㜞㕙ಽ⸃⢻ࡈࡠ࡯ဳࠠࡖࡇ࡜࡝࡯ᓸዊ࠮࡞ߦࠃࠆ᧚ᢱ⴫㕙ዪㇱߩ㔚᳇ൻቇർᶏ㆏ᄢቇᄢቇ㒮Ꮏቇ⎇ⓥ⑼‛⾰ൻቇኾ᡹ ಎᢎ᝼ ફ⷗౏ᔒ㧝㧚✜⸒ 21 ਎♿ߦ౉ࠅ‫ޔ‬ⅣႺ࡮࿾⃿᷷ᥦൻ໧㗴ߣ⋧߹ߞߡࠛࡀ࡞ࠡ࡯࡮⒘ዋ㋶‛⾗Ḯߩᨗᷢߪ‫ޔ‬޿ࠃ޿ࠃ㗼࿷ൻߒߡ߈ߚ‫ޕ‬ᚒ߇࿖ߩ⣣㘩㒐㘩ߦⷐߔࠆᐕ㑆⚻ᷣ៊ᄬߪ‫ޔ‬࿖᳃✚↢↥ߩ 1%ߦ߽෸߮‫ޔ‬ᜬ⛯น⢻ߥ⊒ዷ޽ࠆ␠ળࠍ▽ߊߚ߼ߦߪ‫␠ޔ‬ળၮ⋚ࠍᡰ߃ࠆ᧚ᢱ࡮⚛᧚ߩઍᦧᛛⴚߩ⏕┙ߣߣ߽ߦ⃻᦭ၮ⋚ߩ଻ో߅ࠃ߮᧚ᢱߩᑧ๮ኻ╷߇ᓥ᧪એ਄ߦ㊀ⷐߢ޽ࠆ‫ޕ‬㊄ዻ࡮㋕㍑᧚ᢱߩਇဋ৻⣣㘩‫ߦ․ޔ‬ሹ㘩ߪ‫᧚ޔ‬ᢱኼ๮ࠍ⪺ߒߊ៊ߥ߁ෂ㒾ߥ⣣㘩ᒻᘒߢ޽ࠆ‫ߩߘޕ‬⣣㘩ㅦᐲߩቯ㊂ൻߣ⣣㘩ᯏ᭴ߩ⸃᣿ߦၮߠߊലᨐ⊛ߥ㒐㘩ኻ╷ߩ⸳⸘ߦߪ‫ޔ‬੺࿷‛ߥߤਇဋ৻ߥ㊄ዻ⚵❱ㇱ߇⊒↢⿠ὐߣߥࠆ᧚ᢱ⴫㕙ᓸዊㇱߩ㔚᳇ൻቇ᜼േߩ⹦⚦ߥ⺞ᩏ߇ᔅⷐߢ޽ࠆ‫ޔߚ߹ޕ‬ⅣႺㆡᔕᕈ߅ࠃ߮⋭⾗Ḯߩⷰὐ߆ࠄࠢࡠࡔ࡯࠻߿੝㋦߼ߞ߈ߩઍᦧ⴫㕙ಣℂߩ㐿⊒߇᛼ߒㅴ߼ࠄࠇߡ޿ࠆ߇‫᧚ޔ‬ᢱߩ⠴㘩ᕈߪ⴫㕙ಣℂᰳ㒱ㇱߩ㔚᳇ൻቇ․ᕈߦᄢ߈ߊ㑐ਈߔࠆߩߢߘߩᛠី߇ਇนᰳߢ޽ࠆ‫ߩࠄࠇߎޕ‬ᓸዊ㔚᳇ൻቇߦߪ‫ޔ‬ᢙࡑࠗࠢࡠࡔ࡯࠻࡞એਅߩࠨࠗ࠭ߩ㕙ಽ⸃⢻ࠍ߽ߟᣂߒ޿᷹ቯᴺ߇ᔅⷐߢ޽ࠆ੐ߪ⸒߁߹ߢ߽ߥ޿‫ޕ‬ ᧄ⎇ⓥߢߪ‫ޔ‬਄ㅀߩ໧㗴ࠍ⸃᳿ߔࠆߚ߼ߦ㜞㕙ಽ⸃⢻ߩࡈࡠ࡯ဳࠠࡖࡇ࡜࡝࡯ᓸዊ࠮࡞ᴺ㧔f-CMC㧕ࠍ㐿⊒ߒߡ‫ޔ‬ሹ㘩ߩ⿠ὐߣߥࠆ੺࿷‛ߩ㔚᳇ൻቇ᜼േ߅ࠃ߮੝㋦߼ߞ߈ઍᦧ⴫㕙ಣℂ᧚ᰳ㒱ㇱߩᓸዊ㔚᳇ൻቇ᜼േࠍ⺞ᩏᬌ⸛ߔࠆߎߣࠍᦨ⚳⋡⊛ߣߒߡ޿ࠆ‫ޕ‬ߔߢߦ↳⺧⠪ࠄߪ f-CMC ߩේဳߩ⹜૞ߦᚑഞߒߡ߅ࠅ‫⥄ޔ‬േゞᾲ੤឵ེ㧔࡜ࠫࠛ࡯࠲㧕↪ࠕ࡞ࡒ࠾࠙ࡓว㊄ࠢ࡜࠶࠼᧚ᢿ㕙ߦㆡ↪ߒ 17µm ߩᷓߐಽ⸃⢻ߢ⣣㘩㔚૏ߩಽᏓ᷹ቯߦ೑↪ߒߚታ❣ࠍᜬߟ 1㧕‫ޕ‬f-CMC ߩߐࠄߥࠆ㜞㕙ಽ⸃⢻ൻߦߪ‫࡞࠮ޔ‬ᒻᚑߔࠆࠠࡖࡇ࡜࡝࡯ౝ▤߅ࠃ߮ṁᶧឃ಴ߦ↪޿ࠆࠠࡖࡇ࡜࡝࡯ᄖ▤ࠍࠃࠅዊᓘߣߒ‫ߎߟ߆ޔ‬ࠇࠄࠍ♖ᐲࠃߊゲኻ⒓ߦ㈩⟎ߔࠆߎߣ‫ޔ‬ṁᶧឃ಴ߦߣ߽ߥ߁㔚ᵹᝄേߩシᷫ߇ⷐ᳞ߐࠇࠆ‫ޕ‬ᓥ᧪ߪ⇣ߥࠆ㧞࿑㧝 f-CMC ↪ࠠࡖࡇ࡜࡝࡯వ┵ߩᢿ㕙ᮨᑼ࿑‫ޕ‬ᧄߩࠠࡖࡇ࡜࡝࡯ߦࠃࠅ૞⵾ߒߚ߇‫ ޔ‬㧔Ꮐ㧕ᓥ᧪ߪ㧞ߟߩࠠࡖࡇ࡜࡝࡯ࠍหゲ㈩⟎ߒߡ޿ᧄ⎇ⓥߢߪࡑ࡞࠴ࡃ࡟࡞ࠠࡖࡇ࡜࡝ߚ߇♖ᐲߣᓸዊൻߦ㔍ὐ߇޽ߞߚ‫ޕ‬㧔ฝ㧕㧣ch ࡃ࡟࡯ࠍ೑↪ߒߚᣂဳ f-CMC ࠍ㐿⊒ߒ‫ޔ‬࡞ࠠࡖࡇ࡜࡝࡯ࠍ↪޿ࠆߣ‫ޔ‬ឃ಴ญ߇ಽᢿߐࠇࠆ

