SPring-8ᚢ⇛ᵴ↪ࡊࡠࠣ࡜ࡓ⺖㗴㧦ᚢ⇛ᵴ↪ࡊࡠࠣ࡜ࡓ⺖㗴೑↪ႎ๔ᦠ

1. ⺖㗴⇟ภ㧦2005B0894
2. ⺖㗴ฬ㧦࿕૕㜞ಽሶᒻΆᢱ㔚ᳰ↪ᒻ⁁೙ᓮ⊕㊄⸅ᇦ૞⵾ߦ߅ߌࠆᷝട‛ߩᓇ㗀(Effects of Additives in Preparation of Shape-Controlled Pt Catalyst for Polymer Electrolyte FuelCells)
3. ታ㛎⠪᳁ฬ෸߮ᚲዻᯏ㑐㧦ታ㛎⽿છ⠪㧦Ⓑ⪲ ⒤(Inaba, Minoru)หᔒ␠ᄢቇ Ꮏቇㇱ ᢎ᝼ (0015064)

౒หታ㛎⠪㧦ೋઍ ༀᄦ(Shodai, Yoshio)หᔒ␠ᄢቇ ․೎⎇ⓥຬ(PD) (0007946)

᧻ᴛ ᐘ৻(Matsuzawa, Koichi)ࢃߌ޿ߪࠎߥ ඳ჻⎇ⓥຬ(PD) (0016354)

ጊ↰ ⵨ਭ(Yamada, Hirohisa)หᔒ␠ᄢቇᄢቇ㒮Ꮏቇ⎇ⓥ⑼ D2 (008776)

᦭෹ ብ᮸(Aritomo, Hiroki)หᔒ␠ᄢቇᄢቇ㒮Ꮏቇ⎇ⓥ⑼ M2 (0013741)

ᓟ⮮ 㓉(Goto, Takashi)หᔒ␠ᄢቇᄢቇ㒮Ꮏቇ⎇ⓥ⑼ M2 (0016545)

ᓼ᳗ ⚐ሶ(Tokunaga, Junko)หᔒ␠ᄢቇᄢቇ㒮Ꮏቇ⎇ⓥ⑼ M2 (0016548)⇌ਛ ⏉(Hatanaka, Aoi)หᔒ␠ᄢቇᄢቇ㒮Ꮏቇ⎇ⓥ⑼ M1 (0016356)

㐳⼱Ꮉ ⺈(Hasegawa, Makoto)หᔒ␠ᄢቇᄢቇ㒮Ꮏቇ⎇ⓥ⑼ M1 (0016551)

ᣂฬ ผᴦ(Niina, Fumiharu)หᔒ␠ᄢቇᄢቇ㒮Ꮏቇ⎇ⓥ⑼ M1 (0016547)

4. ૶↪ࡆ࡯ࡓ࡜ࠗࡦ㧦BL04B2
5. ታ㛎⚿ᨐ㧦એਅߦᷝઃ
The size and surface orientation of Pt nanoparticles greatly affect the catalytic activity for oxygen
reduction in polymer electrolyte fuel cells. To understand the effects of size and surface orientation, Ptnanoparticles with controlled size and surface orientation were prepared.

