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ᣧⒷ↰ᄢቇᄢቇ㒮 వㅴℂᎿቇ⎇ⓥ⑼

ඳ჻⺰ᢥክᩏႎ๔ᦠ

⺰ ᢥ 㗴 ⋡

Nanoscale Analysis on the Reaction Mechanism of Reductants for Electroless Deposition Processes using

Surface Enhanced Raman Spectroscopy

ή㔚⸃ᨆ಴ࡊࡠ࠮ࠬߦ߅ߌࠆㆶర೷ߩ෻ᔕᯏ᭴ߦኻߔ ࠆ

⴫㕙Ⴧᒝ࡜ࡑࡦಽశᴺࠍ↪޿ߚ࠽ࡁࠬࠤ࡯࡞⸃ᨆ

↳ ⺧ ⠪

Bin JIANG

ྰ ᕀ

࠽ࡁℂᎿቇኾ᡹ ࠽ࡁᯏ⢻⴫㕙ൻቇ⎇ⓥ

㧞 㧜 㧝 㧟 ᐕ 㧝 㧜 ᦬

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ή 㔚 ⸃ ᨆ ಴ ࡊ ࡠ ࠮ ࠬ ߪ ᓥ ᧪ ߆ ࠄ ⒳ ޘ ߩ ⭯ ⤑ ᒻ ᚑ ߦ ↪ ޿ ࠄ ࠇ ߡ ߅ ࠅ 㧘 ߹ ߚ ㄭ ᐕ ߢ ߪ ᭽ ޘ ߥ ࠽ ࡁ ᭴ ㅧ ૕ ࡮ ࠺ ࡃ ࠗ ࠬ ᒻ ᚑ ߩ ߚ ߼ ߩ ၮ ⋚ ᛛ ⴚ ߣ ߒ ߡ ᵈ ⋡ ߐ ࠇ 㧘 ࠃ ࠅ 㜞 ᐲ ߥ ᯏ ⢻ ⊒ ⃻ ࠍ ታ ⃻ ߔ ࠆ ߚ ߼ 㧘 ࡊ ࡠ ࠮ ࠬ ߩ ৻ ጀ ߩ ♖ ኒ ൻ ߇ ᳞ ߼ ࠄ ࠇ ߡ

޿ ࠆ 㧚 ߘ ߩ ߚ ߼ ߦ ߪ ࡊ ࡠ ࠮ ࠬ ߦ ߅ ߌ ࠆ ෻ ᔕ ࡔ ࠞ ࠾ ࠭ ࡓ ߩ ⹦ ⚦ ߥ ℂ ⸃ ߇ ᕆ ോ ߣ ߥ ߞ ߡ ޿ ࠆ ߇ 㧘 ࿕ ᶧ ⇇ 㕙 ෻ ᔕ ߢ ޽ ࠆ ᧄ ࡊ ࡠ ࠮ ࠬ ߩ ࡔ ࠞ ࠾ ࠭ ࡓ ߦ ߪ ਇ ᣿ ὐ ߇ ᧂ ߛ ᄙ ޿ ߩ ߇ ⃻ ⁁ ߢ ޽ ࠆ 㧚 ߘ ߩ ⸃ ᨆ ߦ ߪ ᓥ ᧪ ࠃ ࠅ 㔚 ᳇ ൻ ቇ ⊛ ߥ ᚻ ᴺ ߿ ⿛ ᩏ ࡊ ࡠ

࡯ ࡉ 㗼 ᓸ ㏜ ᴺ ߥ ߤ ߇ ↪ ࠄ ࠇ ߡ ޿ ࠆ ߇ 㧘 ㆶ ర ೷ ߿ ᷝ ട ೷ ߥ ߤ 㧘 ෻ ᔕ ߦ 㑐 ਈ ߔ ࠆ

⒳ ޘ ߩ ᓸ ㊂ ߥ ൻ ቇ ⒳ ߩ ᜼ േ ࠍ ⋥ ធ ߘ ߩ ႐ ⷰ ኤ ߔ ࠆ ߩ ߪ ࿎ 㔍 ߢ ޽ ࠆ ߎ ߣ ߆ ࠄ 㧘

᦭ ല ߥ ⸃ ᨆ ᚻ Ბ ߇ ᦸ ߹ ࠇ ߡ ޿ ࠆ 㧚

ߎ ߩ ࠃ ߁ ߥ ⁁ ᴫ ਅ 㧘 ᧄ ⺰ ᢥ ߢ ߪ 㧘 ή 㔚 ⸃ ᨆ ಴ ෻ ᔕ ♽ ߦ ߅ ޿ ߡ 㧘 ․ ߦ ၮ ᧼ ⴫ 㕙 ߦ ߅ ߌ ࠆ ㆶ ర ೷ ߿ ᷝ ട ೷ ߥ ߤ ߩ ᜼ േ ࠍ ⹦ ⚦ ߦ ⸃ ᣿ ߔ ࠆ ߚ ߼ 㧘 㗼 ᓸ ဳ ⴫ 㕙 Ⴧ ᒝ ࡜ ࡑ ࡦ ᢔ ੂ ಽ శ ᴺ 㧔S E R S㧕 ࠍ ၮ ߦ ߒ ߚ ᣂ ߒ ޿ ߘ ߩ ႐ ᚻ ᴺ ߩ ឭ ᩺ ߣ 㧘 ߘ ߩ

