2009B2060

                           BL14B2◪㓟ࢪࣝࢥࢽ࣒࢘࠾ࡼࡧ㐣ሷ⣲㓟ࢪࣝࢥࢽ࣒࢘Ỉ⁐ᾮࡢ EXAFS ゎᯒ
EXAFS Analyses of Zirconium Nitrate and Perchlorate Aqueous Solutions㧗ᓮ ྐ㐍 a, ᑠᕝ ಙ᫂ b
Fumiyuki Takasakia, Nobuaki Ogawaba➨୍⛥ඖ⣲໬Ꮫᕤᴗ㻔ᰴ㻕, b ⛅⏣኱ᏛᕤᏛ㈨※Ꮫ㒊Daiichi Kigenso Kagaku Kogyo. CO. LTD., bFaculty of Engineering and Resource Science, Akita University.

aZr ሷỈ⁐ᾮ୰࡛ࠊZr ໬Ꮫ✀ࡣ⁐ᾮࡢᡂศ⃰ᗘ࡟౫Ꮡࡋከᵝ࡞㔜ྜᵓ㐀ࢆᣢࡘࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡇࡢ⁐Ꮡᵓ㐀ࡀࠊZr ⁐ᾮࡢᯫᶫ๣࡜ࡋ࡚ࡢᶵ⬟࡟ᙳ㡪ࡍࡿ࡜⪃࠼ࡽࢀࡿࡓࡵࠊ⁐Ꮡᵓ㐀ไᚚ࡟ࡼࡿᶵ⬟ᨵⰋࢆᮏ◊✲ࡢ᭱⤊┠ᶆ࡜ࡋ࡚࠸ࡿࠋᗈ⠊࡞ᡂศ⤌ᡂ㡿ᇦ࡟࠾ࡅࡿ◪㓟 Zr ࠾ࡼࡧ㐣ሷ⣲㓟 Zr Ỉ⁐ᾮࡢ⁐Ꮡᵓ㐀ࢆㄪ࡭ࡿࡓࡵ EXAFS ゎᯒࢆᐇ᪋ࡋࡓࠋࡑࡢ⤖ᯝࠊ[Zr]ࠊ[H+]ࡀኚ໬ࡋ࡚ࡶࠊZr-Zr 㓄఩ᩘࠊ㊥㞳ࡀ࡯࡜ࢇ࡝ኚ໬ࡋ࡞࠸ࠊ༶ࡕ⎔ቃ࡟ᛂࡌ࡚⁐Ꮡᵓ㐀ࡀኚ໬ࡋ࡞࠸࡜࠸࠺≉ᚩࢆᣢࡘ Zr ⁐ᾮࢆᚓࡿࡓࡵࡢ᮲௳ࡣࠊ[NO3-]/[Zr]ࠊ[ClO4-]/[Zr]= 0.7 ࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ࣮࣮࢟࣡ࢻ㸸 ◪㓟ࢪࣝࢥࢽ࣒࢘Ỉ⁐ᾮࠊ㐣ሷ⣲㓟ࢪࣝࢥࢽ࣒࢘Ỉ⁐ᾮࠊ⁐Ꮡᵓ㐀ࠊ㔜ྜࠊ㓄఩ᩘ⫼ᬒ࡜◊✲┠ⓗ㸸Zr ሷỈ⁐ᾮ୰ࡢ Zr ໬Ꮫ✀ࡣࠊZr ཎᏊྠኈࡀ 2 㔜ࡢ OH ᇶࢆ௓ࡋ࡚⤖ྜࡋࡓ㔜ྜయ࡜ࡋ࡚Ꮡᅾࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿ[1], [2]ࠋࡓ࡜࠼ࡤࠊ1M ࢜࢟ࢩሷ໬ࢪࣝࢥࢽ࣒࢘⁐ᾮ୰࡛ࡣ⎔≧ࡢ 4 㔞య[3]ࡀ୺
ᡂศ࡛࠶ࡿࡇ࡜ࡸࠊࡉࡽ࡟㧗࠸㓟⃰ᗘ࡟࠾࠸࡚ 3 㔞యࡀᏑᅾࡍࡿྍ⬟ᛶࡀሗ࿌ࡉࢀ࡚࠸ࡿ[4]ࠋ➹⪅ࡽࡣࠊᗈ⠊࡟ᡂศ⃰ᗘࢆኚ࠼ࡓሷ໬ Zr Ỉ⁐ᾮ࡟ࡘ࠸࡚ࠊᨺᑕග EXAFS ゎᯒࢆ⾜࠸ࠊࡇࢀࡽࡢ᪤ሗࢆᨭᣢࡍࡿ⤖ᯝࢆᚓࡓࠋࡉࡽ࡟ࠊప㓟⃰ᗘࡢ[Cl-]/[Zr]= 0.7 ⁐ᾮ࡛ࡣࠊ[Zr]ࡸ[H+]࡟ࡼࡽࡎࠊZr-Zr 㓄఩ᩘ࠾ࡼࡧ㓄఩㊥㞳ࡀ୍ᐃࡋ࡚࠾ࡾࠊ⁐Ꮡ໬Ꮫ✀ࡢᵓ㐀ࡀኚ໬ࡋ࡟ࡃ࠸ࡇ࡜ࢆ᪂ࡓ࡟Ⓨぢࡋࡓࠋࡲࡓࠊ[Cl-]/[Zr]ࢆኚ໬ࡉࡏࡓ⁐ᾮࢆᯫᶫ๣࡜ࡋ࡚ῧຍࡋࡓ࣏ࣜࣅࢽࣝ࢔ࣝࢥ࣮ࣝࡢ⪏Ỉᛶ࡟࠾࠸࡚ࠊᯫᶫᛶ⬟࡜⁐Ꮡᵓ㐀ࡢᅉᯝ㛵ಀࢆ⿬௜ࡅࡓ[5]ࠋ