When the sodium

polyacrylate (PAA) as a capping polymer and iodine ion (I-) as a specific absorption anion were added ina molar ratio of Pt/Poly./I- = 1/12/5, tetrahedral Pt nanocrystals were successfully prepared at a yield of70%. The adsorption state of PAA and I- ion on Pt nanoparticles was investigated by high-energy
X-ray diffraction at SPring-8 (BL04B2).
1. ✜⸒⃻࿷‫ޔ‬࿕૕㜞ಽሶᒻΆᢱ㔚ᳰ(PEFC)ߪΆᢱ㔚ᳰ⥄േゞ↪޽ࠆ޿ߪኅᐸ↪ዊဳࠦࠫࠚࡀ࡟࡯࡚ࠪࡦ߳ߩ↪ㅜߦะߌߡ‫⎇ޔ‬ⓥ㐿⊒߇ㅴ߼ࠄࠇߡ޿ࠆ‫ޕ‬PEFC ߩ㔚ᭂ⸅ᇦߦߪ‫ࡦࡏ࡯ࠞޔ‬਄ߦᄙ⚿᥏૕ߩ⊕㊄(Pt) ࠽ࡁ☸ሶ(⚂ 2-3 nm)ࠍᜂᜬߐߖߚ߽ߩࠍ૶↪ߒߡ޿ࠆ‫ޔߦ⥸৻ޕ‬࿕૕⸅ᇦߩᕈ⢻ߪ⸅ᇦ☸ሶߩᒻ⁁ (㕙ᣇ૏) ߣࠨࠗ࠭ߦଐሽߔࠆߎߣ߆ࠄ‫ޔ‬PEFC ߩ㉄⚛ㆶర෻ᔕᯏ᭴ߩࡕ࠺࡞⸅ᇦߣߒߡ‫ޔ‬ᒻ⁁߅ࠃ߮☸ᓘߩ೙ᓮߐࠇߚ Pt ࠽ࡁ☸ሶߩ૞⵾߇㊀ⷐߣߥࠆ‫ޕ‬⊕㊄࠽ࡁ☸ሶߩᒻ⁁೙ᓮᴺߣߒߡ‫ޔ‬Ⴎൻ⊕㊄㉄ࠞ࡝࠙ࡓ᳓ṁᶧ (K2PtCl4) ߣࡐ࡝ࠕࠢ࡝࡞㉄࠽࠻࡝࠙ࡓ᳓ṁᶧ (ࡐ࡝ࡑ࡯) ࠍᷙวߒ‫ޔ‬H2 ࠟࠬࠍᵹㅢߐߖ‫ ޔ‬Pt2+ ߩㆶరࠍⴕ߁ᣇᴺ߇ႎ๔ߐࠇߡ޿ࠆ 1-2)‫ޕ‬− 191 −