㘧べ⊛ߥᓸዊൻ߅ࠃ߮㜞♖ᐲൻࠍ⁓߇‫ޔ‬ଏ⛎ญߦኻߒߡ♖ᐲࠃߊหゲߣߥࠆઁ‫ޔ‬ኈᤃߦ߁㧔࿑㧝ෳᾖ㧕‫ޕ‬ᓸዊൻߢ߈ࠆ‫ޕ‬㧙㧙㧞㧚ࡈࡠ࡯ဳࠠࡖࡇ࡜࡝࡯ᓸዊ࠮࡞ᴺ
㧔f-CMC㧕 f-CMC ߩේဳߢ޽ࠆ CMC ߪ⋥ᓘᢙmm ⒟ᐲߩࠟ࡜ࠬࠠࡖࡇ࡜࡝࡯ࠍടᾲ࡮ᑧિ࡮ಾᢿߒߡᓧߚవ┵㐿ญㇱ߆ࠄ㔚⸃⾰ṁᶧࠍ⹜ᢱ⴫㕙ዪᚲߦଏ⛎ߒ‫ޔ‬ṁᶧߩធ⸅㕙ࠍ⹜ᢱ㔚ᭂߣߔࠆ 2)‫ࡖࠠޕ‬ࡇ࡜࡝࡯ౝㇱߦߪኻᭂ߅ࠃ߮ෳᾖ㔚ᭂ߇㈩⟎ߐࠇߡ߅ࠅ‫ޔ‬ㅢᏱࠨࠗ࠭ߩ㧟㔚ᭂ♽㔚᳇ൻቇ࠮࡞ห᭽ߦ޽ࠄࠁࠆ㔚᳇ൻቇ᷹ቯᴺߦኻᔕน⢻ߢ޽ࠆ‫ޕ‬࿑㧞ߦf-CMC ߩⵝ⟎᭎⇛࿑ࠍ␜ߔ‫ޕ‬f-CMC ߢߪᓸዊ࠮࡞ਛߩ㔚⸃⾰ṁᶧࠍ੤឵ߔࠆ
ߚ߼ߦࠠࡖࡇ࡜࡝࡯ࠍੑ㊀᭴ㅧߣߒṁᶧߩଏ⛎ߣឃ಴ߩᯏ⢻߇ઃਈߐࠇߡ޿ࠆ‫ߩဳ࡯ࡠࡈޕ‬႐ว‫ߦ․ޔ‬⣣㘩෻ᔕߩࠃ߁ߦṁᶧߩᳪᨴ߇໧㗴ߣߥࠆ෻ᔕ♽࿑㧞 f-CMC ⵝ⟎ߩ᭎⇛࿑‫ޕ‬ᓸዊ㔚᳇ൻቇ࠮࡞