[Cl-]/[Zr]= 0.7 ⁐ᾮࡀ㧗࠸ᛶ⬟ࢆⓎ᥹ࡍࡿࡇ࡜ࢆぢฟࡋࠊࡇࡢࡼ࠺࡟ࠊZr ⁐ᾮࡢᶵ⬟ࡣ Zr ໬Ꮫ✀ࡢ⁐Ꮡᵓ㐀࡟ᙉࡃ౫Ꮡࡍࡿࡓࡵࠊ✀ࠎZr ሷ࡟ࡘ࠸࡚ࠊᡂศ⃰ᗘ࡜⁐Ꮡᵓ㐀ࡢ㛵ಀࡢヲ⣽ࢆ▱ࡿࡇ࡜ࡀࠊZr ⁐ᾮࡢᶵ⬟ᨵⰋࡢࡓࡵ࡟ࡣ㔜せ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋሷ໬≀⁐ᾮ࡜୪ࡧ◪㓟ሷ࠾ࡼࡧ㐣ሷ⣲㓟ሷ⁐ᾮࡶ⏘ᴗୖࠊZr 〇ရࡢᇶᮏཎᩱ࡜ࡋ࡚㔜せ࡛࠶ࡿࠋZrཎᏊࡣ㓄఩Ꮚࢆཷᐜࡋࡸࡍ࠸ᛶ㉁ࢆᣢࡘࡇ࡜࠿ࡽࠊZr ⁐Ꮡ໬Ꮫ✀ࡢᵓ㐀ࡣ⁐Ꮡࡍࡿ㝜࢖࢜ࣥ✀ࠊ⃰ᗘ࡟ᙳ㡪ࡉࢀࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿ[6]ࠋࡋ࠿ࡋࠊሷ໬≀ྠᵝ࡟㐣ሷ⣲㓟ሷࠊ◪㓟ሷࡢ⁐Ꮡᵓ㐀ࡢヲ⣽࡞◊✲ࡣ࡞࠸ࠋᮏ◊✲ࡢ᭱⤊┠ᶆࡣࠊZr ໬Ꮫ✀ࡢ⁐Ꮡᵓ㐀ࡢ[Zr]ࠊ[H+]ࠊ㝜࢖࢜ࣥ✀ࠊ㝜࢖࢜ࣥ⃰ᗘ➼ࡢ໬Ꮫ⤌ᡂ౫Ꮡ࡜ᯫᶫᶵ⬟࡜ࡢ㛵ಀࢆゎ᫂ࡋࠊ⮬ᅾ࡞⁐Ꮡᵓ㐀ไᚚ࡟ࡼࡗ࡚ᯫᶫ๣࡜ࡋ࡚ඃࢀࡓ Zr ໬ྜ≀ࢆ㛤Ⓨࡍࡿࡇ࡜࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊ⁐Ꮡᵓ㐀ゎ᫂ࡢࡓࡵ࡟ࠊ[Zr]ࠊ[H+]ࠊ[NO3-]ࡲࡓࡣ[ClO4-]ࢆኚ࠼ࡓ◪㓟
Zr ࠾ࡼࡧ㐣ሷ⣲㓟 Zr ࡢ EXAFS ᵓ㐀ゎᯒࢆᐇ᪋ࡋࡓࠋᐇ㦂㸸 Ⅳ㓟ࢪࣝࢥࢽ࣒࢘㻔➨୍⛥ඖ⣲໬Ꮫᕤᴗ〇ࠊ⢊ᮎ≧ࠊZr㻔OH㻕a㻔CO3㻕b࣭nH2O㸪a§ 3.2㸪b§ 0.4㸪n§ 6.9㻕ࢆ◪㓟㻔SAJ 〇ࠊ≉⣭ࠊ60.8%㻕ࡲࡓࡣ㐣ሷ⣲㓟㻔SAJ 〇ࠊ≉⣭ࠊ70.5%㻕ࢆ⏝࠸࡚⁐ゎࡋࠊ⣧Ỉ࡛ᕼ㔘ࡋࠊ[Zr]ࠊ[H+]ࠊ[NO3-]ࡲࡓࡣ[ClO4-]ࢆኚ࠼ࡓ◪㓟 Zr ࠾ࡼࡧ㐣ሷ⣲㓟 Zr ⁐ᾮࢆᚓࡓࠋBL14B2 ࡟࠾࠸࡚ࠊ㏱
㐣ἲࢡ࢖ࢵࢡࢫ࢟ࣕࣥ࡟ࡼࡗ࡚ྛヨᩱࡢ Zr-K ྾཰➃ XAFS ࢫ࣌ࢡࢺࣝࢆ ᐃࡋࡓࠋ஧⤖ᬗศගჾ࡟
ࡣ Si㻔111㻕ࢆ౑⏝ࡋࡓࠋREX2000 ࠾ࡼࡧ FEFF6[7]ࢆ౑⏝ࡋ࡚ EXAFS ゎᯒࢆᐇ᪋ࡋࡓࠋ◪㓟ሷ⁐ᾮ࠾ࡼࡧ㐣ሷ⣲㓟ሷ⁐ᾮࡢ໬Ꮫ⤌ᡂࢆࡑࢀࡒࢀ⾲ 1 ࡟♧ࡍࠋ

