㔚ᭂ਄ߦ૞⵾ߒߚጀ㑆ൻว‛ࠍ↪޿ࠆ࡟ࠕࡔ࠲࡞ߩ࿁෼ᛛⴚߩ㐿⊒
⎇ⓥઍ⴫⠪ ጊญᄢቇᄢቇ㒮ℂᎿቇ⎇ⓥ⑼‛⾰ൻቇኾ᡹  ಎᢎ᝼ ਛጊ㓷᥍౒ห⎇ⓥ⠪ ጊญᄢቇᄢቇ㒮කቇ♽⎇ⓥ⑼ᔕ↪ಽሶ↢๮⑼ቇ♽ኾ᡹  ಎᢎ᝼ ศᧄ ⺈


1. ✜⸒
ᐔᚑ 19 ᐕ 6 ᦬㧘᡽ᐭߪਛ࿖ߥߤߩᎿᬺൻߦ઻ߞߡ਎⇇⊛ߦ㔛⛎߇ㅼㄼߒߡ޿ࠆ࡟ࠕࡔ࠲࡞㧔Ꮧ
ዋ㊄ዻ㧕ߦߟ޿ߡ㧘⍹ᴤ߿࠙࡜ࡦߥߤߣਗ߱⾗Ḯᄖ੤ߩᩇߩ৻ߟߦ૏⟎ߠߌߡ቟ቯ⏕଻ߦਸ਼ࠅ಴ߔߎߣࠍ᳿߼ߚ‫ߩ࡞࠲ࡔࠕ࡟ޕ‬቟ቯ⏕଻ߦߪ㧘ଏ⛎࡞࡯࠻ࠍᐢߍࠆߚ߼ߩ⺞ᩏ੐ᬺߣਗࠎߢ࿖ౝ
ߩ⵾ㅧᎿ⒟߆ࠄ↢ߓࠆ࡟ࠕࡔ࠲࡞ߩ࿁෼ᛛⴚߩ㐿⊒߇ਇนᰳߢ޽ࠆ‫ޕ‬‫ޟ‬㊄ዻࠍ޽ࠆ⒳ߩṁᶧ㧔৻⥸⊛ߦߪ↥ᬺឃ᳓㧕߆ࠄㆬᛯ⊛ߦ࿁෼ߔࠆᛛⴚߪ޽ࠆࠃ߁ߢߥ޿‫ޠ‬ߣ޿߁ߩ߇᳓ಣℂᬺ⇇ߩ౒ㅢ⹺⼂ߢ޽ࠆ‫․ޕ‬ቯ㊄ዻࠗࠝࡦࠍๆ⌕ߔࠆᣢሽᛛⴚߣߒߡࠠ࡟࡯࠻೷ࠍ↪޿ࠆᣇᴺ߿㔚⸃߼ߞ߈ᴺ߇᜼ߍࠄࠇࠆ߇㧘ઁߩ࿃ሶߩᓇ㗀߇ᄢ߈ߊㆬᛯ⊛ߣߪ⸒߃ߥ޿‫ޕ‬ታ㓙ߦߪ㧘㊄ዻ᳓㉄ൻ‛ߣߒߡᴉᲚ࡮㒰෰ߔࠆᣇᴺ߇৻⥸⊛ߢ޽ࠆ߇㧘ๆ⌕೷㧔☸ሶ㧕ߩੑᰴ⊛࿁෼߇ᔅⷐߢ޽ࠅ㧘⋡⊛ߣߔࠆ㊄ዻࠍㆆ㔌ߢ߈ߥ޿ߣ޿߁໧㗴ࠍ㐳ᐕᛴ߃ߡ޿ࠆ‫ᦨޕ‬ㄭ㧘࠴ࠕࠞ࡟࠶ࠢࠬࠕ࡟ࡦ㧔㊄ዻߣߩⷫ๺ᕈߩ㜞޿Ⅳ⁁ൻว‛㧕ࠍ↪޿ߡᷙวᑄᶧ߆ࠄ㊀㊄ዻࠗࠝࡦࠍㆬᛯ⊛ߦ࿁෼ߔࠆᣇᴺ߇⊒⴫ߐࠇߚ߇㧘ๆ⌕೷߇߈ࠊ߼ߡ㜞ଔߥߎߣ㧘ᶧ̆ᶧ᛽಴ߢ޽ࠆߚ߼ଐὼ㊄ዻߩㆆ㔌ߦ໧㗴߇ᱷࠆߥߤ㧘චಽߣߪ⸒߃ߥ޿‫ޕ‬↥ᬺᵴേߩ⚿ᨐឃ಴ߐࠇࠆ㊀㊄ዻ㘃ࠍ࿁෼ߔࠆߎߣߪ㧘ⅣႺ଻ోߣ޿߁ⷰὐ߆ࠄ߽㊀ⷐߢ޽ࠆ‫ޕ‬଀߃߫㧘౮⌀Ꮏᬺ㧘ࡔ࠶ࠠᎿᬺ߆ࠄឃ಴ߐࠇࠆᑄ᳓ਛߩ㌁ߪ㧘ߘߩⷙ೙߇ㄭᐕ߹ߔ߹ߔ෩ߒߊߥ
ߞߡ޿ࠆ‫ޕ‬㋦ߪੱ૕ߦ᦭ኂߥ㊀㊄ዻߢ޽ࠅ㧘Ꮏᬺᑄ᳓߿ⅣႺ᳓ߦട߃㧘᳓㆏▤߆ࠄṁ಴ߐࠇࠆ㋦ߦࠃࠆ㘶ᢱ᳓ᳪᨴ߽໧㗴ߦߥߞߡ޿ࠆ‫ޕ‬㌁ߩ࿁෼ߦ㑐ߒߡߪ㧘㌁ߦ㈩૏น⢻ߥ⎫㤛ේሶࠍ᦭ߔࠆ