ߎߩᣇᴺߢߪ‫ߩ࡯ࡑ࡝ࡐޔ‬ᷝട㊂ࠍᄌൻߐߖࠆߎߣߢᒻ⁁ߩ⇣ߥࠆ Pt ࠽ࡁ☸ሶߩ૞⵾߇น⢻ߢ޽ࠆߣႎ๔ߐࠇߡ޿ࠆ߇‫ޔ‬ౣ⃻ᕈ‫☸ޔ‬ᓘಽᏓߩ⺖㗴߇ᱷࠆߣߣ߽ߦ‫ߩߎޔ‬ᒻ⁁೙ᓮߩ⹦⚦ߥࡔࠞ࠾࠭ࡓߪ
ᧂߛ᣿ࠄ߆ߦߥߞߡ޿ߥ޿‫ߦ߁ࠃߩߎޔߚ߹ޕ‬ᶧ⋧ᴺߦࠃࠆ࠽ࡁࠬࠤ࡯࡞ߢߩ․⇣⊛ߥᒻ⁁⊒⃻ߦߪPt ☸ሶ਄߳ߩࡐ࡝ࡑ࡯߿․⇣ๆ⌕ࠕ࠾ࠝࡦߩๆ⌕‫ޔ‬0 ଔ㊄ዻේሶߤ߁ߒߩ⚿วߥߤ߇‫ޔ‬දᄼ⊛ߦ૞↪
ߒߡ޿ࠆߣ⠨߃ࠄࠇࠆ߇‫⴫ޔ‬㕙⚿วߦߟ޿ߡᬌ⸛߽޽߹ࠅߥߐࠇߡ޿ߥ޿ 3)‫ޕ‬ᧄ⎇ⓥߢߪㆬᛯ⊛ߦ Pt(111) 㕙ߦๆ⌕ߔࠆߣߐࠇߡ޿ࠆ․⇣ๆ⌕ࠕ࠾ࠝࡦࠍᷝടߔࠆߎߣߢ‫ޔ‬Pt(111) 㕙਄ߢߩ☸ሶᚑ㐳ㅦᐲࠍᛥ೙ߒ‫ޔ‬ᒻ⁁೙ᓮߐࠇߚ Pt ࠽ࡁ☸ሶߩ૞⵾ߣ‫⸃ߩࡓ࠭࠾ࠞࡔߩߘޔ‬᣿ࠍ⋡ᜰߒߚ‫੹ޕ‬࿁ߪ․⇣ๆ⌕ࠕ࠾ࠝࡦߣߒߡ‫ߩࡦࠝ࠾ࠕࡦࠥࡠࡂޔ‬ਛߢ Pt ⚿᥏⴫㕙ߦᦨ߽ᒝߊๆ⌕ߔࠆ࡛࠙ൻ‛ࠗࠝࡦ 4-5)ߦ⌕⋡ߒߡ NaI ࠍࡐ࡝ࡑ࡯ߣߣ߽ߦᷝടߒߚ‫ߡߒߘޕ‬ᒻ⁁⊒⃻ᯏ᭴ߩ⸃᣿ߩߚ߼ߦ⊕㊄⴫㕙ߢߩๆ⌕ߩ⴫㕙⚿ว⁁ᘒࠍ᣿ࠄ߆ߦߔࠆᔅⷐ߇޽ࠆߎߣ߆ࠄ SPring-8 ߩ BL04B2 ࡜ࡦ࠳ࡓ♽ࠬ࠹࡯࡚ࠪࡦߩੑゲ࿁᛬⸘ࠍ↪޿ߡ‫⇣․߿࡯ࡑ࡝ࡐޔ‬ๆ⌕ࠕ࠾ࠝࡦߩ Pt ਄ߢߩ㈩૏‫ޔ‬ๆ⌕⁁ᘒࠍᬌ⸛ߒߚ‫ޕ‬
2. ታ㛎ᣇᴺ
2.1 ⊕㊄࠽ࡁ☸ሶߩ૞⵾Ⴎൻ⊕㊄㉄(K2PtCl4, ๺శ⚐⮎Ꮏᬺ⵾)᳓ṁᶧߦࡐ࡝ࠕࠢ࡝࡞㉄࠽࠻࡝࠙ࡓ ([-CH2CH(CO2Na)-]n,Aldrich ␠⵾) ᳓ṁᶧߣ․⇣ๆ⌕ࠕ࠾ࠝࡦߣߒߡ࡛࠙ൻ‛ࠗࠝࡦࠍᚲቯߩࡕ࡞Ყߢᷙวߒ‫ޔ‬pH = 7 ߦ⺞ᢛߒߡ‫ޔ‬25 oC ߩᕡ᷷ᮏౝߦ౉ࠇߚ‫ߩࡓ࠙࡝࠻࠽㉄࡞࡝ࠢࠕ࡝ࡐߚߒ↪૶ޕ‬ᐔဋಽሶ㊂ (Mw) ߪ 5100