⾲ 1. ◪㓟 Zr ࠾ࡼࡧ㐣ሷ⣲㓟 Zr ⁐ᾮࡢ໬Ꮫ⤌ᡂ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸 [Zr]= 1M ࡢ◪㓟Zr ࠾ࡼࡧ㐣ሷ⣲㓟Zr ⁐ᾮࡢEXAFS ᣺ືࡢࣇ࣮࢚ࣜኚ᥮ࢫ࣌ࢡࢺࣝࢆࡑࢀࡒࢀᅗ1ࠊ
2 ࡟♧ࡍࠋ඲࡚ࡢヨᩱ࡛ᅗ 1ࠊ2 ࡜ྠᵝࡢ 3㹼3.5ύࡢ➨஧ࣆ࣮ࢡࢆほ ࡋࡓࠋࡇࡢࣆ࣮ࢡࢆ Zr-Zr 㓄఩࡜௬ᐃࡋ࡚ࠊFEFF6 ࡛⌮ㄽィ⟬ࡋࡓ Zr-Zr 㓄఩㻔3.559ύ㻕ࡢᚋ᪉ᩓ஘ᙉᗘ࡜఩┦ࢩࣇࢺࢆ⏝࠸࡚ࣇ࢕ࢵࢺࡍࡿࡇ࡜࡛ Zr-Zr 㓄఩ᩘࠊ㓄఩㊥㞳ࢆồࡵࡓࠋ㻜㻝㻞㻟㻾㻌㻔䊅㻕㻠㻡㻢

ᅗ 1. ◪㓟 Zr ࡢ EXAFS ᣺ືࡢࣇ࣮࢚ࣜኚ᥮
ࢫ࣌ࢡࢺࣝ㻔 [Zr]= 1M㻕㼇㻯㼘㻻 㻠㻙㼉㻛㼇㼆㼞㼉 㼇㻯㼘㻻㻠㻙㼉 㻔㻹㻕㼇㻴㻗㼉㻔㻹㻕⣔ิ㻝㻜㻚㻣㻜㻚㻣㻜㻚㻜㻡㻥⣔ิ㻞㻝㻝㻜㻚㻝㻣⣔ิ㻟㻝㻚㻟㻝㻚㻟㻜㻚㻞㻡⣔ิ㻠㻞㻞㻜㻚㻤㻟⣔ิ㻡㻠㻠㻞㻚㻤⣔ิ㻢㻢㻢㻠㻚㻤䝣䞊䝸䜶ኚ᥮ᙉᗘࣇ࣮࢚ࣜኚ᥮ᙉᗘ䝣䞊䝸䜶ኚ᥮ᙉᗘࣇ࣮࢚ࣜኚ᥮ᙉᗘ㼇㻺㻻 㻟㼉㻛㼇㼆㼞㼉 㼇㻺㻻 㻟㼉㻔㻹㻕 㼇㻴㻗㼉 㻔㻹㻕⣔ิ㻝 㻜㻚㻣㻜㻚㻣㻜㻚㻜㻟㻤⣔ิ㻞 㻝㻝㻜㻚㻝㻡⣔ิ㻟 㻝㻚㻟㻝㻚㻟㻜㻚㻞㻡⣔ิ㻠 㻞㻞㻜㻚㻤㻡⣔ิ㻡
㻠㻠
㻞㻚㻤
⣔ิ㻢
㻢
㻢
㻠㻚㻤㻜㻝