ࡐ࡝ࡑ࡯ࠍๆ⌕೷ߣߒߡ↪޿ࠆᣇᴺ㧘㋦ߩ࿁෼ߦߪ㧘ᴤ᳓⋧ಽ㔌⃻⽎ࠍ೑↪ߒߡ㋦ࠍ᳓⋧஥ߦᴉᲚಽ㔌ߔࠆߥߤߩᣇᴺ߇ႎ๔ߐࠇߡ޿ࠆ‫ߒ߆ߒޕ‬㧘ߎࠇࠄߩᚻᴺߪ㧘ᑄ᳓ਛߦᷙ࿷ߔࠆ࠽࠻࡝࠙
ࡓࠗࠝࡦߥߤࠍหᤨߦๆ⌕ߔࠆߚ߼㧘㌁޽ࠆ޿ߪ㋦ࠗࠝࡦߩๆ⌕ല₸ࠍ㜞߼ࠆߎߣ߇࿎㔍ߢ޽ࠆ‫ޕ‬ᚒ‫ߪޘ‬㧘᳓ṁᶧਛߢߩࡑࡦࠟࡦ(II)ࠗࠝࡦߩ㔚⸃㉄ൻߣ޿߁߈ࠊ߼ߡ◲නߥᚻᴺߦࠃߞߡ㔚ᭂၮ᧼਄ߦጀ⁁ࡑࡦࠟࡦ㉄ൻ‛߇⭯⤑ᒻᚑߔࠆߎߣࠍ⷗޿ߛߒߚ 1)‫ߩߎޕ‬ᣇᴺߦࠃࠇ߫㧘ࠕ࡞ࠞ࡝㊄ዻߩઁ㧘ㅢᏱߩࠗࠝࡦ੤឵ߢߪਇน⢻ߢ޽ߞߚᄢ߈ߥࠞ࠴ࠝࡦ㧔ࠕ࡞ࠠ࡞ࠕࡦࡕ࠾࠙ࡓߥߤ㧕ࠍ Mn ㉄ൻ‛ጀ㑆ߦ⋥ធࠗࡦ࠲࡯ࠞ࡟࡯࠻ߢ߈ࠆ 2)‫ޕ‬ᄢ߈ߥࠞ࠴ࠝࡦ㧘ߟ߹ࠅ㔚⩄ኒᐲߩዊߐߥ
ࠞ࠴ࠝࡦߪ㧘ᓟ⛯ߩࠗࠝࡦ੤឵෻ᔕߦ߅ߌࠆ⦟ᅢߥ̌leaving ion̍ߣ⸒߃ࠆ 3)‫ޕ‬ᓥ᧪ߩήᯏ/᦭ᯏ࠽ࡁࠦࡦࡐࠫ࠶࠻ߩวᚑᴺߩᄙߊ߇㧘ᣢᚑߩήᯏ㉄ൻ‛㧔ࡎࠬ࠻㧕ߦ᦭ᯏಽሶ㧔ࠥࠬ࠻㧕ࠍዉ౉ߔࠆߩߦኻߒ㧘ᚒ‫ߩޘ‬⠨᩺ߒߚࡊࡠ࠮ࠬߪࠥࠬ࠻ࠗࠝࡦࠍขࠅㄟߺߥ߇ࠄήᯏ㉄ൻ‛߇ᄙጀᒻᚑߔ㧙㧙ࠆߚ߼㧘ᩰሶ߿㔚⩄ࡑ࠶࠴ࡦࠣߩᔅⷐ߇ߥߊ㧘᳢↪ᕈ߇߈ࠊ߼ߡ㜞޿‫࡝ࠞ࡞ࠕޕ‬㊄ዻ㧘ࠕ࡞ࠠ࡞ࠕࡦࡕ࠾࠙ࡓߩઁߦ߽ࡔ࠴࡞ࡆࠝࡠࠥࡦ 4)㧘ࠞ࠴ࠝࡦᕈࡐ࡞ࡈࠖ࡝ࡦߥߤߩᯏ⢻ᕈಽሶ㧘ࠞ࠴ࠝࡦᕈߩ㔚⸃⾰ࡐ࡝ࡑ࡯5,6)ߦ߽ㆡ↪น⢻ߢ޽ߞߚ‫ߡߒߦ߁ࠃߩߎޕ‬૞⵾ߒߚጀ⁁ࡑࡦࠟࡦ㉄ൻ‛⭯⤑ߪࠗࠝࡦ੤឵᧚ᢱ 7,8)㧘㔚᳇ൻቇࠠࡖࡄࠪ࠲ 9,10)㧘ੑᰴ㔚ᳰ 11)㧘ࠛ࡟ࠢ࠻ࡠࠢࡠࡒ࠶ࠢ᧚ᢱ 12)㧘㔚ᭂ⸅ᇦ 13)ߣߒߡ࡙࠾࡯ࠢߥ᜼േࠍ␜ߔ‫ޕ‬ᧄ⎇ⓥߪ㧘㔚᳇ൻቇᴺߣ޿߁◲න߆ߟᄢⷙᮨ⵾ㅧߦㆡߒߚᣇᴺߦࠃߞߡࠕ࡞ࠠ࡞ࠕࡦࡕ࠾࠙ࡓࠗࠝࡦ㧘޽ࠆ޿ߪࠞ࠴ࠝࡦᕈࡐ࡝ࡑ࡯ࠍࠗࡦ࠲࡯ࠞ࡟࡯࠻ߒߚጀ㑆ൻว‛㧔ࡑࡦࠟࡦ㉄ൻ‛㧕ࠍ㔚ᭂ਄ߦ૞⵾ߒ㧘㊀㊄ዻࠗࠝࡦߦኻߔࠆࠗࠝࡦ੤឵᜼േ㧘߹ߚ㧘ጀ㑆ߢߩ㔚ሶવ㆐᜼േࠍㅊ〔ߒߚ‫ޕ‬
2. ታ㛎