᦭ ല ᕈ ߩ ᬌ ⸽ ࠍ ⴕ ߞ ߚ ⚿ ᨐ ߦ ߟ ޿ ߡ ߹ ߣ ߼ ߡ ㅀ ߴ ࠄ ࠇ ߡ ޿ ࠆ 㧚

ᧄ ⺰ ᢥ ߪ ో 㧡 ┨ ߆ ࠄ ᭴ ᚑ ߐ ࠇ ߡ ޿ ࠆ 㧚 ╙ 㧝 ┨ ߦ ߪ 㧘 ߹ ߕ ᧄ ⎇ ⓥ ߩ ⢛ ᥊ ߣ ߥ ࠆ ή 㔚 ⸃ ᨆ ಴ ࡊ ࡠ ࠮ ࠬ ߩ ෻ ᔕ ࡔ ࠞ ࠾ ࠭ ࡓ ߦ 㑐 ߔ ࠆ ᓥ ᧪ ߩ ታ 㛎 ⊛ ࡮ ℂ ⺰ ⊛ ᬌ ⸛

଀ ߇ ᭎ ⷰ ߐ ࠇ ࠆ ߣ ߣ ߽ ߦ ᧂ ⸃ ᣿ ߩ ⺖ 㗴 ߇ ␜ ߐ ࠇ 㧘 ᧄ ⎇ ⓥ ߩ ૏ ⟎ ߠ ߌ ߇ ߥ ߐ ࠇ ߡ ޿ ࠆ 㧚 ߹ ߚ ᧄ ⎇ ⓥ ߢ ㆡ ↪ ߒ ߚ ⸃ ᨆ ᚻ ᴺ ߩ ၮ ߣ ߥ ࠆ ࡊ ࡜ ࠭ ࡕ ࡦ ࠕ ࡦ ࠹ ࠽ ࠍ ↪

޿ ߚ S E R S ⸃ ᨆ ᴺ ߦ ߟ ޿ ߡ 㧘 ේ ℂ ߿ ߎ ࠇ ߹ ߢ ߦ ㅴ ߼ ࠄ ࠇ ߡ ߈ ߚ ᬌ ⸛ ߩ ⚻ ✲ ߥ ߤ ߇ ߹ ߣ ߼ ࠄ ࠇ ߡ ޿ ࠆ 㧚

╙ 㧞 ┨ ߢ ߪ ᧄ ⎇ ⓥ ߦ ߡ ⏕ ┙ ߒ ߚ ᣂ ⷙ ߥ ⸃ ᨆ ᚻ ᴺ ߦ ߟ ޿ ߡ ᬌ ⸛ ߒ ߚ ⚿ ᨐ ߇ ߹ ߣ ߼ ߡ ㅀ ߴ ࠄ ࠇ ߡ ޿ ࠆ 㧚S E R S ߦ ߅ ߌ ࠆ ⴫ 㕙 Ⴧ ᒝ ല ᨐ ߪ 㧘A g ߥ ߤ ․ ቯ ߩ ㊄ ዻ

⴫ 㕙 ߦ ච 㨪 ⊖ ࠽ ࡁ ࡔ ࡯ ࠻ ࡞ ࠝ ࡯ ࠳ ࡯ ߩ ᓸ ⚦ ಳ ಲ ᭴ ㅧ ߇ ሽ ࿷ ߔ ࠆ ႐ ว 㧘 ߘ ߩ ᒻ

⁁ ߦ ↱ ᧪ ߔ ࠆ ࡊ ࡜ ࠭ ࡕ ࡦ ౒ 㡆 ല ᨐ ߦ ࠃ ࠅ 㧘 ᓧ ࠄ ࠇ ࠆ ࡜ ࡑ ࡦ ࠪ ࠣ ࠽ ࡞ ߇ ᢙ ⊖ 㨪 ᢙ ජ ୚ Ⴧ ᒝ ߐ ࠇ ࠆ ߽ ߩ ߢ ޽ ࠆ 㧚 ߘ ߩ ല ᨐ ࠍ ࠃ ࠅ 㜞 ߼ ࠆ ߚ ߼ 㧘 ᓸ ☸ ሶ ࠍ ⴫ 㕙 ߦ ⷙ ೣ ⊛ ߦ ㈩ ೉ ᒻ ᚑ ߔ ࠆ ߥ ߤ ߩ ⹜ ߺ ߇ ߥ ߐ ࠇ ߡ ޿ ࠆ ߇ 㧘 ᧄ ⎇ ⓥ ߢ ߪ 㧘 ౉ ኿ ࡟ ࡯

