡍࡿ X ⥺ࡢ࢚ࢿࣝࢠ࣮㡿ᇦࡀ␗࡞ࡿࡇ ྜࢃࡏ࡚ࠊࡑࢀࡽ X ⥺ࡢ㏱㐣⬟ࡁ࡞ᕪࡀ࠶ࡿࠋࡲࡓࠊ⏝࡛ࡁࡿ࢞ࢫ✀ ไ㝈ࡀ࠶ࡿࡓࡵ௨ୗࡢ ᐃ᮲௳࡛ XAFS ᐃࢆᐇࡋࡓࠋ 㸦㸯㸧BL5S1㸸Ni ࢼࣀ⢏Ꮚࡽᡂࡿⷧ⭷ヨᩱࡘ࠸࡚Ỉ⣲(100%)࢞ࢫࡢ྾ⶶ࣭ ᨺฟ࠾ࡅࡿ XAFS ᐃࠋ 㸦㸰㸧BL6N1㸸Pd ࢼࣀ⢏Ꮚࢆྵࡴⷧ⭷ヨᩱࡘ࠸࡚◲㯤⿕ẘ≧ែ࠾ࡅࡿ XAFS ᐃࠋ 㸬⤖ᯝ࠾ࡼࡧ⪃ᐹ 㸦㸯㸧Ni ࢼࣀ⢏Ꮚࡽᡂࡿⷧ⭷ヨᩱࡢỈ⣲࢞ࢫࡢ྾ⶶ࣭ᨺฟ࠾ࡅࡿ XAFS ᐃ Ni ࢼࣀ⢏Ꮚࡣࠊ࠶ࡽࡌࡵྡྂᒇᏛ࢚ࢥࢺࣆ⛉Ꮫ◊✲ᡤ࡚స〇ࡋࠊ┿ ✵ᑒṆࡋࡓ≧ែ࡛Ỉ⣲ᭀ㟢ࢳࣕࣥࣂࡶ BL5S1 ᦙධࡋࠊᐇ㦂ྎᅛᐃࡋ ࡓࠋᐇ㦂⨨ࡘ࠸࡚ࠊᅗ㸯♧ࡍࠋ ᅗ 1㸸BL5S1 ᮎ➃㒊タ⨨ ࡋࡓỈ⣲ᭀ㟢ࢳࣕࣥࣂࡢ ᬒ┿ ᨺᑕගࡢᑟධ㒊⺯ග X ⥺ࡢྲྀࡾฟࡋ㒊ࡣࠊ┿✵⏝ࣇࣛࣥࢪ ICF70 ཌࡉ 20ȣm ࡢ࢝ࣉࢺࣥ⭷ࢆ࢚࣏࢟ࢩ⣔ᶞ⬡࡛ᅛᐃࡋ࡚⏝࠸ࡓࠋỈ⣲ࡣࠊ1 Ẽ ᅽࡲ࡛⣧Ỉ⣲࢞ࢫ㸦⣧ᗘ㸸99.99%㸧ࢆᚎࠎᑟධࡋࠊ⬺Ỉ⣲ࡣỈ⣲࢞ࢫ ࢆẼࡋࡓᚋ࣒࣊ࣜ࢘࢞ࢫࢆ 1 Ẽᅽࡲ࡛ᑟධࡋ࡚⨨ࡋࡓࠋ BL5S1 ࡚ XAFS ᐃࢆ⾜࠺๓ࠊNi ࢼࣀ⢏Ꮚⷧ⭷ࡘ࠸࡚Ỉ⣲྾ⶶ࣭ᨺ ฟ≉ᛶࢆỈᬗືᏊ࣐ࢡࣟࣂࣛࣥࢫ(QCM)ἲ࡛ ᐃࡋࡓ⤖ᯝࡘ࠸࡚ᅗ㸰 ♧ࡍࠋ ᅗ㸰㸸QCM ἲ ࡼࡿ Ni ࢼࣀ⢏Ꮚ ⷧ⭷ࡢỈ⣲྾ ⶶ࣭ᨺฟ≉ᛶ ᐃ ⤖ᯝ ࡇࡢ⤖ᯝࡼࡿࠊึᅇࡢỈ⣲ᭀ㟢࡛ࡣᐊ ࡛ 7 Torr ࡢపᅽୗ࡛Ỉ⣲྾ⶶࡀ ᐇ⌧࡛ࡁ࡚࠸ࡿࡇࡀࢃࡿࠋ࡞࠾ࠊ7 Torr ࡛ࡢ྾ⶶ㔞ࡣ⣙ 0.5 wt%࡛࠶ࡿࠋ 㸦ᅗ 㸰ࡢᶓ㍈ࡣࠊ1.0 = 1.7 wt%ᑐᛂࡍࡿ㸧ࡑࡢᚋࡣ 50 Torr ㏆࡛Ỉ⣲࢞ࢫࡢ Ni ࢼࣀ⢏Ꮚ⾲㠃ࡢ྾╔࣭⬺㞳ᛂࢆ♧ࡋࡓࠋࡋࡋࠊ2 ᅇ┠ࡸ 3 ᅇ┠࡛ࡣỈ⣲྾ ⶶࢆ♧ࡉ࡞ࡗࡓࠋࡇࡢ⤖ᯝࡼࡾࠊNi