2. 1. ⹜⮎ߣⵝ⟎䊁䊃䊤䊑䉼䊦䉝䊮䊝䊆䉡䊛䋨TBA䋬99%䋬Aldrich䋩䉪䊨䊤䉟䊄䋬ࡐ࡝ࠫࠕ࡝࡞ࠫࡔ࠴࡞ࠕࡦࡕ࠾࠙ࡓ㧔PDDA㧕ࠢࡠ࡜ࠗ࠼㧔20% solution in water, Aldrich㧕㧘⎣㉄㌁㧔99.8%,ጊൻቇᎿᬺ㧕㧘⎣㉄㋦㧔99.5%,๺శ⚐⮎Ꮏᬺ㧕㧘⎣㉄㌃㧔99.0 ~ 104.0%, ๺శ⚐⮎Ꮏᬺ㧕㧘⎣㉄ࠦࡃ࡞࠻㧔98.0%, ⍹ᵤ⵾⮎㧕㧘⎣㉄ࡑࠣࡀࠪ࠙ࡓ㧔99.5%, ๺శ⚐⮎Ꮏᬺ㧕ࠍߘߩ߹߹↪޿ߚ‫ޕ‬㔚᳇ൻቇ෻ᔕ䈲ㅢᏱ䈱ਃ㔚ᭂ䉶䊦ਛ䋬䊘䊁䊮䉲䊢䉴䉺䉾䊃䋨ർ᢯㔚Ꮏ䋬CHI812A䋩䉕↪䈇䈩Ᏹ᷷䈪ⴕ䈦䈢䇯㔚⸃ᶧߪੑ࿁⫳⇐ߒߚ᳓ࠍ↪޿ߡ⺞⵾ߒ㧘૶↪⋥೨ߦ♖⵾⓸⚛ࠟࠬࠍࡃࡉ࡝ࡦࠣߔࠆߎߣߦࠃߞߡ⣕㉄⚛ߒߚ䇯䉨䊞䊤䉪䉺䊥䉷䊷䉲䊢䊮䈮䈲䋬X ✢࿁᛬ᴺ䋨Shimadzu XD-D1; CuKĮ ᡼኿ 30 kV䋬30 mA䋩䋬X ✢శ㔚ሶಽశᴺ䋨Escalab 210; 㕖න⦡ൻ AlKĮ ᡼኿ 15 kV, 20 mA䋩䉕↪䈇䈢䇯
2. 2. TBA/ࡑࡦࠟࡦ㉄ൻ‛⤑ߩ૞⵾ߣ㊀㊄ዻࠗࠝࡦߩ࿁෼
૞↪ᭂ䈮䈲⊕㊄᧼䋨1×1 cm2䋩䉕↪䈇䈢䇯㔚ᨆᶎ䈮 MnSO4 2 mM 䈫 TBACl 50 mM 䉕฽䉃᳓ṁᶧ䉕↪
䈇䋬+1.0 V 䋨vs Ag/AgCl䋩䈪 60 ಽ㑆㔚⸃㉄ൻ䉕ⴕ䈉䈖䈫䈪ጀ⁁䊙䊮䉧䊮㉄ൻ‛⭯⤑䉕૞⵾䈚䈢䇯䈖䈱䉋䈉䈮䈚䈩ᓧ䉌䉏䈢⤑䉕 0.5 M 䈱㊀㊄ዻ䉟䉥䊮䋨Co2+䋬Ni2+䋬Cr3+䋬Cu2+䋩䉕฽䉃᳓ṁᶧ䈮 24 ᤨ㑆ᶐẃ䈚䋬䉟䉥䊮੤឵䈮䉋䉎㊀㊄ዻ䉟䉥䊮䈱࿁෼䉕⹜䉂䈢䇯
2. 3. PDDA/ࡑࡦࠟࡦ㉄ൻ‛⤑ߩ૞⵾ߣ㊀㊄ዻࠗࠝࡦߩ࿁෼ ૞↪ᭂ䈮䈲⊕㊄᧼䋨1×1 cm2䋩䉕↪䈇䈢䇯㔚ᨆᶎ䈮 MnSO4 2 mM 䈫 PDDACl 5.6 mM䋨䊝䊉䊙䊷ၮḰ䋩䉕฽䉃᳓ṁᶧ䉕↪䈇䋬+1.0 V 䋨vs Ag/AgCl䋩䈪 60 ಽ㑆㔚⸃㉄ൻ䉕ⴕ䈉䈖䈫䈪ጀ⁁䊙䊮䉧䊮㉄ൻ‛⭯⤑䉕૞⵾䈚䈢䇯䈖䈱䉋䈉䈮䈚䈩ᓧ䉌䉏䈢⤑䉕⒳䇱䈱㊄ዻ䉟䉥䊮䋨Ag+䋬Pb2+, K+䋬Mg2+, Co2+, Cu2+䋩䉕฽䉃᳓ṁᶧ䈮 24 ᤨ㑆ᶐẃ䈚䋬䉟䉥䊮੤឵䉕⹜䉂䈢䇯㧙㧙