㻞

㻟㻾㻌㻔䊅㻕

㻠㻡㻢

ᅗ 2. 㐣ሷ⣲㓟 Zr ࡢ EXAFS ᣺ືࡢࣇ࣮࢚ࣜ
ኚ᥮ࢫ࣌ࢡࢺࣝ㻔 [Zr]= 1M㻕◪㓟 Zr ࠾ࡼࡧ㐣ሷ⣲㓟 Zr ࡢ[Zr]ࠊ[NO3-]/[Zr]ࡲࡓࡣ[ClO4-]/[Zr]࡜ Zr-Zr 㓄఩ᩘ࠾ࡼࡧ㊥㞳ࡢ㛵ಀࢆࠊᅗ 3㹼6 ࡟♧ࡍࠋ[NO3-]/[Zr]࠾ࡼࡧ[ClO4-]/[Zr]= 0.7 ࡛ࡣࠊ[Zr]࡟ࡼࡗ࡚ Zr-Zr 㓄఩ᩘࠊ㊥㞳ࡀ࡯࡜ࢇ࡝ኚ໬ࡋ࡞࠿ࡗࡓ㻔ᅗ 3㹼6㻕ࠋ⁐Ꮡᵓ㐀ࡀኚ໬ࡋ࡟ࡃ࠸໬Ꮫ✀ࢆᚓࡿ᮲௳ࡀࡇࡢẚ࡛࠶ࡿ࡜≉ᐃࡉࢀࡓࡇ࡜ࡣ᪂ࡓ࡞Ⓨぢ࡛࠶ࡿࠋᯫᶫ๣࡟㝈ࡽࡎࠊᕤᴗⓗ࡟ Zr ⁐ᾮࡀ౑⏝ࡉࢀࡿሙྜࠊᕼ㔘ࡸ௚ࡢᮦᩱ࡜ࡢΰྜ
࡟ࡼࡗ࡚[Zr]ࠊ[H+]➼ࡀኚ໬ࡍࡿࡢ࡛ࠊ[Zr]ࠊ[H+]࡟౫Ꮡࡋ࡚⁐Ꮡᵓ㐀ࡀኚ໬ࡋ࡞࠸ࡇ࡜ࡣᯫᶫ➼ࡢᛂ⏝ᛶ⬟ࢆᏳᐃࡋ࡚Ⓨ᥹ࡍࡿࡓࡵ࡟᭷฼࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ

㼆㼞㻙㼆㼞㓄఩ᩘ㻡㻠㻟㻞㻝㻟㻚㻡㻥㻟㻚㻡㻤㻟㻚㻡㻣㻟㻚㻡㻢㻟㻚㻡㻡㻟㻚㻡㻠

㻜㻟㻚㻡㻟
㻜㻚㻝

㻝

㻝㻜㼇㻺㻻㻟㻙㼉㻌㻛㻌㼇㼆㼞㼉㻝㻜㻜㻜㻚㻝

ᅗ 3. ◪㓟 Zr ࡢ[Zr]ࠊ[NO3-]/[Zr]࡜ Zr-Zr
㓄఩ᩘࡢ㛵ಀ㻡㻠㻟㻞㻝㻝㼇㻺㻻㻟 㻙㼉㻌㻛㻌㼇㼆㼞㼉㻝㻜㻝㻜㻜ᅗ 4. ◪㓟 Zr ࡢ[Zr]ࠊ[NO3-]/[Zr]࡜ Zr-Zr㓄఩㊥㞳ࡢ㛵ಀ㼇㼆㼞㼉㻌㻩㻌㻜㻚㻜㻝㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻜㻡㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻝㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻡㻹㼇㼆㼞㼉㻌㻩㻌㻝㻚㻜㻹㼇㼆㼞㼉㻌㻩㻌㻞㻹㻟㻚㻢㻜㻟㻚㻡㻥㼆㼞㻙㼆㼞㓄఩㊥㞳㻌㻔䊅㻕㼇㼆㼞㼉㻌㻩㻌㻜㻚㻜㻝㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻜㻡㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻝㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻡㻹㼇㼆㼞㼉㻌㻩㻌㻝㻚㻜㻹㼇㼆㼞㼉㻌㻩㻌㻞㻹㻢㼆㼞㻙㼆㼞㓄఩ᩘ㼇㼆㼞㼉㻌㻩㻌㻜㻚㻜㻝㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻜㻡㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻝㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻡㻹㼇㼆㼞㼉㻌㻩㻌㻝㻚㻜㻹㼇㼆㼞㼉㻌㻩㻌㻞㻹㻟㻚㻢㻜㼆㼞㻙㼆㼞㓄఩㊥㞳㻌㻔䊅㻕㼇㼆㼞㼉㻌㻩㻌㻜㻚㻜㻝㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻜㻡㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻝㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻡㻹㼇㼆㼞㼉㻌㻩㻌㻝㻚㻜㻹㼇㼆㼞㼉㻌㻩㻌㻞㻹㻢㻟㻚㻡㻤㻟㻚㻡㻣㻟㻚㻡㻢㻟㻚㻡㻡㻟㻚㻡㻠㻟㻚㻡㻟㻜㻜㻚㻝㻝㻝㻜㼇㻯㼘㻻㻠㻙 㼉㻌㻛㻌㼇㼆㼞㼉㻝㻜㻜