ߢ޽ࠆ‫ߩߎޕ‬ᷙวṁᶧࠍలಽߦᡬᜈߒߥ߇ࠄ‫ޔ‬ṁᶧߦ Ar ࠟࠬ (ᄥ㓁᧲ᵗ㉄⚛, G2 ⚐ᐲ 99.9995%) ࠍ90 ಽ㑆ᵹߒ‫ޔ‬లಽߦ⣕᳇ࠍⴕ޿‫ߩߘޔ‬ᓟ H2 ࠟࠬ(᳓⚛⵾ㅧⵝ⟎, Round Science, RHG-1000)ߢ 10 ಽ㑆ᵹㅢߒ‫ޔ‬Pt2+ ߩㆶరࠍⴕߞߚ‫ޕ‬෻ᔕ᷷ᐲߪ 25oC ߣߒߚ‫ޕ‬H2 ࠟࠬᵹㅢᓟ‫ࠍࠦࠬ࡜ࡈ߹߹ߩߘޔ‬ኒ㐽ߒ৻᥅ᡬᜈߒ‫ޔ‬Pt ࠽ࡁ☸ሶߩࠦࡠࠗ࠼ṁᶧࠍ૞⵾ߒߚ 2)‫ޕ‬૞⵾ߒߚ Pt ࠦࡠࠗ࠼ṁᶧߪㅘㆊဳ㔚ሶ㗼ᓸ㏜ (TEM, HITACHI ⵾:H-9000) ߦࠃߞߡ☸ሶߩᒻ⁁ߣ☸ᓘߩⷰኤࠍⴕߞߚ‫ޕ‬TEM ⷰኤߦߪ‫ޔ‬Cu ࡔ࠶ࠪࡘ 200 (ࡎ࡞ࡓࡃ࡯࡞ࡑࠗࠢࡠࠣ࡝࠶࠼) ߦ᳓ࠍṢਅߒቶ᷷ߢੇ῎ߔࠆߎߣߢⷫ᳓ൻߐߖߚᓟ‫ޔ‬Pt ࠦࡠࠗ࠼ṁᶧࠍṢਅߒ‫ޔ‬ቶ᷷ߢੇ῎ߐߖ‫⹜ޔ‬ᢱߣߒߚ‫ޕ‬
2.2 ⊕㊄࠽ࡁ☸ሶߩ㔚᳇ൻቇ⹏ଔ㔚᳇ൻቇ᷹ቯߦߪ‫ࠢࠬࠖ࠺ޔ‬㔚ᭂ߇ࠣ࡜࠶ࠪ࡯ࠞ࡯ࡏࡦ(GC)‫ࠣࡦ࡝ޔ‬㔚ᭂ߇ Pt ߆ࠄߥࠆ࿁ォ࡝ࡦࠣ࠺ࠖࠬࠢ㔚ᭂ(RRDE)ࠍ↪޿ߚ‫ޕ‬Pt ࠦࡠࠗ࠼ṁᶧࠍ㆙ᔃಽ㔌ᴺߦࠃࠅỚ❗ߒ‫ޔ‬GC ਄ߦࠠࡖࠬ࠻ᓟ‫ޔ‬
30oC‫ޔ‬2 ᤨ㑆ⓨ᳇ਛߢੇ῎ߐߖߚ߽ߩࠍ૞↪ᭂߣߒߡ↪޿ߚ‫ޕ‬㆙ᔃಽ㔌(TOMY, GRX-220)ߪ 20,000 rpm ߢ 17ಽ㑆ⴕ޿‫ޔ‬᷷ᐲߪ 15oC ߣߒߚ‫ޕ‬ኻᭂߦ Pt ✢‫ޔ‬ෳᾖᭂ߇นㅒ᳓⚛㔚ᭂ (RHE)ߩਃᭂᑼ࠮࡞ࠍ‫ޔ‬㔚⸃ᶧ
ߦߪ 0.5 M H2SO4 (ᄙ៺ൻቇᎿᬺ, 98 %, ⿥㜞⚐ᐲ)ࠍ↪޿ߚ‫ޕ‬ᓴⅣᑼૐ᷷ᕡ᷷᳓ᮏ (AS ONE㧘LTB-125)ࠍ↪޿ߡ‫ߩ࡞࠮ޔ‬᷷ᐲࠍ 25oC ৻ቯߣߒߚ‫ޕ‬
0.5 M H2SO4 ṁᶧਛߦ Ar ࠟࠬࠍ 30 ಽ㑆ࡃࡉ࡝ࡦࠣߒ‫ޔ‬ṁሽ㉄⚛ࠍ㒰෰ߒߚ‫ޕ‬ᰴߦ‫ޔ‬Ar 㔓࿐᳇ਅߢ࡝ࡦࠣ㔚ᭂࠍ㔚૏⿛ᩏࠍ➅ࠅ㄰ߒߡᵴᕈൻߐߖߚ‫ࠢࠬࠖ࠺ޔߚ߹ޕ‬㔚ᭂߢߪ㜞㔚૏▸࿐߹ߢ㔚૏⿛ᩏࠍⴕ߁ߣ‫ޔ‬㔚ᭂ਄ߦࠠࡖࠬ࠻ߒߚ Pt ࠽ࡁ☸ሶߩ⚿᥏㕙߇ੂࠇߡߒ߹߁น⢻ᕈ߇޽ࠆߚ߼ 6)‫ޔ‬㔚૏▸࿐
0.05 ~ 1.4 V ࠍ 50 mV s-1 ߢ 15 ࠨࠗࠢ࡞ⴕ޿㔚ᭂࠍᵴᕈൻߐߖ‫ߩߘޔ‬ᓟߪ 0.05 ~ 0.85 V ߩ㔚૏▸࿐ߢ‫ޔ‬቟ቯߥࡏ࡞࠲ࡕࠣ࡜ࡓ߇ᓧࠄࠇࠆ߹ߢ㔚૏⿛ᩏࠍ➅ࠅ㄰ߒߚ‫ޕ‬− 192 −