ࠩ ࡯ శ ߩ ᵄ 㐳 ߦ ᔕ ߓ ߚ ࠨ ࠗ ࠭ ߩ ห ᔃ ౞ ⁁ ߩ ⷙ ೣ ᭴ ㅧ ߩ ᒻ ᚑ ߦ ࠃ ࠅ ↢ ߓ ࠆ વ ᠞

ဳ ࡊ ࡜ ࠭ ࡕ ࡦ Ⴧ ᒝ ല ᨐ ࠍ ೑ ↪ ߒ 㧘 ߘ ߩ ᭴ ㅧ ૕ ߩ ਛ ᔃ ઃ ㄭ ߦ ᓥ ᧪ ဳ ࠃ ࠅ ߐ ࠄ ߦ ᢙ ජ ୚ ߩ 㜞 ޿ Ⴧ ᒝ ല ᨐ ߇ ᓧ ࠄ ࠇ ࠆ ޟ ࡊ ࡜ ࠭ ࡕ ࡦ ࠕ ࡦ ࠹ ࠽ ޠ ࠍ ↪ ޿ ߡ ޿ ࠆ 㧚 ߎ ߩ ࡊ ࡜ ࠭ ࡕ ࡦ ࠕ ࡦ ࠹ ࠽ ߩ ㆡ ↪ ߪ 㧘 Ⴧ ᒝ ല ᨐ ߩ 㜞 ޿ ㊄ ዻ ⒳ ߢ ޽ ࠆ A g ࠍ ↪ ޿ ߚ

଀ ߇ ႎ ๔ ߐ ࠇ ߡ ޿ ࠆ ߇ 㧘 ή 㔚 ⸃ ᨆ ಴ ෻ ᔕ ♽ ߩ ⸃ ᨆ ߣ ޿ ߁ ⷰ ὐ ߆ ࠄ ߪ 㧘 ห ♽ ߦ ਥ ߦ ↪ ޿ ࠄ ࠇ ߡ ޿ ࠆ C u ߅ ࠃ ߮ N i ߥ ߤ 㧘A g ߦ Ყ セ ߒ ߡ Ⴧ ᒝ ല ᨐ ߩ ૐ ޿ ㊄ ዻ

⒳ ߩ ㆡ ↪ ࠍ ⹜ ߺ ࠆ ᔅ ⷐ ߇ ޽ ࠆ 㧚 ߘ ߎ ߢ ᧄ ⎇ ⓥ ߢ ߪ ห ᔃ ౞ ⁁ ߩ ᭴ ㅧ ૕ ࠍ U V ࠽ ࡁ ࠗ ࡦ ࡊ ࡝ ࡦ ࠻ ᴺ ࠍ ↪ ޿ ߡ ᒻ ᚑ ߒ ߚ ᓟ C u޽ ࠆ ޿ ߪ N iߢ ⵍ ⷒ ߔ ࠆ ߎ ߣ ߦ ࠃ ࠅ 㧘 㜞 ♖ ᐲ ߦ ࡊ ࡜ ࠭ ࡕ ࡦ ࠕ ࡦ ࠹ ࠽ ࠍ ᒻ ᚑ ߢ ߈ ࠆ ࡊ ࡠ ࠮ ࠬ ࠍ ⏕ ┙ ߒ ߡ ޿ ࠆ 㧚 ߐ ࠄ ߦ ߎ ࠇ ࠍ ၮ ᧼ ߣ ߔ ࠆ 㔚 ᳇ ൻ ቇ ෻ ᔕ ࠮ ࡞ ࠍ ᭴ ▽ ߒ 㧘 ߎ ߩ ࠮ ࡞ ࠍ 㜞 ߐ ᣇ ะ ߦ ࠨ ࡉ ࠽ ࡁ ࡔ ࡯ ࠻ ࡞ ߩ ಽ ⸃ ⢻ ߢ 㜞 ♖ ᐲ 㚟 േ ߐ ߖ ࠆ ᯏ ᭴ ߣ ⚵ ߺ ว ࠊ ߖ 㧘 ᨆ ಴ ෻ ᔕ ߩ ⿠ ߎ ߞ ߡ ޿ ࠆ ၮ ᧼ ߔ ߥ ࠊ ߜ ࡊ ࡜ ࠭ ࡕ ࡦ ࠕ ࡦ ࠹ ࠽ ⴫ 㕙 ㄭ ற ߩ ߺ ߦ ὶ ὐ ࠍ ⛉ ߞ ߚ ⸃ ᨆ ߇ น ⢻ ߥ ࠪ ࠬ ࠹ ࡓ ࠍ ᣂ ߚ ߦ ᭴ ▽ ߒ ߚ 㧚⛯ ޿ ߡ ߎ ߩ ࠪ ࠬ ࠹ ࡓ ߩ ᦭ ല ᕈ ߦ ߟ ޿ ߡ 㧘