ᅗ 5. 㐣ሷ⣲㓟 Zr ࡢ[Zr]ࠊ[ClO4-]/[Zr]࡜
Zr-Zr 㓄఩ᩘࡢ㛵ಀ㻜㻚㻝㻝㻝㻜㼇㻯㼘㻻㻠 㻙㼉㻌㻛㻌㼇㼆㼞㼉㻝㻜㻜ᅗ 6. 㐣ሷ⣲㓟 Zr ࡢ[Zr]ࠊ[ClO4-]/[Zr]࡜
Zr-Zr 㓄఩㊥㞳ࡢ㛵ಀᅗ 7㹼10 ࡟◪㓟 Zr ࠾ࡼࡧ㐣ሷ⣲㓟 Zr ࡢ[Zr]ࠊ[H+]࡜ Zr-Zr 㓄఩ᩘ࠾ࡼࡧ㓄఩㊥㞳ࡢ㛵ಀࢆ♧ࡍࠋ◪㓟ሷࠊ㐣ሷ⣲㓟ሷ࡜ࡶ࡟ࠊ[H+]ࡢቑຍ࡟క࠸ Zr-Zr 㓄఩ᩘࡀῶᑡࡍࡿഴྥࡣྠᵝ࡛࠶ࡗࡓࠋ㐣ሷ⣲㓟ሷࡣ[H+]> 1M ࡢ㡿ᇦ࡛ Zr-Zr 㓄఩ᩘ= 2ࠊ㓄㊥㞳= 3.56ύ࡟཰᮰ࡋࡓ㻔ᅗ 9ࠊ10㻕ࠋࡇࢀࡣࠊ࢜
࢟ࢩሷ໬ࢪࣝࢥࢽ࣒࢘㻔ZrOCl2࣭8H2O㻕ࡸ࢜࢟ࢩ㐣ሷ⣲㓟ࢪࣝࢥࢽ࣒࢘㻔ZrO㻔ClO4㻕2࣭8H2O㻕ࡢᵓᡂ༢఩࡛
࠶ࡿ⎔≧ 4 㔞య[3]ࡢ໬Ꮫ✀ࡀ୺ᡂศ࡛࠶ࡿࡓࡵ࡜⪃࠼ࡽࢀࡿࠋࡇࡢ⎔≧ 4 㔞యࡢ Zr-Zr 㓄఩ᩘࡣ 2 ࡛㓄఩㊥㞳ࡣ 3.559ύ࡛࠶ࡿࠋࡲࡓࠊᅗ 5ࠊ6 ࡟࠾࠸࡚ࠊ[Zr]= 2Mࠊ[ClO4-]/[Zr]= 2 ࡢ⁐ᾮࡢ Zr-Zr 㓄఩ᩘࡀ 2.0 ࡛ࠊ㓄఩㊥㞳ࡀ 3.560ύ࡛࠶ࡗࡓࡇ࡜ࡣࠊZrO(lO4㻕2࣭8H2O ࡢ[Zr]= 2M ⁐ᾮ࡛ࡣ⎔≧ 4 㔞యࡢᵓ㐀ࡀಖᣢࡉࢀࡿ࡜ࡍࡿ Camelia ࡽࡢㄽᩥ[8]࡜୍⮴ࡋ࡚࠸ࡿࠋ୍᪉ࠊ◪㓟ሷ࡛ࡣࠊྠࡌ[H+]> 1M ࡢ㡿ᇦ࡛ Zr-Zr 㓄఩ᩘ= 2㹼2.5 ࡟཰᮰ࡋࡓࡀࠊ㓄఩㊥㞳ࡣ[H+]ቑ
ຍ࡟కࡗ࡚ῶᑡࡋࡓ㻔ᅗ 7ࠊ8㻕ࠋ◪㓟 Zr ࡢ୍✀࡛࠶ࡿ Zr㻔OH㻕2㻔NO3㻕2࣭4.7H2O ࡢ⤖ᬗᵓ㐀ࢆᅗ 11 ࡟♧ࡍ[9]ࠋ⤖ᬗࡣᅗ 11 ࡟♧ࡍࣘࢽࢵࢺࡀ⧞ࡾ㏉ࡋ┤㙐≧࡟⤖ྜࡋࡓ㔜ྜయ࡟ࡼࡗ࡚ᵓᡂࡉࢀࡿࠋࡇࡢ㔜ྜయࡢ⌮ㄽ Zr-Zr 㓄఩ᩘࡣ 2 ࡛ࠊ㓄఩㊥㞳ࡣ 3.536ύ࡛࠶ࡿࠋᅗ 8 ࡟࠾࠸࡚ࠊ[Zr]= 0.1Mࠊ[H+]= 3.5M ࡢ⁐ᾮࡣࠊZr-Zr 㓄఩ᩘ= 2.0ࠊ㓄఩㊥㞳= 3.535ύ࡛࠶ࡗࡓࡇ࡜࠿ࡽࠊ◪㓟ሷ࡛ࡣࠊ[H+]ࡢቑຍ࡟కࡗ࡚ࠊ
ᅗ11ࡢ㔜ྜయ࡜ྠᵝࡢᵓ㐀ࡀᙧᡂࡉࢀࡿࡇ࡜ࡀ⪃࠼ࡽࢀࡿࠋᅗ12࡟◪㓟Zr࠾ࡼࡧ㐣ሷ⣲㓟Zrࡢ[NO3-]ࠊ
[ClO4 ]࡜ Debye-Waller ᅉᏊࡢ㛵ಀࢆ♧ࡍࠋ◪㓟 Zr ࡟࠾࠸࡚ Debye-Waller ᅉᏊࡣᴟᑠࢆᣢࡕࠊ㧗[NO3-]㡿ᇦ࡛ቑຍࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࡢ Debye-Waller ᅉᏊࡢᣲືࡶࠊ2 ✀㢮ࡢ Zr-Zr 㓄఩㊥㞳ࢆᣢࡘᅗ11 ࡢᵓ㐀ࡢ⏕ᡂࢆ♧၀ࡍࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋᅗ 13 ࡟ࠊFEFF6 ࢆ⏝࠸࡚⌮ㄽィ⟬ࡋࡓࠊᅗ 11 ୰ࡢ㔜ྜయࡢ 2 ✀ࡢ Zr-Zr 㓄఩㻔3.513ύࠊ3.559ύ㻕࠾ࡼࡧࡑࢀࡽࡢ Zr-Zr 㓄఩࡜ Zr㻔n㻕-N㻔n㻕-O7㻔n㻕-Zr㻔n㻕ࠊZr㻔n㻕-N㻔n㻕-O7㻔n㻕-N㻔n㻕-Zr㻔n㻕㻔 n= 1, 2, 3㻕⤒㊰ࡢᩓ஘࡟ࡼ
ࡿ EXAFS ᣺ືࢆ♧ࡍࠋࡇࡢከ㔜ᩓ஘⤒㊰ࡢཎᏊࡣ┤⥺ⓗ࡟㓄⨨ࡋ࡚࠾ࡾࠊ⤒㊰㛗ࡢ஧ศࡢ୍ࡀ Zr-Zr
㓄఩࡜ྠ⛬ᗘࡢ㊥㞳࡛࠶ࡿࡓࡵࠊEXAFS ᣺ື࡬ࡢᙳ㡪ࡀ኱ࡁ࠸࡜⪃࠼ࡽࢀࡿࠋᅗ 13 ࡟࠾࠸࡚ࠊከ㔜ᩓ஘ࡢᙳ㡪ࡀ࠶ࡿሙྜࡣ EXAFS ᣺ືࡢ᣺ᖜ࡜ k ቑຍ࡟క࠺ῶ⾶ࡀࡼࡾ኱ࡁࡃ࡞ࡗ࡚࠸ࡿࡇ࡜ࡀࢃ࠿
ࡿࠋ◪㓟 Zr ࡢ㧗[NO3-]㡿ᇦ࡟࠾ࡅࡿ Debye-Waller ᅉᏊࡢቑຍࡣࠊNO3-ࡢ㓄఩࡟ࡼࡿከ㔜ᩓ஘ࡀᙳ㡪ࡋ࡚࠸ࡿྍ⬟ᛶࡶ⪃࠼ࡽࢀࡿࠋ㼆㼞㻙㼆㼞㓄఩ᩘ㻡㻠㻟㻞㻝㻜㻝㻜㻙㻟㻝㻜㻙㻞㻜㻚㻝㻝㼇㼆㼞㼉㻌㻩㻌㻜㻚㻜㻝㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻜㻡㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻝㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻡㻹㼇㼆㼞㼉㻌㻩㻌㻝㻚㻜㻹㼇㼆㼞㼉㻌㻩㻌㻞㻹㻟㻚㻢㻜㻟㻚㻡㻥㼆㼞㻙㼆㼞㓄఩㊥㞳㻌㻔䊅㻕㼇㼆㼞㼉㻌㻩㻌㻜㻚㻜㻝㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻜㻡㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻝㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻡㻹㼇㼆㼞㼉㻌㻩㻌㻝㻚㻜㻹㼇㼆㼞㼉㻌㻩㻌㻞㻹㻢㻟㻚㻡㻤㻟㻚㻡㻣㻟㻚㻡㻢㻟㻚㻡㻡㻟㻚㻡㻠㻟㻚㻡㻟㻝㻜㻝㻜㻙㻟㻝㻜㻙㻞㻗㻝㻜㻡㻠㻟㻞㻝㼇㼆㼞㼉㻌㻩㻌㻜㻚㻜㻝㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻜㻡㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻝㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻡㻹㼇㼆㼞㼉㻌㻩㻌㻝㻚㻜㻹㼇㼆㼞㼉㻌㻩㻌㻞㻹㻟㻚㻢㻜㼆㼞㻙㼆㼞㓄఩㊥㞳㻌㻔䊅㻕㼇㼆㼞㼉㻌㻩㻌㻜㻚㻜㻝㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻜㻡㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻝㻹㼇㼆㼞㼉㻌㻩㻌㻜㻚㻡㻹㼇㼆㼞㼉㻌㻩㻌㻝㻚㻜㻹㼇㼆㼞㼉㻌㻩㻌㻞㻹㻢㼆㼞㻙㼆㼞㓄఩ᩘ㻝