− 193 −3.2 ⊕㊄࠽ࡁ☸ሶߩ㔚᳇ൻቇ⹏ଔ
0.8M)ߩ᧦ઙߢ૞⵾ߒߚ Pt ࠽ࡁ☸ሶ߅ࠃ߮‫ࠍࠇߘޔ‬㔚૏ࠨ

0.6ࠗࠢ࡞ߒߡᄙ⚿᥏ൻߐߖߚࠨࠗࠢ࡝࠶ࠢࡏ࡞࠲ࡕࠣ࡜

0.4ࡓߩ⚿ᨐࠍ␜ߔ‫⊕ޕ‬㊄ߩන⚿᥏㔚ᭂߩࠨࠗࠢ࡝࠶ࠢࡏ࡞
࠲ࡕࠣ࡜ࡓߦߟ޿ߡߪ 0.55 V ߦ Pt(111) 㕙‫ޔ‬0.27 V ߦPt(100) 㕙‫ޔ‬0.12 V ߦ Pt(110) 㕙ߦ⿠࿃ߔࠆ᳓⚛ๆ⣕⌕ᵄ߇⃻ࠇࠆߣႎ๔ߐࠇߡ޿ࠆ 10-11)‫ޕ‬Pt/PAA/I- = 1/12/5 ߩ႐ว‫ޔ‬ࠨࠗࠢ࡞ೋᦼߦߪ᳓⚛ๆ⣕⌕ᵄߪ⷗ࠄࠇߥ߆ߞߚ‫ࠇߎޕ‬I / mA

Fig. 2 ߦ Pt/PAA/I- = 1/12/5 (10-4 M)‫ޔ‬Pt/ PAA= 1/50 (10-4ࠆน⢻ᕈ߇޽ࠆߣ⠨߃‫ޔ‬᳓⚛㔚૏஥ (-0.1-0.05 V) ߢ 10ࠨࠗࠢ࡞ⴕ޿‫࡛࠙ޔ‬ൻ‛ࠗࠝࡦࠍ Pt(111) 㕙߆ࠄ⣕⌕ߒߡ᷹ቯߒߚߣߎࠈ 12)‫ޔ‬0.55 V ઃㄭߦ Pt(111) 㕙ߦ⿠࿃ߔ

Pt/Poly.=1/50

0.2
0-0.2-0.4-0.6-0.8

ߪ‫⇣․ޔ‬ๆ⌕ࠗࠝࡦߢ޽ࠆ࡛࠙ൻ‛ࠗࠝࡦ߇ Pt(111) 㕙߳ߩๆ⌕ജ߇ᒝߔ߉ߡ Pt(111) 㕙਄ࠍⷒߞߡߒ߹ߞߡ޿

Pt/Poly./I-=1/12/5
After cycled

00.2

0.40.6

E / V vs. RHE0.8

Fig. 2 Cyclic voltammograms of Ptnanoparticles before and after repeatedpotential cycling at 50 mVs-1 in 0.5 M
H2SO4 under Ar atmosphere.