3. ⚿ᨐߣ⠨ኤ
3. 1. TBA/Mn ㉄ൻ‛⭯⤑ࠍ↪޿ࠆ㊀㊄ዻࠗࠝࡦߩ࿁෼
Fig. 1(a)䈲 TBA 䈫 Mn2+䉟䉥䊮䉕฽䉃᳓ṁᶧਛ䈎䉌㔚ᨆ䈚䈢 Mn ㉄ൻ‛⤑䈱 XRD 䊌䉺䊷䊮䈪䈅䉎䇯2ș = 7.2°䋬14.4°䋬
21.6°䈱࿁᛬䊏䊷䉪䈲 Bragg ᑼ䉋䉍 1.23 nm䋬0.61 nm䋬0.41nm 䈫⷗Ⓧ䉅䉌䉏䋬Mn ㉄ൻ‛䉲䊷䊃䈎䉌䈱࿁᛬䋨001䋩䈫䈠䈱ੑᰴ䋨002䋩䋬ਃᰴ䋨003䋩䈱࿁᛬䈮Ꮻዻ䈘䉏䋬䊋䊷䊈䉰䉟䊃ဳጀ⁁ Mn ㉄ൻ‛䈏ᒻᚑ䈚䈢䈖䈫䉕␜䈜䇯Mn ㉄ൻ‛䉲䊷䊃䈱⚿᥏ቇ⊛䈭ෘ䉂䋨~0.45 nm䋩䈫 TBA 䈱䉟䉥䊮ඨᓘ䋨0.5 nm䋩䉕⠨ᘦ䈜䉎䈫䋬ᓧ䉌䉏䈢ጀ㑆〒㔌䋨d001=1.23 nm䋩䈲 TBA 䈏䊝䊉䊧䉟䊟䊷䈪䉟䊮䉺䊷䉦䊧䊷䊃䈚䋬䈠䈱 C2 ࿁ォゲ䈏 Mn ㉄ൻ‛䉲䊷䊃䈮ኻ䈚䈩ု⋥䈮䈭䉎䉋䈉䈮㈩ะ䈜䉎䈖䈫䉕␜ໂ䈚䈩䈇䉎䇯(b)䌾(e)䈱䊌䉺䊷䊮䈲ฦ⒳㊀㊄ዻ䉟䉥䊮䉕฽䉃᳓ṁᶧ䈮ᶐẃ䈚䈢ᓟ䈮ᓧ䉌䉏䈢䉅䈱䈪䈅䉎䇯䈇䈝䉏䈱႐ว䉅

Fig. 1 㔚ᨆ⋥ᓟ(a)䋬䈍䉋䈶 Co2+ (b)䋬Cr3+(c), Ni2+ (d)䋬Cu2+ (e)䈱⎣㉄Ⴎ᳓ṁᶧ䈮ᶐẃ䈚䈢ᓟ䈱 XRD 䊌䉺䊷䊮䋮䊏䊷䉪䈲 12 䈫 24°ઃㄭ䈮⃻䉏䈩䈇䉎䇯䈖䉏䉌䉅 001 䈫 002 䈮䈠䉏䈡䉏Ꮻዻ䈘䉏䋬ጀ㑆〒㔌䋨d001䋩䈲~0.7 nm 䈫⷗Ⓧ䉅䉌
䉏䈢䇯䈖䉏䈲᳓ಽሶ䋨⋥ᓘ 0.28 nm䋩䉋䉍䉅ዊ䈘䈭䉦䉼䉥䊮䉕䉟䊮䉺䊷䉦䊧䊷䊃䈚䈢䊋䊷䊈䉰䉟䊃䈮ౖဳ⊛䈪䈅䉍䋬㊀㊄ዻ䉟䉥䊮䈏᳓⋧䈎䉌ጀ㑆䈮⒖േ䈚䈢䈖䈫䉕␜䈜䇯
Fig. 2 䈲䋬Fig. 1 䈪૞⵾䈚䈢⤑䉕 0.5 M Na2SO4 ᳓ṁᶧਛ䈮⒖䈚䋬᝹ᒁㅦᐲ 20 mV/s 䈪᷹ቯ䈚䈢䉰䉟䉪䊥䉾䉪䊗䊦䉺䊝䉫䊤䊛䋨CV䋩䈪䈅䉎䇯(a)䈲 TBA/Mn ㉄ൻ‛䈱䉅䈱䈪䈅䉍䋬⤑ਛ䈱 Mn 䉟䉥䊮⥄り䈱㔚᳇ൻቇᔕ╵䈮䉋䉎䇯䈖䈱㔚૏㗔ၞ䈪䈲 Mn2+ļMn3+ļMn4+㑆䈱ㆫ⒖䈏น⢻䈪䈅䉎䇯(b)䈪