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S E R S ߦ ࠃ ࠆ Ⴧ ᒝ ല ᨐ ࠍ ↪ ޿ ߥ ޿ ㅢ Ᏹ ߩ ࡜ ࡑ ࡦ ᷹ ቯ ߣ ߩ Ყ セ ߆ ࠄ ᬌ ⸽ ߒ ߡ ޿ ࠆ 㧚 ή 㔚 ⸃ ᨆ ಴ ᴺ ߦ ㆡ ↪ ߐ ࠇ ࠆ ㆶ ర ೷ ߢ ޽ ࠆ ࡅ ࠼ ࡜ ࠫ ࡦ ࠍ ኻ ⽎ ߦ 㧘 ߹ ߕ Ớ ᐲ 5 . 0 m o l / L ߩ ᳓ ṁ ᶧ ߦ ߡ ᷹ ቯ ࠍ ⴕ ߞ ߚ ߣ ߎ ࠈ 㧘ㅢ Ᏹ ߩ ᚻ ᴺ ߢ ߽ ච ಽ ߥ ᒝ ᐲ ߩ ࠬ ࡍ ࠢ ࠻ ࡞ ߇ ᓧ ࠄ ࠇ ߚ 㧚 ߎ ࠇ ߪ ࡃ ࡞ ࠢ ṁ ᶧ ਛ ߩ ಽ ሶ ߦ ↱ ᧪ ߔ ࠆ ߽ ߩ ߢ ޽ ࠆ ߇ 㧘 1 0 0 m m o l / L ߣ ޿ ߁ ૐ Ớ ᐲ ߩ ṁ ᶧ ߩ ႐ ว 㧘ࠬ ࡍ ࠢ ࠻ ࡞ ߪ ᓧ ࠄ ࠇ ߥ ߆ ߞ ߚ 㧚৻ ᣇ 㧘 ߎ ߩ Ớ ᐲ ߦ ߅ ޿ ߡ ߽ ࡊ ࡜ ࠭ ࡕ ࡦ ࠕ ࡦ ࠹ ࠽ ࠍ ၮ ᧼ ߦ ↪ ޿ ߚ ႐ ว ߦ ߪ ᣿ ⍎ ߥ ࠬ ࡍ

ࠢ ࠻ ࡞ ߇ ᓧ ࠄ ࠇ 㧘 ߹ ߚ ၮ ᧼ ⴫ 㕙 ߣ ࡅ ࠼ ࡜ ࠫ ࡦ ߣ ߩ ⚿ ว ߩ ᒻ ᚑ ߦ ↱ ᧪ ߔ ࠆ ࡇ ࡯

ࠢ ߽ ⏕ ⹺ ߐ ࠇ ߚ 㧚ߐ ࠄ ߦ 㜞 ߐ ᣇ ะ ࠍ 0 . 5 n m ࠬ ࠹ ࠶ ࡊ ߢ ᄌ ൻ ߐ ߖ ߥ ߇ ࠄ ⸘ ᷹ ࠍ ⴕ ߁ ߎ ߣ ߦ ࠃ ࠅ 㧘 ߎ ߩ ࠃ ߁ ߥ ࠬ ࡍ ࠢ ࠻ ࡞ ߪ ၮ ᧼ ⴫ 㕙 ㄭ ற ߦ ὶ ὐ ߇ ว ࠊ ߖ ࠄ ࠇ ߡ ޿ ࠆ ႐ ว ߩ ߺ ᓧ ࠄ ࠇ ࠆ ߎ ߣ ࠍ ⏕ ⹺ ߒ ߚ 㧚 ߎ ࠇ ࠄ ߩ ⚿ ᨐ ߆ ࠄ 㧘 ࡊ ࡜ ࠭ ࡕ ࡦ ࠕ ࡦ ࠹ ࠽ ࠍ ㆡ ↪ ߔ ࠆ ߎ ߣ ߦ ࠃ ࠅ 㧘 ၮ ᧼ ⴫ 㕙 ߦ ሽ ࿷ ߔ ࠆ ᓸ ㊂ ߥ ಽ ሶ ⒳ ߩ ⁁ ᘒ ࠍ 㧘 ࡃ ࡞ ࠢ ṁ ᶧ ਛ ߦ ሽ ࿷ ߔ ࠆ ห ⒳ ಽ ሶ ߩ ᓇ 㗀 ߥ ߊ ߘ ߩ ႐ ⷰ ኤ ߢ ߈ ࠆ ߎ ߣ ࠍ ᣿ ࠄ ߆ ߣ ߒ ߚ 㧚 ߐ ࠄ ߦ ၮ ᧼ ⴫ 㕙 ㊄ ዻ ߣ ߒ ߡ 㧘A g ߩ ߺ ߢ ߥ ߊ C u ߦ ߅ ޿ ߡ ߽ ࠬ ࡍ ࠢ ࠻

࡞ ߇ ᓧ ࠄ ࠇ ࠆ ߎ ߣ ࠍ ⏕ ⹺ ߒ ߡ ޿ ࠆ 㧚 ߎ ߩ ࠃ ߁ ߦ 㧘 ᧄ ⎇ ⓥ ߢ ᣂ ߚ ߦ ⏕ ┙ ߒ ߚ ᚻ ᴺ ߪ 㧘ή 㔚 ⸃ ᨆ ಴ ෻ ᔕ ߩ ߘ ߩ ႐ ⷰ ኤ ߇ น ⢻ ߥ ᣂ ߚ ߥ ᚻ ᴺ ߣ ߒ ߡ ᣂ ⷙ ᕈ ߽ 㜞 ߊ 㧘 ߐ ࠄ ߦ 㧘 ᓥ ᧪ ဳ ߩ ᚻ ᴺ ߢ ߪ ࿎ 㔍 ߢ ޽ ߞ ߚ ⒳ ޘ ߩ ࿕ ᶧ ⇇ 㕙 ෻ ᔕ ߩ ⸃ ᨆ ߳ ߩ ㆡ ↪