ࠆߣ⠨߃ࠄࠇࠆ᳓⚛ๆ⣕⌕ᵄ߇⃻ࠇߚ‫⚿ߩߎޕ‬ᨐ‫ޔ‬Pt/PAA/I- = 1/12/5 ߩ᧦ઙߢ૞⵾ߒߚ߽ߩߪ Pt(111)㕙ࠍᜬߟ tetrahedral Pt ࠽ࡁ☸ሶߢ޽ࠆߣ⠨߃ࠄࠇࠆ‫ߩߘޔߒ߆ߒޕ‬᳓⚛ๆ⣕⌕ᵄߪ㗼⪺ߥ߽ߩߢߪߥ
߆ߞߚ‫ߩߘޕ‬ℂ↱ߣߒߡ⣕⌕ߒߚ࡛࠙ൻ‛ࠗࠝࡦ߇ౣ߮ Pt(111) 㕙ߦๆ⌕ߒߡ޿ࠆน⢻ᕈ߇޽ࠆ‫߹ޕ‬ߚ‫ޔ‬Pt/ PAA= 1/50 (10-4 M)ߩ᧦ઙߢ૞⵾ߒߚ Pt ࠽ࡁ☸ሶߦߟ޿ߡᄙ⚿᥏ Pt ߩ․ᓽߢ޽ࠆ 0.13 V ߣ 0.27
V ߩ㔚૏ߦࡉࡠ࡯࠼ߥ᳓⚛ๆ⣕⌕ᵄ߇⷗ࠄࠇ‫ޔ‬ᄙ⚿᥏☸ሶߢ޽ࠆߣ⠨߃ࠄࠇࠆ‫ޕ‬
3.3 ⊕㊄࠽ࡁ☸ሶߩ᭴ㅧ⸃ᨆ
Pt/Poly./I- = 1/12/5 (10-4 M)ߩ᧦ઙߢ૞⵾ߒߚ Pt ࠽ࡁ☸

5ሶṁᶧߩ᭴ㅧ࿃ሶ S(Q)ࠍ৻଀ߣߒߡ Fig. 3 ߦ␜ߔ‫ޕ‬Q < 64ࠢߪ‫ࠍߺߩࡓ࠙࡝࠻࠽㉄࡞࡝ࠢࠕ࡝ࡐޔ‬᳓ߦṁ⸃ߐߖߚ3⹜ᢱߦኻߒߡ߽᷹ⷰߐࠇߡ߅ࠅ‫࡝࠻࠽㉄࡞࡝ࠢࠕ࡝ࡐޔ‬࠙ࡓ߇ή⒎ᐨߦಽᢔߒߡ޿ࠆߩߢߪߥߊ‫ޔ‬ṁᇦਛߦ৻ቯ

S(Q)Å-1 ߦ㕖Ᏹߦ㍈޿ࡇ࡯ࠢ߇ᄙᢙ᷹ⷰߐࠇߚ‫࡯ࡇߩࠄࠇߎޕ‬2ߩ㐳〒㔌⒎ᐨࠍ଻ߞߡሽ࿷ߒߡ޿ࠆߎߣࠍ੍᷹ߐߖߚ‫ޕ‬1ᓧࠄࠇߚ S(Q)ࠍ߽ߣߦో⋧㑐㑐ᢙ T(r)ࠍ▚಴ߒ‫ߩߘޔ‬0⚿ᨐࠍ Fig. 4 ߦ␜ߔ‫࡯ࡑ࡝ࡐޕ‬ౝߦሽ࿷ߔࠆ C-H ⋧㑐߿᳓ಽሶౝߦሽ࿷ߔࠆ O-H ⋧㑐ߪ‫ޔ‬᳓⚛ߩᢔੂ⢻߇ૐ޿ߚ߼߶ߣࠎߤ⏕⹺ߐࠇߥ޿‫ޕ‬1.6 Å ઃㄭߦ⷗ࠄࠇࠆ⋧㑐ߪ‫ޔ‬ࡐ࡝ࡑ࡯ౝߦሽ࿷ߔࠆ C-C ⋧㑐ߦ⋧ᒰߔࠆ‫ޕ‬Pt-Pt ߩ⚿ว

05r/Å

1015

Fig. 3 Structure factor (S(Q)) of Pt
nanoparticle colloids of Pt/Poly./I=1/12/5 (10-4 M).