ߢ߽ṁᶧỚᐲࠍ৻ቯߦ଻ᜬߢ߈ࠆઁ‫ޔ‬ߪ‫࡯࡝࡜ࡇࡖࠠޔ‬ౝ▤ߣ⹜ᢱߩ㑆ߦᒻᚑߒ‫ޔ‬ㆊ

‛⾰⒖േ߇ଦㅴߐࠇࠆߚ߼ߦㅢ㔚㔚ᵹ೾ߥṁᶧߪๆᒁࡐࡦࡊߦធ⛯ߒߚࠠࡖࡇ࡜࡝࡯߇৻ᩴએ਄ᄢ߈ߊߥࠆലᨐ߇޽ࠆ‫ߎޕ‬ᄖ▤߆ࠄឃ಴ߔࠆ‫ޕ‬ߩ㔚ᵹჇᄢലᨐߪ‫ߩ࡞࠮ޔ‬ᓸዊൻߦߣ
߽ߥ޿ࠃࠅᓸᒙߦߥࠆㅢ㔚㔚ᵹߩᬌ಴ߦኻ᛫ߔࠆߩߢ‫ޔ‬CMC ᴺߩ㜞㕙ಽ⸃⢻ൻߦᭂ߼ߡ㊀ቲߢ޽ࠆߣᦼᓙߐࠇࠆ‫ޕ‬
3. ṁᶧࡈࡠ࡯ߦߣ߽ߥ߁‛⾰⒖േଦ
ㅴലᨐ 3)
 ‛⾰⒖േଦㅴߩᵹ૕ജቇ⊛ലᨐࠍᬌ⸛ߔࠆߚ߼‫ޔ‬ᄖ࿤㔚ሶ⒖ォ෻ᔕဳ࡟࠼࠶
ࠢࠬࡔ࠺ࠖࠛ࡯࠲ߩਇᵴᕈ㊄ዻ㔚ᭂ਄ߢߩಽᭂታ㛎ࠍⴕ޿‫ޔ‬㒢⇇㔚ᵹታ㛎ᑼߩዉ಴ࠍ⹜ߺߚ‫ޕ‬㔚⸃ᶧߦߪK4[Fe(CN)6]
᳓ṁᶧࠍ‫ޔ‬㔚ᭂ⹜ᢱߦߪPt᧼ࠍ↪޿‫ޔ‬2บߩࡐࡦࡊࠍ↪޿ߡหゲੑ㊀᭴ㅧ࿑㧟 หゲੑ㊀ဳ f-CMC ࠍ↪޿ߚ 1 mol m-3f-CMCߩࠠࡖࡇ࡜࡝࡯ౝ▤߆ࠄ㔚⸃ᶧ