߽ น ⢻ ߥ 㧘 ᭂ ߼ ߡ ᦭ ല ߥ ߽ ߩ ߣ ߒ ߡ ⹏ ଔ ߢ ߈ ࠆ 㧚

╙ 㧟 ┨ ߅ ࠃ ߮ ╙ 㧠 ┨ ߦ ߅ ޿ ߡ ߪ 㧘 ਄ ⸥ ߩ ᬌ ⸛ ߢ ᓧ ࠄ ࠇ ߚ ᚻ ᴺ ߩ ታ 㓙 ߩ ή 㔚

⸃ ᨆ ಴ ࡊ ࡠ ࠮ ࠬ ߩ ⸃ ᨆ ߳ ߩ ㆡ ↪ ࠍ ⹜ ߺ ߚ ⚿ ᨐ ߦ ߟ ޿ ߡ ㅀ ߴ ߡ ޿ ࠆ 㧚 ߹ ߕ ╙ 㧟

┨ ߢ ߪ 㧘C u ၮ ᧼ ߦ ኻ ߒ ࡅ ࠼ ࡜ ࠫ ࡦ ߣ ࡎ ࠬ ࡈ ࠖ ࡦ ㉄ ߩ ੑ ⒳ ߩ ㆶ ర ೷ ࠍ ↪ ޿ ߚ ႐ ว ߩ ਔ ⠪ ߩ ⋧ ੕ ૞ ↪ ߩ ⸃ ᨆ ࠍ ⹜ ߺ ߡ ޿ ࠆ 㧚 ߎ ߩ ♽ ߪ 㧘 ု ⋥ ⏛ ᳇ ⇣ ᣇ ᕈ ࠍ ᦭ ߔ ࠆ ή 㔚 ⸃ C o N i P⭯ ⤑ ࠍ ᒻ ᚑ ߔ ࠆ ߚ ߼ ߦ( 111 )㈩ ะ ߒ ߚ C uਅ ࿾ ࠍ ㆡ ↪ ߒ ⚿ ᥏

㈩ ะ ࠍ ೙ ᓮ ߔ ࠆ 㓙 㧘 ㆶ ర ೷ ߦ ↪ ޿ ࠄ ࠇ ߡ ޿ ࠆ ࡎ ࠬ ࡈ ࠖ ࡦ ㉄ ߦ ኻ ߒ C u ⴫ 㕙 ߇

⸅ ᇦ ᵴ ᕈ ࠍ ␜ ߐ ߥ ޿ ߚ ߼ ෻ ᔕ ߖ ߕ 㧘 ᓥ ߞ ߡ ㊄ ዻ ᨆ ಴ ߇ ⿠ ߎ ࠄ ߥ ޿ ߣ ޿ ߁ ໧ 㗴 ࠍ 㧘C u ⴫ 㕙 ߦ ߅ ޿ ߡ ෻ ᔕ ᵴ ᕈ ࠍ ␜ ߔ ࡅ ࠼ ࡜ ࠫ ࡦ ߩ ᷝ ട ߦ ࠃ ࠅ ⸃ ᳿ ߒ ߚ ߽ ߩ ߢ ޽ ࠆ 㧚 ߎ ߩ ♽ ߦ ߅ ޿ ߡ ߪ 㧘 ੑ ⒳ ߩ ㆶ ర ೷ ࠍ න ⁛ ޽ ࠆ ޿ ߪ ᷙ ว ߒ ߚ ႐ ว ߩ ㇱ ಽ ಽ ᭂ ᦛ ✢ ߩ ⸃ ᨆ ߆ ࠄ 㧘 ࡎ ࠬ ࡈ ࠖ ࡦ ㉄ ߩ ౒ ሽ ߦ ࠃ ࠅ ࡅ ࠼ ࡜ ࠫ ࡦ ߩ C u ⴫ 㕙 ߢ ߩ ෻ ᔕ ߇ ଦ ㅴ ߐ ࠇ ࠆ ߎ ߣ ߇ ␜ ໂ ߐ ࠇ ߡ ޿ ࠆ ߇ 㧘 ߘ ߩ ࡔ ࠞ ࠾ ࠭ ࡓ ߪ ਇ ᣿ ߢ ޽ ߞ ߚ 㧚 ߘ ߎ ߢ 㧘 ਄ ⸥ ߩ ᬌ ⸛ ߢ ᓧ ࠄ ࠇ ߚ ᚻ ᴺ ࠍ ߎ ߩ ♽ ߩ ⸃ ᨆ ߦ ㆡ ↪ ߒ ߚ 㧚 ߘ ߩ ⚿ ᨐ 㧘ࡎ ࠬ ࡈ ࠖ ࡦ ㉄ ࠍ න ⁛ ᷝ ട ߒ ߚ ႐ ว 㧘਄ ㅀ ߩ ࡅ ࠼ ࡜ ࠫ ࡦ ߩ ႐ ว ߣ ߪ ⇣ ߥ ࠅ 㧘 C u ၮ ᧼ ߣ ߩ ⚿ ว ᒻ ᚑ ࠍ ␜ ໂ ߔ ࠆ ࡇ ࡯ ࠢ ߪ ⹺ ߼ ࠄ ࠇ ߕ 㧘 ಽ ሶ ౝ ⚿ ว ߦ ↱ ᧪ ߔ ࠆ ࡇ ࡯ ࠢ ߩ ߺ ߇ ⏕ ⹺ ߐ ࠇ ߚ 㧚 ߎ ߩ ߎ ߣ ߪ 㧘 ࡎ ࠬ ࡈ ࠖ ࡦ ㉄ ߪ C u ၮ ᧼ ⴫ 㕙 ㄭ ற ߦ ሽ ࿷ ߒ ߡ ޿ ࠆ ߽ ߩ ߩ 㧘 ၮ ᧼ ߣ ߩ ൻ ቇ ⊛ ߥ ⋧ ੕ ૞ ↪ ߪ ␜ ߐ ߥ ޿ ߎ ߣ ࠍ ␜ ໂ ߒ ߡ ޿ ࠆ 㧚 ߎ ࠇ ߪ 㧘 ਄ ㅀ ߩ ࠃ ߁ ߦ 㧘C u ⴫ 㕙 ߇ ࡎ ࠬ ࡈ ࠖ ࡦ ㉄ ߩ ෻ ᔕ ߦ ኻ ߒ ਇ ᵴ ᕈ ߢ ޽ ࠆ ߎ ߣ ߣ ৻ ⥌ ߔ ࠆ 㧚 ৻ ᣇ 㧘 ੑ ⒳ ߩ ㆶ ర ೷ ࠍ ᷙ ว ߒ ߚ ♽ ߦ ߅ ޿ ߡ ߪ 㧘 ࡅ