㑆〒㔌ߪ⚂ 2.7 Å16)ߣႎ๔ߐࠇߡ޿ࠆ߇‫੹ޔ‬࿁ߩ᷹ቯߢߪ‫ޔ‬ṁᇦߣߒߡ↪޿ߚ᳓ߩ O-O ⋧㑐(⚂ 2.9 Å)
ߣ㊀ߥࠆߎߣ߇੍᷹ߐࠇߚ‫ޔࠄ߇ߥߒ߆ߒޕ‬Fig. 4(a)ߩ Pt ߇ሽ࿷ߔࠆ T(r)ߢߪ‫⋧ޔ‬㑐ࡇ࡯ࠢ߇ 3 Å ߆ࠄ2.8 Å ߦࠪࡈ࠻ߒߡ޿ࠆߎߣ߇᷹ⷰߐࠇ‫ޔ‬Pt-Pt ⋧㑐ߩሽ࿷ࠍ␜ໂߒߚ‫ޕ‬4 㨪6 Å ߩ▸࿐ߢ⋧㑐ࡇ࡯ࠢߦ㆑޿߇⷗ࠄࠇߚ‫ޕ‬FT-IR ߩ⚿ᨐ߆ࠄࡐ࡝ࠕࠢ࡝࡞㉄ࠍ↪޿ߡ૞⵾ߒߚ Pt ࠽ࡁ☸ሶߢߪ Pt ේሶߩ਄ߦࠞ

− 194 −࡞ࡏࠠࠪ࡞ၮߩ O ේሶ߇⚿วߒߡ޿ࠆߣႎ๔ߐࠇߡ߅ࠅ 3)‫⋧ߩߘޔ‬㑐ߦ⋧ᒰߔࠆߣᦼᓙߐࠇߚ߇‫ޔ‬Ớᐲߩ㜞޿♽ Pt/Poly. = 1/50 (10-2 M)ߦኻߔࠆ T(r)ਛ(Fig.4(b))ߢߪ‫⋧ߩߘޔ‬㑐߇චಽߦ᷹ⷰߐࠇߡ߅ࠄߕ‫ޔ‬ᢿቯߔࠆߦߪ⥋ࠄߥ߆ߞߚ‫ޕ‬
2020a)

Pt+Poly.+I-15I-T(r) /4(r)T(r) /4(r)1510500.5 2

46r/Å8b)10500.5 2

10Pt+Poly.
Poly.

46r/Å810Fig. 4 Total correlation function (T(r)) of Pt nanoparticle colloids of a) Pt/Poly./I=1/12/5 (10-4 M) and b) Pt/Poly. =1/50 (10-2 M) with and without Pt nanoparticle.

4. ⚿⸒PEFC ߩ㉄⚛ㆶర෻ᔕᯏ᭴ߩࡕ࠺࡞⸅ᇦࠍ⋡ᜰߒߡ‫ޔ‬ᒻ⁁ߩ೙ᓮߐࠇߚ Pt ࠽ࡁ☸ሶߩ૞⵾ࠍ⹜ߺߚ‫ޕ‬․⇣ๆ⌕ࠕ࠾ࠝࡦߣߒߡ‫࡛࠙ޔ‬ൻ‛ࠗࠝࡦࠍ↪޿‫ޔ‬Pt/PAA/I-=1/12/5 ߩ᧦ઙߢ‫ޔ‬tetrahedral Pt ࠽ࡁ☸ሶ
߇⚂ 7 ഀ⒟ᐲ૞⵾ߐࠇߚ‫ޕ‬㔚᳇ൻቇ᷹ቯߦࠃߞߡ Pt(111)㕙ߦࠃߞߡ᭴ᚑߐࠇࠆ Pt ࠽ࡁ☸ሶߢ޽ࠆߎߣ
߇⏕⹺ߐࠇߚ‫ޔࠄ߇ߥߒ߆ߒޕ‬᭴ㅧ⊛ߥ⸃ᨆ߆ࠄߪࡐ࡝ࡑ࡯ߣ․⇣ๆ⌕ࠕ࠾ࠝࡦߣߩᷝടߩ᦭ήߦࠃ
ࠆᏅߪ⷗ࠄࠇߕ‫ޔ‬tetrahedral Pt ࠽ࡁ☸ሶߩᒻᚑߩᩮ᜚ߣߥࠆๆ⌕⁁ᘒߪ㗼⪺ߦ⏕⹺ߢ߈ߥ߆ߞߚ‫ޕ‬ෳ⠨ᢥ₂1)

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