K4[Fe(CN)6]᳓ṁᶧߩ CV‫ޕ‬dE/dt = 10 mV s-1, wࠍଏᶧ㧔ଏ⛎㊂Vf=0–17.9x10-9 m3 s-1㧕‫ޔ‬= 86 µm, rin = 290 µm, h = 56 µm

㧙㧙ᄖ▤߆ࠄឃᶧߒ‫࡯࡝࡜ࡇࡖࠠޔ‬వ┵ߣ⹜ᢱߣߩ㑆ߦ㔚⸃ᶧߩᶧṢࠍᒻᚑߒߚ‫࡜ࡇࡖࠠޕ‬࡝࡯ౝ▤ߦ⊕㊄ኻᭂ߅ࠃ߮㌁/Ⴎൻ㌁ෳᾖ㔚ᭂࠍ㈩⟎ߒ‫ޔ‬ᶧṢធ⸅㕙ࠍ⹜ᢱ㔚ᭂߣߔࠆਃ
㔚ᭂᴺߦࠃࠅേ㔚૏ಽᭂߒߚߣߎࠈ‫ޔ‬f-CMCࡄ࡜ࡔ࡯࠲࡯ߦଐሽߒߚ[Fe(CN)6]4-ߩ㉄ൻ෻ᔕߦߣ߽ߥ߁㒢⇇㔚ᵹIL߇ᵹࠇࠆ‫ߩߎޕ‬ILߪ‫ޔ‬ଏ⛎㊂VfࠍჇ߿ߔߥߤf-CMCࡄ࡜ࡔ࡯࠲࡯
ߩᄌᦝߦࠃࠅ㗼⪺ߦჇടߔࠆ㧔࿑3ෳᾖ㧕ߎߣ߆ࠄ‫ޔ‬ṁᶧࡈࡠ࡯ߦߣ߽ߥ޿㔚ᭂ⇇㕙߳ߩ
‛⾰⒖േ߇ᵹ૕ജቇ⊛ߦଦㅴߐࠇࠆߎߣߪ᣿ࠄ߆ߢ޽ࠆ‫ޕ‬ILߩฦf-CMCࡄ࡜ࡔ࡯࠲࡯ߦኻ
ߔࠆଐሽᕈࠍᬌ⸛ߒߚ⚿ᨐ㧔Table 1ෳᾖ㧕‫ޔ‬หゲဳf-CMCߩ㒢⇇㔚ᵹታ㛎ᑼߪએਅߩࠃ
߁ߦਈ߃ࠄࠇࠆ‫ޕ‬

I limit2S nFDcw1 2 1.19Vf rin-1 3h 1 6Q 1  99rin1 2(1)ߎߎߢ㧘n ߪ෻ᔕ㔚ሶᢙ㧘F ߪࡈࠔ࡜࠺࡯ቯᢙ㧘D ߪ෻ᔕ‛ߩ᜛ᢔଥᢙ㧘c ߪ෻ᔕ‛Ớᐲ㧘w ߪࠠࡖࡇ࡜࡝࡯ౝ▤ოෘ㧘rin ߪࠠࡖࡇ࡜࡝࡯ౝ஥ඨᓘ㧘h ߪ࠮࡞㜞ߐ㧘Qߪṁᶧേ☼ᐲߢ޽ࠆ‫(ޕ‬1)ᑼߦ߅ߌࠆ‛⾰⒖േߦ㑐ࠊࠆ㗄ࠍએਅߩࠃ߁ߦᢛℂߔࠆߎߣ߇ߢ߈ࠆ‫ޕ‬km,D2S w1 2 1.19Vf rin-1 3h 1 6Q 1  99rin1 2(2)I limitnFkm,D Dc(3)ߎߩ‛⾰⒖േଥᢙ km,D ߪหゲဳ f-CMC ߦᵹࠇࠆ㔚ᵹߩᵹ૕ജቇ⊛ലᨐߦଐሽߒߚ‛⾰⒖േࠍⷙᩰൻߔࠆ㓙‫᦭ޔ‬ലߢ޽ࠆ‫ޔ߅ߥޕ‬ฦ᧦ઙߦ߅ߌࠆ㒢⇇㔚ᵹታ㛎୯ߣ(1)ᑼߦၮߠߊ
⸘▚୯ߩ஍Ꮕߪ 9.5㧑એౝߢ޽ߞߚ‫ޕ‬
Table 1

Dependence of f-CMC parameters.