࠼ ࡜ ࠫ ࡦ ↱ ᧪ ߩ ࡇ ࡯ ࠢ ߦ ࠪ ࡈ ࠻ ߇ ⹺ ߼ ࠄ ࠇ ߚ 㧚 ߎ ߩ ὐ ߦ ߟ ޿ ߡ 㧘 ኒ ᐲ ᳢ 㑐 ᢙ ᴺ ࠍ ↪ ޿ ߚ ℂ ⺰ ⸘ ▚ ߆ ࠄ ࠬ ࡍ ࠢ ࠻ ࡞ ߅ ࠃ ߮ ߘ ߩ ࠪ ࡈ ࠻ ࠍ ੍ ᷹ ߒ 㧘 ᓧ ࠄ ࠇ ߚ ࠬ ࡍ ࠢ ࠻ ࡞ ߣ ߩ Ყ セ ᬌ ⸛ ࠍ ⴕ ߞ ߚ 㧚 ߘ ߩ ⚿ ᨐ 㧘 ࡅ ࠼ ࡜ ࠫ ࡦ ಽ ሶ ౝ ߩ ᳓ ⚛ ߣ ࡎ ࠬ

(4)

3

ࡈ ࠖ ࡦ ㉄ ಽ ሶ ౝ ߩ ㉄ ⚛ ߇ ⋧ ੕ ૞ ↪ ߒ 㧘଀ ߃ ߫ C u -ࡅ ࠼ ࡜ ࠫ ࡦ-ࡎ ࠬ ࡈ ࠖ ࡦ ㉄ ߢ

⴫ ߐ ࠇ ࠆ ᭴ ㅧ ߣ ߥ ࠆ ߎ ߣ ߇ ࡇ ࡯ ࠢ ࠪ ࡈ ࠻ ߩ ේ ࿃ ߢ ޽ ࠅ 㧘 ߹ ߚ ߎ ߩ ࠃ ߁ ߥ ᭴ ㅧ ߇ ࡅ ࠼ ࡜ ࠫ ࡦ ߩ ෻ ᔕ ࠍ ଦ ㅴ ߔ ࠆ ߎ ߣ ߇ ␜ ໂ ߐ ࠇ ߚ 㧚

⛯ ޿ ߡ ╙ 㧠 ┨ ߢ ߪ 㧘 ή 㔚 ⸃ ᨆ ಴ ෻ ᔕ ࡊ ࡠ ࠮ ࠬ ߦ ߅ ޿ ߡ ㊀ ⷐ ߥ ᓎ ഀ ࠍ ᜂ ߁ ᷝ ട ೷ ߩ ૞ ↪ ߩ ⸃ ᨆ ߳ ߩ ㆡ ↪ ࠍ ⹜ ߺ ߚ ⚿ ᨐ ߇ ߹ ߣ ߼ ࠄ ࠇ ߡ ޿ ࠆ 㧚 ή 㔚 ⸃ ᨆ ಴ ෻ ᔕ ߦ ߪ ᭽ ޘ ߥ ᷝ ട ೷ ߇ ↪ ޿ ࠄ ࠇ ߡ ޿ ࠆ ߇ 㧘 ᧄ ⎇ ⓥ ߢ ߪ ߘ ߩ ౖ ဳ ଀ ߣ ߒ ߡ ࠴ ࠝ ዩ ⚛ ߦ ⌕ ⋡ ߒ 㧘 ή 㔚 ⸃ N i P ♽ ࠍ ኻ ⽎ ߦ ⸃ ᨆ ࠍ ⴕ ߞ ߡ ޿ ࠆ 㧚N i ߪ A g㧘A u ޽ ࠆ ޿ ߪ C u ߥ ߤ ߦ Ყ セ ߒ ߡ ⴫ 㕙 ࡊ ࡜ ࠭ ࡕ ࡦ Ⴧ ᒝ ല ᨐ ߇ ᒙ ޿ ߎ ߣ ߇ ⍮ ࠄ ࠇ ߡ ޿ ࠆ ߇ 㧘 ᧄ ⎇ ⓥ ߦ ߅ ޿ ߡ 㐿 ⊒ ߒ ߚ ਄ ⸥ ࡊ ࡠ ࠮ ࠬ ࠍ ↪ ޿ ߡ ࡊ ࡜ ࠭ ࡕ ࡦ ࠕ ࡦ ࠹ ࠽ ᭴ ㅧ ࠍ ᒻ ᚑ ߔ ࠆ ߎ ߣ ߦ ࠃ ࠅ 㧘0 . 5 m m o l / L ߣ ޿ ߁ ᭂ ߼ ߡ ૐ ޿ Ớ ᐲ 㗔 ၞ ߦ ߅ ޿ ߡ ߽ N i ၮ ᧼ ⴫ 㕙 ߦ ሽ ࿷ ߔ ࠆ ࠴ ࠝ ዩ ⚛ ߩ ࠬ ࡍ ࠢ ࠻ ࡞ ࠍ ⹏ ଔ น ⢻ ߢ ޽ ࠆ ߎ ߣ ࠍ ⏕ ⹺ ߒ ߚ 㧚 ߎ ߩ ࠃ ߁ ߦ 㧘 ή 㔚 ⸃ ᨆ ಴ ࡊ ࡠ ࠮ ࠬ ߢ ਥ ߦ ↪ ޿ ࠄ ࠇ ߡ ޿ ࠆ N i ޽ ࠆ ޿ ߪ C u ⴫ 㕙 ߦ ߅ ߌ ࠆ ᓸ ㊂ ൻ ቇ ⒳ ߩ ᜼ േ ࠍ ߘ ߩ ႐ ⸃ ᨆ ߢ ߈ ࠆ ᚻ ᴺ ࠍ ⏕ ┙ ߒ ߚ ὐ ߪ 㧘 ห ࡊ ࡠ ࠮ ࠬ ߩ ♖ ኒ ߥ ⸃ ᨆ ߩ ㅴ ዷ ߦ ᄢ ߈ ߊ ⽸ ₂ ߔ ࠆ ᚑ ᨐ ߣ ߒ ߡ ߽ 㜞 ߊ ⹏ ଔ ߢ ߈ ࠆ 㧚 ߐ ࠄ ߦ ࠴ ࠝ ዩ ⚛ ߣ ࡎ ࠬ ࡈ ࠖ ࡦ ㉄ ߇ ౒ ሽ ߔ ࠆ ♽ ߦ ߟ ޿ ߡ ᬌ ⸛ ࠍ ⴕ ߞ ߚ ߣ ߎ ࠈ 㧘 ਄ ⸥ ╙ 3 ┨ ߦ ␜ ߒ ߚ ଀ ߣ ߪ ⇣ ߥ ࠅ ࡜ ࡑ ࡦ ࡇ ࡯ ࠢ ߩ ࠪ ࡈ ࠻ ߪ ⹺ ߼ ࠄ ࠇ ߥ ߆ ߞ ߚ 㧚 ߎ ߩ ⚿ ᨐ ߦ ኒ ᐲ ᳢ 㑐 ᢙ ᴺ ߦ ࠃ ࠆ ℂ ⺰ ⸃ ᨆ ࠍ ว ࠊ ߖ ߡ ᬌ ⸛ ࠍ ⴕ ޿ 㧘 ࡎ ࠬ ࡈ ࠖ ࡦ ㉄ ߣ ࠴ ࠝ ዩ ⚛ ߪ ୘ ޘ ߦ N i ⴫ 㕙 ߦ ౒ ๆ ⌕ ߒ ߚ ⁁ ᘒ ࠍ ߣ ࠅ 㧘 ߎ ࠇ ߇ ․ ߦ 㜞 p H 㗔 ၞ ߦ ߅ ߌ ࠆ ࡎ ࠬ ࡈ ࠖ ࡦ ㉄ ߩ ෻ ᔕ ᛥ ೙ ߩ ේ ࿃ ߢ ޽ ࠆ ߣ ⠨ ኤ ߒ ߡ ޿ ࠆ 㧚 ߎ ߩ ࠃ ߁ ߦ 㧘 ㆶ ర ೷ ߿ ᷝ ട ೷ ߩ ෻ ᔕ ߿ ⋧ ੕ ૞ ↪ ߩ ࡔ ࠞ ࠾ ࠭ ࡓ ࠍ ⋥ ធ ⊛ ߦ ⏕ ⹺ ߔ ࠆ ᚻ ᴺ ࠍ ᓧ ߚ ߎ ߣ ߪ 㜞 ߊ ⹏ ଔ ߢ ߈ ࠆ 㧚