ࢼࣀ⢏Ꮚࡣࣂࣝࢡࡣࡁࡃ␗࡞ࡿ⎔ቃ ᮲௳࡛࠶ࡿࠊᐊ ࣭7 Torr ࡛Ỉ⣲ࢆ྾ⶶࡍࡿࡇࡀ♧ࡉࢀࡓࠋࡋࡋࠊ྾ⶶࡉ ࢀࡓỈ⣲ࡣ Ni ࢼࣀ⢏Ꮚෆ㒊࡛ᏛⓗᏳᐃࡋ࡚࠸ࡿࡇࡀணࡉࢀࡿࠋ ᅗ㸱 Ni ࢼࣀ⢏Ꮚⷧ⭷ࡢỈ⣲ᭀ㟢๓ᚋ Ỉ⣲᭚㟢๓ Ỉ⣲㞺ᅖẼୗ ᶆ‽ヨᩱࡢ NEXAFS ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋ Ni ࢼࣀ⢏Ꮚⷧ⭷ࡢ NEXAFS ࢫ࣌ࢡࢺࣝࡣࠊ Intensity [a. u.] Ni foil (ࣂࣝࢡ㸧ࡸ㓟ࢽࢵࢣࣝヨᩱࡢࢫ࣌ ࢡࢺࣝࡣ␗࡞ࡗࡓᙧ≧ࢆ♧ࡋ࡚࠸ࡿࠋࡲ ࡓࠊB. Lengeler ࡽ[1]ࡼࡗ࡚ሗ࿌ࡉࢀ࡚ NiH 0.85 ࠸ࡿ Ni Ỉ⣲≀(NiH0.85)ẚ㍑ࡍࡿࠊ㢮 ఝᙧ≧࡛࠶ࡿࡇࡀࢃࡿࠋ NiO*0.5 Ni foil ᅗ㸱㸸Ni ࢼࣀ⢏Ꮚⷧ⭷ࡢỈ⣲ᭀ㟢๓ᚋ Ni K-edge NEXAFS @Aichi SR BL5S1 8320 8340 8360 Photon energy [eV] 8380 ᶆ‽ヨᩱࡢ྾➃㏆ഐ(NEXAFS)ࢫ࣌ࢡࢺ ࣝ ࡋࡋࠊࣆ࣮ࢡࢺࢵࣉࡢ⨨ࢆヲ⣽ぢ࡚ࡳࡿ B. Lengeler ࡽࡢࢫ࣌ࢡࢺࣝ ࡣᕪࡀ࠶ࡿࠋලయⓗࡣࠊᡃࠎࡢ Ni ࢼࣀ⢏Ꮚⷧ⭷ヨᩱࡢሙྜࡣࠊỈ⣲ᭀ㟢ᚋ 㓟ᛂࡀ⏕ࡌࠊࣆ࣮ࢡ⨨ࡀ NiO ࡰྠࡌ⨨ࢩࣇࢺࡋ࡚࠸ࡿࠋඛࡢ QCM ᐃࡢ⤖ᯝ㸦ᅗ 2㸧ྜࢃࡏ࡚⪃࠼ࡿࠊNi ࢼࣀ⢏ᏊࡣỈ⣲ᭀ㟢㓟 ࡉࢀࡿ⪃࠼ࡽࢀࡿࠋࡑࡢ⤖ᯝࠊ྾ⶶࡉࢀࡓỈ⣲ࡣᏛⓗᏳᐃࡉࢀࠊỈ⣲ ᨺฟࡣ⮳ࡽ࡞ࡗࡓ᥎ ࡉࢀࡿࠋ 㸦㸰㸧Pd ࢼࣀ⢏Ꮚࢆྵࡴⷧ⭷ヨᩱࡢ◲㯤⿕ẘ≧ែ࠾ࡅࡿ XAFS ᐃ 㸦㸯㸧ྠᵝ Pd ࢼࣀ⢏Ꮚࢆస〇ࡋࠊNi ᇶᯈ⾲㠃ᅛ╔ࡋࡓࡶࡢࢆヨᩱ ࡋࡓࠋࡋࡋࠊPd ࢼࣀ⢏Ꮚࡢᅛ╔㔞ࡀ㠀ᖖపࡃࠊ┠ⓗࡍࡿヨᩱࡀ࡛ࡁ࡞ ࡗࡓࠋᅗ㸲ࡣࠊᖹᡂ 24 ᖺᗘస〇ࡋࡓ Pd ࢼࣀ⢏Ꮚヨᩱ DMS ࢞ࢫࢆᭀ㟢ࡋ ◲㯤⿕ẘࢆࡋࡓヨᩱࠊ᭦Ỉ⣲ࢧࢡࣝ㸦Ỉ⣲ᭀ㟢㸫┿✵Ẽ㸧ࢆᐇ ࡋࡓヨᩱ࡛ ᐃࡋࡓࠊS K ྾➃ NEXAFS ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋ࠶ࢃࡏ࡚ࠊᶆ‽ ヨᩱࡋ࡚ࠊ DMSࠊ◲㯤ࡑࡋ࡚◲㓟ྜ≀(SO4)ࡢ NEXAFS ࢫ࣌ࢡࢺࣝࡶ♧ࡍࠋ స〇ࡋࡓ Pd ࢼࣀ⢏Ꮚࡢᅛ╔㔞ࡀࡁࢃࡵ࡚ᚤ㔞ࡢࡓࡵࠊ◲㯤⿕ẘせࡋࡓ◲㯤 ࡢ྾╔㔞ࡣࢃࡎ࡛࠶ࡾᐃ㔞ⓗ࡞ゎᯒࡣ㞴ࡋ࠸ࡀࠊᐃᛶⓗࡣ DMS ᭀ㟢ࡼࡗ ࡚ Pd ࢼࣀ⢏Ꮚ⾲㠃ࡣ◲㯤྾╔ ࡀ⏕ࡌࡿࡇࡀࢃࡗࡓࠋࡲࡓࠊ DMS ᭀ㟢Ỉ⣲ࢧࢡࣝࢆィ 8 ࢧࢡࣝᐇࡋࡓᚋ࡛ࡣࠊ◲㯤ࡢ ྾╔㔞ࡀቑຍࡋࡘࡘ DMS ࡢ྾╔ 㔞ࡶቑຍࡋ࡚ࠊ◲㯤⿕ẘ≧ែࡀᙧ ᡂࡉࢀࡿࡇࡀ᫂ࡽ࡞ࡗࡓࠋ ᅗ㸲㸸Pd ࢼࣀ⢏Ꮚࡢ DMS ࡼࡿ ◲㯤⿕ẘᚋỈ⣲ࢧࢡࣝࢆᐇ ࡋࡓヨᩱࡢ S K ྾➃ NEXAFS ࢫ࣌ࢡࢺࣝ ᚋࡢㄢ㢟 ᚋࡢㄢ㢟ࡣࠊ௨ୗࡢ࠾ࡾ࡛࠶ࡿࠋ ࣭Ni ࢼࣀ⢏Ꮚࡣᐇ㦂ᐊࡽᨺᑕගタࡢ㍺㏦ࡢ㐣⛬࡛ṧ␃࢞ࢫᡂศࡼࡗ࡚ 㓟ࡋ࡚࠸ࡓࡓࡵࠊヨᩱࡀ㓟ࡋࡃ࠸㍺㏦ᶵᵓࡢ㛤Ⓨࡀᚲせ࡛࠶ࡿࠋලయⓗ ࡣࠊ㠀Ⓨࢤࢵࢱ࣮࣏ࣥࣉ(NEG)ࡸᑠᆺ࣏࢜ࣥࣥࣉ➼ࢆά⏝ࡋࡓ㧗┿✵ᑐ ᛂࢺࣛࣥࢫࣇ࣮࣋ࢵࢭࣝࡢ㛤Ⓨࢆᚲせࡍࡿࠋ ࣭BL5S1 ࡢᮎ➃ࣁࢵࢳෆ࡚ࢼࣀ⢏Ꮚࢆస〇ࡋࠊ༶Ỉ⣲ᭀ㟢ᐇ㦂ࡀ in-situ ᮲௳ୗ࡛ᐇ࡛ࡁࡿࡼ࠺࡞⨨ഃࡢᕤኵࢆᚲせࡍࡿࠋ ࣭Pd ࢼࣀ⢏Ꮚࡀຠ⋡ࡼࡃᅛ╔࡛ࡁࡿヨᩱస〇ഃࡢᕤኵࢆᚲせࡍࡿࠋ ཧ⪃ᩥ⊩ [1] B. Lengeler and R. Zeller, Solid State Commun. 51, 889 (1984).
© Copyright 2024 ExpyDoc