Parameter

equationconstants

c0IL

ac0

a = 1.51x10-5 A m3 mol-1ILaDa = 3.09x103 A s m-2ILara = 1.51x10-2 A m-1

ILcaVf  I L,0a = 4.17x102 A s m-3

Dr
VfI L,0c r

b = 1.11x10-2 A m-1

bwd log r d log w

hd log( I L / r ) d log hrind log d I L r dVf^

a = 0.57 ( | 1/2)a` log rd log( I Lc ,0 w1/2 ) d log rin

Qd log I L d log Q

a = -0.17 ( | -1/6)

ainaaa㧙㧙a = -0.33 ( | -1/3)
a = 0.46 ( | 1/2)
a = -0.99 ( | -1)㧠㧚ࡑ࡞࠴ࡃ࡟࡞ဳ f-CMC ߩ૞⵾ ౝᓘ 1 mm‫ޔ‬ᄖᓘ 1.4 mm ߩࡄࠗ࡟࠶ࠢࠬࠟ࡜ࠬࠠࡖࡇ࡜࡝࡯ࠍ㧣▤᧤ߨ‫ޔ‬ടᾲ‫ᝳޔ‬ォ‫ޔ‬ᑧિߒߥ߇ࠄಾᢿߒߚᓟ‫ޔ‬వ┵ࠍ⎇⏴ߒߚ‫ޕ‬Ⴎൻ㌁ߢⷒࠊࠇߚ㌁✢㧔ෳᾖ㔚ᭂ㧕ߣ⊕㊄✢㧔ኻᭂ㧕ࠍࠠࡖࡇ࡜࡝࡯ਛᔃ▤ߦᝌ౉ߒ‫ࠍࠇߎޔ‬ṁᶧߩଏ⛎ߦ‫ޔ‬ᄖ஥㧢▤ࠍṁᶧߩឃ಴ߦ↪޿ߡ f-CMC ߣߒߚ‫▤࡞࡟ࡃ࠴࡞ࡑߥ⊛ဳౖޕ‬వ┵ߩశቇ౮⌀ࠍ࿑ 4 ߦ␜ߔ‫ޕ‬஥▤߇ਛᔃ▤ߩ๟ࠅࠍゲኻ⽎ߦขࠅ࿐ߺ‫ޔ‬f-CMC ߦⷐ᳞ߐࠇࠆࠠࡖࡇ࡜࡝࡯వ┵ߩ࡟ࠗࠕ࠙࠻ࠍหゲੑ㊀ဳࠃࠅ߽ኈᤃߦᓧࠆߎߣ߇ߢ߈ߚ‫ޕ‬ᶧṢ࠮࡞ߩᓸዊൻ‫ࡃ࠴࡞ࡑߜࠊߥߔޔ‬࡟࡞▤వ┵ߩᓸዊൻߪ‫ޔઁߩ࠭ࠗࠨ࡯࡝࡜ࡇࡖࠠࠆ޿↪ޔ‬ടᾲ‫ᝳޔ‬ォ‫ޔ‬ᑧિ᧦ઙߦ㗼⪺ߦᏀฝߐࠇߚ‫᧦ޕ‬ઙ߇ᢛࠊߥ޿႐ว‫ޔ‬ᄖ▤߇஍⧌ߒߚࠠࡖࡇ࡜࡝࡯▤వ┵߇ᓧࠄࠇ‫ޔ‬ᒻᚑߔࠆᶧṢ࠮࡞ߩゲኻ⒓ᕈ߇៊ߥࠊࠇߚ‫⃻ޕ‬࿷ߩߣߎࠈ‫ޔ‬ゲኻ⒓ᕈߩ⦟ᅢߥࡑ࡞࠴ࡃ࡟
࡞ဳ f-CMC ਛᔃ▤ߩᦨዊౝᓘߪ‫ޔ‬27 µm ߢ޽ࠆ‫ޕ‬ ࿑ 5 ߦࡑ࡞࠴ࡃ࡟࡞ဳ f-CMC ࠍ↪޿ߡᓧࠄࠇߚᄖ࿤㔚ሶ⒖ォ෻ᔕဳ࡟࠼࠶ࠢࠬࡔ࠺ࠖࠛ࡯࠲ߩਇᵴᕈ㊄ዻ㔚ᭂ਄ߢߩࠨࠗࠢ࡝࠶ࠢࡏ࡞࠲ࡕࠣ࡜ࡓࠍ␜ߔ‫ޕ‬หゲੑ㊀▤᭴ㅧߩᓥ᧪ဳߣᲧߴᣂဳߢߪ‫ޔ‬㔚ᵹࡁࠗ࠭߇ỗᷫߒ‫ߥ߆ࠄߛߥޔ‬㔚ᵹ゠〔߇ឬ߆ࠇߡ޿ࠆߎߣߪ᣿ࠄ߆ߢ޽ࠆ‫ޔߪࠇߎޕ‬ᓥ᧪ဳߢߪᄖ▤ౝߢᄙዋᝄേߒߡ޿ߚਛᔃ▤߇‫ޔ‬ᣂဳߢߪࠠࡖࡇ࡜࡝࡯వ┵ߦ߅޿ߡ߽ᄖ▤ߣ࿕ቯߐࠇߚߚ߼‫ޔ‬ṁᶧࠍ࿁෼ឃ಴ߔࠆ㓙ߩ࿶ജᄌേ╬ࠍᶧṢ࠮࡞߇ฃߌߥߊߥߞߚߎߣߦࠃࠆߣ⺑᣿ߐࠇࠆ‫ޔߚ߹ޕ‬㔚૏⿛ᩏㅦᐲࠍ 500 mV s-1
߹ߢჇ߿ߒߡ߽ห᭽ߥ㔚ᵹ゠〔߇ᓧࠄࠇ‫ޔ‬㒢⇇㔚ᵹ୯ߦᄌൻߪ⷗ࠄࠇߥ߆ߞߚ‫ޔߪࠇߎޕ‬ᵹ૕ജቇ⊛ߦ‛⾰⒖േ߇ⷙ೙ߐࠇߡ޿ࠆߚ߼‫ޔ‬㔚ᭂ⴫㕙ߦ᜛ᢔጀ߇቟ቯߒߡᒻᚑߔࠆߎߣࠍᗧ๧ߔࠆ‫ޕ‬4-6