Co ⥄り䈱䊧䊄䉾䉪䉴䈲ⷰኤ䈘䉏䈭䈎䈦䈢䈏䋬Mn ㉄ൻ‛䈱ᔕ╵䈲᣿䉌䈎䈮ᄌൻ䈚䈩䈇䉎䇯ห᭽䈮䋬Ni 䉟䉥䊮䈱ᔕ╵䈲⷗䉌䉏䈭䈇䈏䋬CV 䈲⇣䈭䈦䈩䈇䉎䇯৻ᣇ䋬Cu/Mn ㉄ൻ‛⤑䈪䈲ᦨೋ䈱䉦䉸䊷䊄᝹ᒁ䈪 Cu2+ 䈱ㆶర䈮䉋䉎䊏䊷䉪䈏–0.01 V 䈮䋬ㅒ᝹ᒁ䈪䈲ㆶర↢ᚑ䈚䈢 Cu1+䈱ౣ㉄ൻ䊏䊷䉪䈏 0.09 V 䈮⃻䉏䈢䇯䈖䉏䈲 Mn ㉄ൻ‛䉲䊷䊃䉕੺䈚䈩ጀ㑆䈱 Cu 䈮㔚ሶ䈏વ㆐䈘䉏䈢䈖䈫䉕ᗧ๧䈚䈩䈇䉎䇯ⷰኤ䈘䉏䈢Cu 䈱䊧䊄䉾䉪䉴᜼േ䈲䊋䊦䉪䈱䈠䉏䈫䈲⇣䈭䉍䋬㐽䈙䈘䉏䈢ⓨ㑆䈮䈍䈔䉎ቅ┙ Cu 䉟䉥䊮䈮䉋䉎䉅䈱䈫ℂ⸃䈘䉏䉎䇯⚿⺰䈫䈚䈩䋬㔚ᨆᴺ䈮䉋䈦䈩૞⵾䈚䈢ጀ⁁䊙䊮䉧䊮㉄ൻ‛䈱ጀ㑆䉴䊕䊷䉴䈲㊀㊄ዻ䉟䉥䊮䈱࿁෼䈮᦭↪䈪䈅䉎䈖䈫䈏ಽ䈎䈦䈢䇯䉁䈢䋬Cu 䉟䉥䊮䈻䈱㔚ሶવ㆐䈏น⢻䈪䈅䉎䈫䈇䈉੐ታ䈲䋬ጀ㑆䈪䈱ੑᰴ⊛䈭䊒䊨䉶䉾䉲䊮䉫䉇䉶䊮䉰䊷㧙㧙

Fig. 2 TBA (a)䋬Co2+ (b)䋬Cr3+ (c), Ni2+(d)䋬Cu2+ (e)䉕䉟䊮䉺䊷䉦䊧䊷䊃䈚䈢ጀ⁁Mn ㉄ൻ‛⭯⤑䈱䉰䉟䉪䊥䉾䉪䊗䊦䉺䊝䉫䊤䊛䋮㔚⸃ᶧ䋬0.5 M Na2SO4; ᝹ᒁㅦᐲ䋬
20 mV/s䋮䈫䈚䈩䈱ᔕ↪䈏น⢻䈪䈅䉎䈖䈫䉕␜ໂ䈚䈩䈇䉎䇯
3. 2. PDDA/Mn ㉄ൻ‛ࠍ↪޿ࠆ㊀㊄ዻࠗࠝࡦߩ࿁෼
Fig. 3(a)ߪ㧘PDDA ࠍ฽߻ MnSO4 ᳓ṁᶧ߆ࠄ㔚ᨆߒߚ Mn ㉄ൻ‛⤑ߩ XRD ࡄ࠲࡯ࡦߢ޽ࠆ‫ޕ‬9.1°,18.2°, 27.3°ߦ╬㑆㓒ߩ࿁᛬ࡇ࡯ࠢ߇⃻ࠇߚ‫╬ޕ‬㑆㓒ߩ࿁᛬ࡇ࡯ࠢߪ㧘ጀ᭴ㅧߦ․᦭ߢ޽ࠅ㧘Mn ㉄ൻ‛ጀ߆ࠄߩ࿁᛬㧔00l, l=1, 2, 3㧕ߦᏫዻߐࠇࠆ 5)‫ߚ߹ޕ‬㧘001 ࡇ࡯ࠢߩᩰሶቯᢙ㧔=d001㧕ߪጀ㑆〒㔌ߦኻᔕߒ㧘Bragg ᑼࠃࠅ 0.97 nm ߣ⷗Ⓧ߽ࠄࠇߚ‫ޕ‬Mn ㉄ൻ‛න৻ࠪ࡯࠻߅ࠃ߮ PDDA