ᅗ 8. ◪㓟 Zr ࡢ[Zr]ࠊ
[H+]࡜ Zr-Zr
㓄఩㊥㞳ࡢ㛵ಀᅗ 7. ◪㓟 Zr ࡢ[Zr]ࠊ[H+]࡜ Zr-Zr
㓄఩ᩘࡢ㛵ಀ

㻜㻜㻚㻝㼇㻴㻗㼉㻌㻔㻹㻕㼇㻴 㼉㻌㻔㻹㻕

㻟㻚㻡㻥㻟㻚㻡㻤
㻟㻚㻡㻣㻟㻚㻡㻢㻟㻚㻡㻡㻟㻚㻡㻠㻝㻜㻙㻟㻝㻜㻙㻞㻜㻚㻝㻝㻝㻜㼇㻴㻗㼉㻌㻔㻹㻕ᅗ 9. 㐣ሷ⣲㓟 Zr ࡢ[Zr]ࠊ[H+]࡜ Zr-Zr 㓄఩ᩘࡢ㛵ಀ㻟㻚㻡㻟㻝㻜㻙㻟㻝㻜㻙㻞㻜㻚㻝㻝㻝㻜㼇㻴㻗㼉㻌㻔㻹㻕ᅗ 10. 㐣ሷ⣲㓟 Zr ࡢ[Zr]ࠊ[H+]࡜ Zr-Zr 㓄఩㊥㞳ࡢ㛵ಀ㻰㼑㼎㼥㼑㻌㼃㼍㼘㼘㼑㼞㻌ᅉᏊ㻌㻔䊅㻕