I / 10 A32
100.0

0.2

0.4

0.6

0.8

E / V vs. Ag/AgCl

1.0࿑ 5 ࡑ࡞࠴ࡃ࡟࡞ဳ f-CMC ࠠࡖࡇ࡜࡝࡯࿑ 4 ࡑ࡞࠴ࡃ࡟࡞ဳ f-CMC ࠠࡖࡇ࡜࡝࡯వ┵ߩశቇ౮⌀ࠍ↪޿ߡᓧࠄࠇߚ 1 mol m-3 K4[Fe(CN)6]᳓

ṁᶧߩ CV‫ޕ‬dE/dt = 10 mV s-1, w = 50 µm,
rin = 150 µm, h = 30 µm

㧙㧙㧡㧚fгCMC ᓸዊൻߦߣ߽ߥ߁ᑷኂ หゲੑ㊀ဳ f-CMC ࠍ↪޿ߚ NaCl ᳓ṁᶧ(pH=3)ਛߩࠕ࡞ࡒ࠾࠙ࡓߩಽᭂᦛ✢ࠍ࿑ 6ߦ␜ߔ‫ޔߪߢߎߎޕ‬ㅢ㔚㔚ᵹࠍ‛⾰⒖േଥᢙߢ㒰ߒ‫ޔ‬ᵹ૕ജቇ⊛ലᨐࠍⷙᩰൻߒߚ㔚ᵹゲࠍ↪޿ߡ޿ࠆ‫ߩࡓ࠙࠾ࡒ࡞ࠕޕ‬ṁ⸃෻ᔕߦኻᔕߔࠆࠕࡁ࡯࠼㔚ᵹߪ rin ߦଐࠄߥ޿߇㧘৻ᣇߢ᳓⚛⊒↢߅ࠃ߮ṁሽ㉄⚛ߩㆶర෻ᔕߦ⿠࿃ߔࠆࠞ࠰࡯࠼㔚ᵹߪ rin < 50 µm ߢᄢ߈3-210844266235-510-610-710-1.2-1.0

E / V (SHE)-1.1-1.0-0.9

2-3-1(I / km,D) / A m s-410(-I / km,D) / 10 A m s-310-1rin / µm38-0.8-0.6-0.4

E / V (SHE)-0.2

100.0050100150

rin / µm

200250࿑ 6㧔Ꮐ) f-CMC ࠍ↪޿ߚ NaCl ᳓ṁᶧ(pH=3)ਛߩࠕ࡞ࡒ࠾࠙ࡓ㧔⚐ᐲ 99.9%㧕ߩ-1-6I / 10 A

3-60-I (E = -0.4 V vs. Ag/AgCl) / 10 Aേ㔚૏ಽᭂᦛ✢㧔ฝ) f-CMC ࠞ࠰࡯࠼㔚ᵹߩࠠࡖࡇ࡜࡝࡯ౝ▤ rin ଐሽᕈArgon
Air-2