╙ 㧡 ┨ ߢ ߪ 㧘 ⎇ ⓥ ᚑ ᨐ ࠍ ✚ ᜝ ߒ 㧘 ᧄ ⎇ ⓥ ᚑ ᨐ ߩ ή 㔚 ⸃ ᨆ ಴ ෻ ᔕ ࡊ ࡠ ࠮ ࠬ ߩ

⸃ ᨆ ߦ ኻ ߔ ࠆ ᦭ ↪ ᕈ 㧘 ߐ ࠄ ߦ ࿕ ᶧ ⇇ 㕙 ෻ ᔕ ⸃ ᨆ ో ⥸ ߦ ኻ ߒ ᦼ ᓙ ߐ ࠇ ࠆ ⽸ ₂ ߣ

੹ ᓟ ߩ ዷ ᦸ ߇ ߹ ߣ ߼ ߡ ㅀ ߴ ࠄ ࠇ ߡ ޿ ࠆ 㧚

એ ਄ ߩ ࠃ ߁ ߦ 㧘 ᧄ ⺰ ᢥ ߢ ߪ 㧘 ࿕ ᶧ ⇇ 㕙 ߦ ߅ ߌ ࠆ ⴫ 㕙 ෻ ᔕ ߦ 㑐 ਈ ߔ ࠆ ൻ ቇ ⒳ ߩ ᜼ േ ࠍ 㧘 ᶧ ਛ ṁ ሽ ⒳ ߩ ᓇ 㗀 ࠍ ฃ ߌ ߕ ߦ 㜞 ᗵ ᐲ ߢ ߘ ߩ ႐ ⷰ ኤ น ⢻ ߥ ᣂ ߚ ߥ ᚻ ᴺ ࠍ ⏕ ┙ ߒ 㧘 ߎ ࠇ ࠍ ↪ ޿ ߡ ή 㔚 ⸃ ᨆ ಴ ෻ ᔕ ߦ ߅ ߌ ࠆ ㆶ ర ೷ ࡮ ᷝ ട ೷ ߩ ᜼ േ ⸃ ᨆ ࠍ ⴕ ߞ ߚ ᚑ ᨐ ߇ ␜ ߐ ࠇ ߡ ޿ ࠆ ߽ ߩ ߢ ޽ ࠅ 㧘 ᓧ ࠄ ࠇ ߚ ⍮ ⷗ ߪ ᭽ ޘ ߥ ࿕ ᶧ ⇇ 㕙

෻ ᔕ ߩ ♖ ኒ ߥ ⸃ ᨆ ߦ ᏷ ᐢ ߊ ዷ 㐿 น ⢻ ߥ ⁛ ഃ ⊛ ߥ ౝ ኈ ߣ ್ ᢿ ߐ ࠇ ࠆ 㧚 ࠃ ߞ ߡ ᧄ

⺰ ᢥ ߪ ඳ ჻ 㧔 Ꮏ ቇ 㧕 ߩ ቇ ૏ ⺰ ᢥ ߣ ߒ ߡ ଔ ୯ ޽ ࠆ ߽ ߩ ߣ ⹺ ߼ ࠆ 㧚 㧞 㧜 㧝 㧟 ᐕ 㧥 ᦬

ክ ᩏ ຬ ਥ ᩏ ᣧ Ⓑ ↰ ᄢ ቇ ᢎ ᝼ ඳ ჻ Ꮏ ቇ ᣧ Ⓑ ↰ ᄢ ቇ ᧄ 㑆 ᢘ ਯ ᣧ Ⓑ ↰ ᄢ ቇ ᢎ ᝼ Ꮏ ቇ ඳ ჻ 㧔 ᣧ Ⓑ ↰ ᄢ ቇ 㧕 ㅩ ဈ ື ᒫ ᣧ Ⓑ ↰ ᄢ ቇ ᢎ ᝼ Ꮏ ቇ ඳ ჻ 㧔 ᣧ Ⓑ ↰ ᄢ ቇ 㧕 㤥 ↰ ৻ ᐘ ᣧ Ⓑ ↰ ᄢ ቇ ᢎ ᝼ Ꮏ ቇ ඳ ჻ 㧔 ᣧ Ⓑ ↰ ᄢ ቇ 㧕 ⩲ ේ ⟵ ਯ ᣧ Ⓑ ↰ ᄢ ቇ ಎ ᢎ ᝼ ඳ ჻ Ꮏ ቇ ᣧ Ⓑ ↰ ᄢ ቇ 㐷 㑆 ⡨ ਯ

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