ߩ⚿᥏ቇ⊛ߥෘߺߪ㧘ߘࠇߙࠇ 0.45㧘0.5 nm ߢ޽ࠆߎߣ߆ࠄ㧘ᓧࠄࠇߚጀ㑆〒㔌ߪ㧘PDDA ࠞ࠴ࠝࡦ߇ࡕࡁ࡟ࠗࡗ࡯ߣߒߡߘߩಽሶ㕙߇ Mn ㉄ൻ‛ࠪ࡯࠻ߦኻߒߡᐔⴕߦߥࠆࠃ߁ߦࠗࡦ࠲࡯ࠞ࡟࡯࠻ߒߚߎߣࠍ␜ໂߒߡ޿ࠆ‫(ࡦ࡯࠲ࡄޕ‬b)㨪(f)ߪ(a)ߩ PDDA/Mn ㉄ൻ‛⭯⤑ࠍ⇣ߥࠆỚᐲߩ AgNO3ṁᶧߦ 12 ᤨ㑆ᶐẃߐߖߚᓟߩ XRD ࡄ࠲࡯ࡦߢ޽ࠆ‫ޕ‬ᶐẃᓟߩ XRD ࡄ࠲࡯ࡦߪ㧘AgNO3 ߩỚᐲ߇㜞ߊߥࠆߦߟࠇߡᒝᐲ߇ዊߐߊߥߞߡ߅ࠅ㧘0.05 M ߢቢోߦᶖᄬߒߚ‫ޕ‬PDDA ⭯⤑ߩ㔚ᨆ⋥ᓟ(a)㧘߅ࠃ߮ 0.025 M AgNO3 ṁᶧߦ 12 ᤨ㑆ᶐẃߐߖߚᓟ(b)ߩ X ✢శ㔚ሶࠬࡍࠢ࠻࡞ࠍ Fig. 4 ߦ␜ߔ‫(࡞࠻ࠢࡍࠬޕ‬a)ߦ߅޿ߡ㧘650㧘530㧘85 eV ઃㄭߦᬌ಴ߐࠇߚࡇ࡯ࠢߪMn ㉄ൻ‛ߦ↱᧪ߔࠆ‫(࡞࠻ࠢࡍࠬޕ‬b)ߢߪ Mn ㉄ൻ‛ߦട߃ߡ㧘604 eV ߣ 574 eV ߦ Ag 3p ߦ⿠࿃ߔࠆࡇ࡯ࠢ㧘߅ࠃ߮ 376 eV ߣ 370 eV ߦ Ag 3d ߦ⿠࿃ߔࠆࡇ࡯ࠢ߇ᬌ಴ߐࠇߚ‫ߚ߹ޕ‬㧘PDDA ߩࠕࡦࡕ࠾࠙ࡓၮߦ↱᧪ߔࠆࡇ࡯ࠢ㧔402 eV㧕ߪᶐẃᓟᷫዋߒߚ‫ߢߎߎޕ‬㧘C 1s ࠪࠣ࠽࡞㧔270 eV㧕ߪ PDDA ࠞ࠴ࠝࡦߦ↱᧪ߔࠆ߽ߩߢߪߥߊ㧘XPS ⵝ⟎ౝߩ὇ൻ᳓⚛ࠦࡦ࠲ࡒߦࠃࠆ߽ߩߣ⠨߃ࠄࠇࠆ‫ޕ‬એ਄ߩ⚿ᨐߪ㧘᳓ṁᶧਛߩ Ag+ࠗࠝࡦ߇ጀౝߩ PDDA ߣ⟎឵ߒ㧘⭯⤑ౝߦ࿁෼ߐࠇߚߎߣࠍ␜ߒߡ޿ࠆ‫߈ߣߩߎޕ‬㧘Mn ㉄ൻ‛ߪ⚿᥏ᕈ㧔ጀ᭴ㅧ㧕ࠍᄬ߁‫ޕ‬

Fig. 3 㔚ᨆ⋥ᓟ(a)䈍䉋䈶 AgNO3 ṁᶧ䈮 12h ᶐẃᓟ(b䌾f)䈱 PDDA/Mn ㉄ൻ‛⤑䈱 XRD 䊌䉺䊷䊮䋮[AgNO3]: (b) 0.001, (c) 0.01, (d) 0.025, (e) 0.05,(f) 0.1 M䋮

Fig. 4 㔚ᨆ⋥ᓟ(a)䈍䉋䈶 AgNO3 ṁᶧ䈮ᶐẃᓟ(b)䈱