Oxygen-3-0.50.00.5

E / V vs. Ag/AgCl

1.0210020406080100120

3poxygen / 10 Pa࿑ 7㧔Ꮐ㧕ࡑ࡞࠴ࡃ࡟࡞ဳ f-CMC ࠠࡖࡇ࡜࡝࡯ࠍ↪޿ߡᓧࠄࠇߚ 0.5 mol m-3 H2SO4 ᳓ṁᶧߩ⊕㊄਄ߢߩ CV‫ޕ‬dE/dt = 50 mV s-1, r = 175 µm, h = 200 µm㧔ฝ㧕ṁሽ㉄⚛ㆶర㔚ᵹ㧔E= -0.4 V vs. Ag/AgCl㧕ߩ᳇⋧㔓࿐᳇ਛ㉄⚛ಽ࿶ଐሽᕈ㧙㧙޿‫ ߩߎޕ‬rin ߩ 50 µm ߪ࠮࡞㜞ߐ h ߦ৻⥌ߒߡ߅ࠅ‫ޔ‬rin ߇ h ࠃࠅ߽ዊߐߊߥࠆߣࠞ࠰࡯࠼㔚ᵹ߇㗼⪺ߦߥࠆߎߣ߇ࠊ߆ߞߚ‫ޕ‬ ࿑ 7 ߦฦ⒳᳇⋧㔓࿐᳇㧔ࠕ࡞ࠧࡦ㧘ⓨ᳇㧘㉄⚛㧕ਛ‫ޔ‬0.5 mol dm-3 H2SO4 ᳓ṁᶧࡑ࡞࠴ࡃ࡟࡞ဳ f-CMC ࠍ↪޿ߚ⊕㊄ߩಽᭂᦛ✢ࠍ␜ߔ‫ޕ‬ṁሽ㉄⚛ߩㆶర㔚ᵹߪ᳇⋧㔓࿐᳇ਛߩ㉄⚛Ớᐲߣߣ߽ߦჇടߒߡ߅ࠅ‫ޔ‬᳇⋧㔓࿐᳇ਛ㉄⚛ߩṁሽߣ㔚ᭂ߳ߩ᜛ᢔ߇⏕߆߼ࠄࠇߚ‫ޕ‬ṁᶧࠍࡈࡠ࡯ߔࠆߎߣߦࠃࠅ‫ޔ‬᳇⋧㔓࿐᳇ਛߩ㉄⚛ಽ࿶ߦኻᔕߔࠆ㉄⚛߇᳇ᶧ⇇㕙߆ࠄṁߌㄟߺ‫ޔ‬㔚ᭂ⴫㕙߳᜛ᢔߐࠇ‫ޔ‬㔚ᭂ෻ᔕߦነਈߔࠆߎߣ߇⏕⹺ߐࠇߚ‫ࠕޔ߅ߥޕ‬࡞ࠧࡦ㔓࿐᳇ߦ߅޿ߡ߽⋧ᒰ㊂ߩṁሽ㉄⚛ߩㆶర㔚ᵹ߇ᬌ಴ߐࠇࠆ߇‫ߪࠇߎޔ‬ਛᔃ▤߆ࠄଏ⛎ߐࠇࠆ *51 ᳓ṁᶧਛߦ੍߼ṁሽߒߡ޿ࠆ㉄⚛ߦࠃࠆ߽ߩߢ޽ࠆ‫ࡦࠧ࡞ࠕޔ߅ߥޕ‬⣕᳇ߒߚṁᶧࠍ↪޿ߡ‫ߩߎޔ‬ṁሽ㉄⚛ߩᓇ㗀ࠍ㒰෰ߔࠆ⹜ߺࠍⴕߞߚ߇‫࠲࡯ࡠߩ⁁⃻ޔ‬࡯ࡐࡦࡊࠍ↪޿ࠆଏᶧࠪࠬ࠹ࡓߢߪ࠴ࡘ࡯ࡉߥߤࠍ੺ߒߡଚ౉ߔࠆ㉄⚛ࠍቢోߦ㒰෰ߒ߈ࠇߕ‫ޔ‬ṁሽ㉄⚛ߩᓇ㗀ࠍήⷞߢ߈ࠆ H%/% ᷹ቯⅣႺ߇ᢛ஻ߢ߈ߡ޿ߥ޿‫ޕ‬ᶧṢߩߺߥࠄߕ‫ో⟎ⵝޔ‬૕ࠍࠣࡠ࡯ࡉࡏ࠶ࠢࠬߦ⸳⟎ߒߡ߽⸃᳿น⢻ߛ߇‫ޔ‬ᠲ૞ᕈ߇ᖡߊߥࠆ‫੹ޕ‬ᓟ‫ဳࠫࡦ࡝ࠪޔ‬ଏᶧࠪࠬ࠹ࡓߥߤ‫ޔ‬ᠲ૞ᕈࠍ៊ߥࠊߥ޿㉄⚛ㆤᢿဳଏᶧࠪࠬ࠹ࡓߦ⟎߈឵߃ࠆ૛࿾߇ᱷߐࠇߡ޿ࠆ‫ޕ‬㧢㧚㜞㕙ಽ⸃⢻ fгCMC ߩ᧚ᢱ⴫㕙ዪㇱ㔚᳇ൻቇ߳ߩዷᦸ ೨ㅀߩࠃ߁ߦ‫᧚ޔ‬ᢱ⴫㕙ዪㇱࠍᢙච µm ߩಽ⸃⢻ߢߩᓸዊ㔚᳇ൻቇ᷹ቯࠍኈᤃߦታ⃻ߔࠆࡑ࡞࠴ࡃ࡟࡞ဳ f-CMC ࠍ㐿⊒ߔࠆߎߣ߇ߢ߈ߚ‫ߩဳ࡞࡟ࡃ࠴࡞ࡑޕ‬㒢⇇㔚ᵹࠍ⴫⃻ߔࠆ‛⾰⒖േଥᢙ߇ᧂᬌ⸛ߢ޽ࠅ‫ߚ߹ޔ‬ṁሽ㉄⚛ߩᓇ㗀ࠍቢోߦ㒰෰ߔࠆⵝ⟎ߩᡷༀ߇ᔅⷐߢ޽ࠆ߇‫ ဳ࡞࡟ࡃ࠴࡞ࡑޔ‬f-CMC ߪ㔚ᵹᔕ╵߅ࠃ߮ S/N Ყߦఝࠇߡ߅ࠅ‫ޔ‬ᓥ᧪ߩหゲੑ㊀ဳࠃࠅ߽ᓸዊ߆ߟ◲ଢߦ૞⵾ߔࠆߎߣ߇ߢ߈ࠆ․㐳ࠍᜬߟ‫⺖ߥ߁ࠃߩߎޕ‬㗴ࠍస᦯ᰴ╙‫ ဳ࡞࡟ࡃ࠴࡞ࡑޔ‬f-CMC ߪฦ⒳ߩ㊄ዻ᧚ᢱߦኻߒߡ᭽‫ߥޘ‬ᓸዊ㔚᳇ൻቇ᷹ቯࠍଏਈߔࠆ᦭ജ࠷࡯࡞ߦߥࠅᓧࠆߣᦼᓙߐࠇࠆ‫ޕ‬㧣㧚⻢ㄉ ᧄ⎇ⓥࠍߏេഥ޿ߚߛ߈߹ߒߚ⽷࿅ᴺੱ JFE21 ਎♿⽷࿅ߦෘߊᗵ⻢޿ߚߒ߹ߔ‫ޕ‬ෳ⠨ᢥ₂
1. K. Fushimi, S. Yamamoto, R. Ozaki, H. Habazaki; Electrochim. Acta, 53, 2529 (2008).
2. ફ⷗౏ᔒ㧘ဈ౉ᱜᢅ㧘᏷ፒᶈ᮸㧧‫࡝࡜ࡇࡖࠠޟ‬ᓸዊ࠮࡞ᴺߦࠃࠆ᧚ᢱ⴫㕙⹏ଔ‫ޠ‬㧘⴫㕙ᛛⴚ, 59(12), 863-868 (2008).
3. K. Fushimi, S. Yamamoto, H. Konno, H. Habazaki; ChemPhysChem, 10, 420 (2009).

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