3.513ύ
3.559ύ

㻜㻚㻝㻜◪㓟㼆㼞㻌㻌㻌㻌㻌㼇㼆㼞㼉㻩㻌㻜㻚㻝㻹㻜㻚㻜㻥◪㓟㼆㼞㻌㻌㻌㻌㻌㻌㼇㼆㼞㼉㻩㻌㻝㻹㻜㻚㻜㻤㐣ሷ⣲㓟㼆㼞㼇㼆㼞㼉㻩㻌㻜㻚㻝㻹㻜㻚㻜㻣㐣ሷ⣲㓟㼆㼞㼇㼆㼞㼉㻩㻌㻝㻹㻜㻚㻜㻢㻜㻚㻜㻡㻜㻚㻜㻠㻜㻚㻜㻝㻜㻚㻝㻝㻝㻜㼇㻺㻻㻟㻙㼉㻌㼛㼞㻌㼇㻯㼘㻻㻠㻙㼉㻌㻌㻔㻹㻕ᅗ 11. ◪㓟ࢪࣝࢥࢽ࣒࢘ Zr㻔OH㻕2㻔NO3㻕2࣭4.7H2O
୰ࡢ㔜ྜయࡢᵓ㐀ᅗ 12. ◪㓟 Zr ࠾ࡼࡧ㐣ሷ⣲㓟 Zr ࡢ[NO3-]ࠊ
[ClO4-]࡜ Debye-Waller ᅉᏊࡢ㛵ಀ

ᅗ 13. ◪㓟ࢪࣝࢥࢽ࣒࢘ Zr㻔OH㻕2㻔NO3㻕2࣭4.7H2O ୰ࡢ Zr-Zr 㓄఩࠾ࡼࡧ NO3-ࢆ௓ࡋࡓከ㔜ᩓ஘⤒㊰࡟ࡼࡿ⌮ㄽィ⟬
EXAFS ᣺ື㻔ཎᏊࡢ㆑ู࠾ࡼࡧ㓄⨨ࡣᅗ 11 ࡟♧ࡋࡓࠋ㻕௒ᚋࡢㄢ㢟㸸
Zr-O 㓄఩࡜᥎ᐃࡉࢀࡿ➨୍㓄఩ᅪࡢゎᯒࡸ௚ࡢศᯒᡭἲ࡜ࡢ㐃ಀ࡟ࡼࡾ⁐Ꮡ໬Ꮫ✀ࡢࣔࢹࣝᵓ㐀ࢆࡼࡾලయ໬ࡍࡿࠋࡲࡓࠊᅗ 1ࠊ2 ࡢࣇ࣮࢚ࣜኚ᥮࡛ぢࡽࢀࡿ 5ύᙅࡢ㐲࠸ Zr-Zr 㓄఩ࢆゎᯒࡍࡿࡇ࡜࡛ࠊࡉࡽ࡟⁐Ꮡᵓ㐀ࣔࢹࣝࢆලయ໬࡛ࡁࡿྍ⬟ᛶࡀ࠶ࡿࠋ⏘ᴗ฼⏝ୖࡣ⁐Ꮡᵓ㐀࡜ᯫᶫᛶ⬟ࠊࡑࡢ௚ᶵ⬟࡜ࡢ┦㛵ࢆ᫂ࡽ࠿࡟ࡋࠊᛂ⏝ᶵ⬟ᨵⰋࡢࡓࡵ࡟ᚲせ࡞⁐Ꮡᵓ㐀ࢆ≉ᐃࡍࡿࡇ࡜ࡀㄢ㢟࡜࡞ࡿࠋZr ⁐Ꮡ໬Ꮫ✀ࡢ㔜ྜᵓ㐀ࡣ࢚࣮ࢪࣥࢢຠᯝ࡟ࡼࡗ࡚ኚ໬ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠾ࡾ[4]ࠊࡑࡢᖹ⾮฿㐩᫬㛫࡜཯ᛂ㏿ᗘࢆᢕᥱࡍࡿࡇ࡜ࡶᕤᴗⓗ࡟㔜せ࡛࠶ࡿࠋཧ⪃ᩥ⊩㸸[1] George M. Muha, et. al., J. Chem. Phys., 33, 194 㻔1960㻕
[2] A. Singhal, et. al., J. Am. Chem. Soc., 118, 11529 㻔1996㻕
[3] Thomas C. W. Mak, Can. J. Chem., 46, 3491 㻔1968㻕
[4] ᑠᕝಙ᫂ࡽ, ศᯒ໬Ꮫ, 35, 785 㻔1986㻕
[5] 㧗ᓮྐ㐍ࡽ, ᪥ᮏࢭ࣑ࣛࢵࢡࢫ༠఍ 2010 ᖺ఍ㅮ₇ண✏㞟, 80 㻔2010㻕
[6] A. Clearfield, J. Mater. Res., 5, 161 㻔1990㻕
[7] S. I. Zabinsky, et. al., J. Phys. Rev. B, 52, 2995㻌㻔1995㻕
[8] Camelia Hagfeldt, et. al., Dalton Trans., 2142 㻔2004㻕
[9] P. Bénard, et. al., J. Sol. St. Chem. 94, 27 㻔1991㻕