PDDA/Mn ㉄ൻ‛⤑䈱 XPS 䉴䊕䉪䊃䊦䋮㧙㧙

Fig. 5 ߪ 0.1 M Pb(NO3)2 ṁᶧߦᶐẃߔࠆ೨ᓟߢ᷹ቯߒߚ PDDA/Mn ㉄ൻ‛⭯⤑ߩ XRD ࡄ࠲࡯ࡦߢ޽ࠆ‫ޕ‬ᶐẃᤨ㑆ߪ 12 ᤨ㑆ߣߒߚ‫ޕ‬ᶐẃᓟ(b)ߩ XRD ࡄ࠲࡯ࡦߦ߅޿ߡ㧘PDDA ߇ࠗࡦ࠲࡯ࠞ࡟࡯࠻ߒߚጀ᭴ㅧߦ․᦭ߥࡇ࡯ࠢߪᶖᄬߒ㧘Ag ߩ႐วߣห᭽ߦࠕࡕ࡞ࡈࠔࠬൻߒߚߎߣ߇ಽ߆ࠆ‫ޕ‬ߐࠄߦ㧘ᶐẃᓟߩ⤑ߩ XPS ࠬࡍࠢ࠻࡞ࠍ Fig. 6 ߦ␜ߔ‫ޕ‬650㧘530㧘85 eV ઃㄭߦ Mn ㉄ൻ‛ߦ↱᧪ߔࠆࡇ࡯ࠢߦട߃㧘436㧘413 eV ߦ Pb 4d ߦࠃࠆ࠳ࡉ࡟࠶࠻ࡇ࡯ࠢ㧘143㧘138 eV ߦ Pb 4f ߦ⿠࿃ߔࠆ࠳ࡉ࡟࠶࠻ࡇ࡯ࠢ߇ᬌ಴ߐࠇߚ‫৻ޕ‬ᣇ㧘PDDA ߩࠕࡦࡕ࠾࠙ࡓၮߦ↱᧪ߔࠆࡇ࡯ࠢߪቢో
ߦᶖᄬߒߚ‫ޕ‬એ਄ࠃࠅ㧘᳓ṁᶧਛߩ Pb2+ࠗࠝࡦߪጀ㑆ߩ PDDA ࠗࠝࡦߣ⟎឵ߒ㧘⤑ౝߦ࿁෼ߐࠇࠆ‫߈ߣߩߎޕ‬㧘Mn ㉄ൻ‛ߪ⚿᥏ᕈ㧔ጀ᭴ㅧ㧕ࠍᄬ߁‫ޕ‬

Fig. 5 㔚ᨆ⋥ᓟ(a)䈍䉋䈶 Pb(NO3)2 ṁᶧ䈮 12h ᶐẃᓟ(b)䈱 PDDA/Mn ㉄ൻ‛⤑䈱 XRD 䊌䉺䊷䊮䋮

Fig. 6 㔚ᨆ⋥ᓟ(a)䈍䉋䈶 Pb(NO3)2 ṁᶧ䈮 12h ᶐẃᓟ(b)䈱 PDDA/Mn ㉄ൻ‛⤑䈱 XPS 䉴䊕䉪䊃䊦䋮

PDDA/Mn ㉄ൻ‛⤑ࠍ K+, H+, Mg2+, Co2+, Cu2+ߩ⎣㉄Ⴎ᳓ṁᶧߦᶐẃᓟߒߚᓟߩ XRD ࡄ࠲࡯ࡦࠍ Fig. 7 ߦ␜ߔ‫ޕ‬KCl ᳓ṁᶧߦᶐẃᓟ(b)ߩ XRD ࡄ࠲࡯ࡦߪᶐẃ೨(a)ߩ߽ߩߣ߶߷หߓᒝᐲߩ࿁᛬
ࡇ࡯ࠢࠍ␜ߔ‫(ࡦ࡯࠲ࡄޕ‬c)㨪(f)ߦ߅޿ߡᒝᐲߪዊߐߊߥࠅ㧘(f)ߢߪࡉࡠ࡯࠼࠾ࡦࠣ߇⹺߼ࠄࠇࠆ‫ޕ‬ߒ߆ߒ㧘ጀ᭴ㅧ⥄りߪ޿ߕࠇߩ႐ว߽⛽ᜬߐࠇߡ޿ࠆ‫ޕ‬Fig. 7㩷 㔚ᨆ⋥ᓟ(a)䈍䉋䈶⒳䇱䈱䉦䉼䉥䊮䈱⎣㉄Ⴎ᳓ṁᶧ䈮 12h ᶐẃᓟ(b䌾f)䈱 PDDA/Mn ㉄ൻ‛⤑䈱 XRD 䊌䉺䊷䊮䋮(b) K+, (c) H+, (d) Mg2+, (e) Co2+, (f) Cu2+䋮

Fig. 8㩷 㔚ᨆ⋥ᓟ(a)䈍䉋䈶⒳䇱䈱䉦䉼䉥䊮䈱⎣㉄Ⴎ᳓ṁᶧ䈮 12h ᶐẃᓟ(b䌾d)䈱 PDDA/Mn ㉄ൻ‛⤑䈱 XPS+2+2+䉴䊕䉪䊃䊦䋮(b) H , (c) Co , (d) Mg 䋮㧙㧙ห᭽ߦߒߡᓧࠄࠇߚࠨࡦࡊ࡞⭯⤑ߩ XPS ࠬࡍࠢ࠻࡞ࠍ Fig. 8 ߦ␜ߔ‫ߩࠇߕ޿ޕ‬႐ว߽ Mn ㉄ൻ‛ߦ↱᧪ߔࠆࡇ࡯ࠢߦട߃㧘PDDA ߩࠕࡦࡕ࠾࠙ࡓၮߦࠃࠆ N 1s ࡇ࡯ࠢ߇ⷰኤߐࠇߚ‫ޕ‬N 1s ࠬࡍࠢ࠻࡞ߪ㧘ߎࠇࠄߩṁᶧߦᶐẃߔࠆ೨ߣታ⾰⊛ߦหߓᒝᐲߢ޽ߞߚ‫ ߪࠇߎޕ‬Mn ㉄ൻ‛ߩጀ㑆ߦሽ࿷ߔࠆ PDDA ߩ฽᦭㊂߇⎣㉄ṁᶧߦᶐẃߔࠆ೨ᓟߢᄌൻߒߥ޿ߎߣࠍ␜ߒߡ޿ࠆ‫ߚ߹ޕ‬㧘਄ㅀߩ Ag+㧘Pb2+ࠍ฽߻႐วߣߪ⇣ߥࠅ㧘ኻᔕߔࠆࠞ࠴ࠝࡦߦࠃࠆࡇ࡯ࠢߪᬌ಴ߐࠇߥ߆ߞߚ‫⚿ߩߎޕ‬ᨐߪ㧘PDDA/Mn ㉄ൻ‛ߩ PDDA ߇ Ag+㧘Pb2+ߦࠃߞߡߩߺ⟎឵ߐࠇࠆߎߣࠍᗧ๧ߒߡ߅ࠅ㧘ߎߩ㉄ൻ‛⤑߇㌁ࠗࠝࡦ㧘㋦ࠗࠝࡦߩㆬᛯ⊛࿁෼ߦ᦭↪ߢ޽ࠆߎߣࠍ␜ߒߡ޿ࠆ‫ޕ‬

4. ⚿⺰
㔚ᨆߦࠃࠅ૞⵾ߒߚጀ⁁ TBA/Mn ㉄ൻ‛⭯⤑ߪጀ㑆 TBA ߣߩࠗࠝࡦ੤឵ߦࠃߞߡᶧ⋧ߩ㊀㊄ዻࠗࠝࡦ㧔Co2+䋬Cr3+, Ni2+䋬Cu2+㧕ࠍ࿁෼ߔࠆߎߣ߇ߢ߈ࠆ‫߈ߣߩߎޕ‬㧘ጀ᭴ㅧߪ⛽ᜬߐࠇࠆ‫৻ޕ‬ᣇ㧘ጀ⁁ PDDA/Mn ㉄ൻ‛⤑ߪ㌁㧘㋦ࠗࠝࡦߩߺࠍㆬᛯ⊛ߦ࿁෼ߔࠆ‫ޕ‬PDDA ߇⟎឵ߐࠇࠆߣหᤨߦ
ጀ᭴ㅧߪᶖᄬߔࠆ‫ޕ‬⻢ㄉᧄ⎇ⓥ䈲䋬⽷࿅ᴺੱ JFE21 ਎♿⽷࿅ 2007 ᐕᐲᛛⴚ⎇ⓥഥᚑ䈱ᡰេ䈮䉋䈦䈩ⴕ䉒䉏䉁䈚䈢䇯䈖䈖䈮⸥䈚䈩ᗵ⻢⥌䈚䉁䈜䇯
ෳ⠨ᢥ₂㩷
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