2009A1857                          BL14B2

㑄⛣㔠ᒓࣇࢱࣟࢩ࢔ࢽࣥࢆ࣮࣋ࢫ࡟ࡋࡓⅣ⣲ᮦᩱゐ፹࡟࠾ࡅࡿ㑄⛣㔠ᒓࡢ㓟⣲㑏ඖάᛶ࡟ᑐࡍࡿᙺ๭
Roles of Transition-Metal Atoms for Oxygen Reduction Reaction inTransition-Metal Phthalocyanine-Based Carbon Catalystsᑠᯘ ṇ㉳ a,b, ୹⩚ ⚽἞ a, 㰻⸨ ಙ a, ཎ⏣ ឿஂ a,b, ᑿᔱ ṇ἞ a,b,኱ῲ ༤ᐉ c, ᑎ಴ Ύஅ d, ụ⏣ 㝯ྖ e, ⭜㉺ ᝆ㤶 f, ᑿᓮ ⣧୍ f, ᐑ⏣ Ύ⸝ g
Masaki Kobayashia,b, Hideharu Niwaa, Makoto Saitoa, Yoshihisa Haradaa,b, Masaharu Oshimaa,b,
Hironori Ofuchic, Kiyoyuki Terakurad, Takashi Ikedae, Yuka Koshigoef, Jun-ichi Ozakif, Seizo Miyatagaᮾி኱Ꮫ ኱Ꮫ㝔ᕤᏛ⣔◊✲⛉, b ᮾி኱Ꮫᨺᑕග㐃ᦠ◊✲ᶵᵓ, c㻔㈈㻕㧗㍤ᗘග⛉Ꮫ◊✲ࢭࣥࢱ࣮,d໭㝣ඛ➃⛉Ꮫᢏ⾡኱Ꮫ㝔኱Ꮫ, e ᪥ᮏཎᏊຊ◊✲㛤Ⓨᶵᵓ, f ⩌㤿኱Ꮫ ኱Ꮫ㝔ᕤᏛ◊✲⛉,e᪂࢚ࢿࣝࢠ࣮࣭⏘ᴗᢏ⾡⥲ྜ㛤Ⓨᶵᵓa School of Engineering, University of Tokyo, bSRRO, The University of Tokyo, cJASRI, dJAIST, eJAEA,f
Graduate School of Engineering, Gunma University, gNEDO㑄⛣㔠ᒓ㻔Fe, Co㻕ࣇࢱࣟࢩ࢔ࢽࣥࢆཎᩱ࡟ྵࡴⅣ⣲ᮦᩱゐ፹࡟࠾ࡅࡿ㑄⛣㔠ᒓࡢ㟁Ꮚᵓ㐀ࢆ X⥺྾཰➃ᚤ⣽ᵓ㐀࡟ࡼࡗ࡚ㄪ࡭ࡓࠋCo ࣇࢱࣟࢩ࢔ࢽࣥ⏤᮶Ⅳ⣲ゐ፹࡛ࡣࠊ⣙ 8 ๭ࡢ Co ࡀ㔠ᒓ≧ែ࡛Ꮡᅾࡋ࡚࠸ࡓࠋFe ࣇࢱࣟࢩ࢔ࢽࣥ⏤᮶Ⅳ⣲ゐ፹࡛ࡣࠊ༙ศࡢ Fe ࡀ Fe3C ࡜࡞ࡗ࡚࠸ࡓࠋ୧᪉ࡢヨᩱ࡟࠾࠸࡚㔠ᒓࢆྲྀࡾ㝖ࡃࡓࡵࡢ㓟ฎ⌮ࢆࡋ࡚ࡶ㓟⣲㑏ඖάᛶࡀ࡯ࡰኚ໬ࡋ࡚࠸࡞࠸ࡇ࡜࠿ࡽࠊ㑄⛣㔠ᒓ⮬㌟ࡀάᛶⅬ࡟࡞ࡗ࡚࠸ࡿࡢ࡛ࡣ࡞ࡃࠊⅣ⣲ᵓ㐀ࡢⓎ㐩࡟ᐤ୚ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ࣮࣮࢟࣡ࢻ㸸 ᅛయ㧗ศᏊᙧ⇞ᩱ㟁ụࠊṇᴟゐ፹ࠊⅣ⣲ᮦᩱゐ፹ࠊ㑄⛣㔠ᒓ⫼ᬒ࡜◊✲┠ⓗ㸸ᑗ᮶ࡢ࢚ࢿࣝࢠ࣮ၥ㢟ࢆゎỴࡍࡿ᭱᪝ᡭ࡜ࡋ࡚ࠊ໬Ꮫ࢚ࢿࣝࢠ࣮ࢆ┤᥋㟁Ẽ࢚ࢿࣝࢠ࣮࡟ኚ᥮ࡍࡿࡓࡵ࡟ࠊ⌮ㄽຠ⋡ࡀ㧗࠸⇞ᩱ㟁ụࡀ⬮ගࢆᾎࡧ࡚࠸ࡿࠋ୰࡛ࡶࠊᅛయ㧗ศᏊᙧ⇞ᩱ㟁ụ㻔PEFC:Polymer Electrolyte Fuel Cell㻕ࡣప ࡛సືࡍࡿࡇ࡜࠿ࡽᖜᗈ࠸ᮦᩱࢆ⏝࠸ࡿࡇ࡜ࡀฟ᮶ࡿࡓࡵࠊᐇ
⏝໬ࠊᬑཬࡀᮇᚅࡉࢀ࡚࠸ࡿࠋPEFC ࡣࠊ2 ᯛࡢ㟁ᴟ࡛ࣉࣟࢺࣥఏᑟᛶ㟁ゎ㉁ࢆᣳࡳ㎸ࢇࡔᵓ㐀࠿ࡽ࡞ࡾࠊṇᴟ࡟㓟⣲࢞ࢫࠊ㈇ᴟ࡟Ỉ⣲࢞ࢫࢆ౪⤥ࡋࠊ㟁ᴟ࡛⏕ࡌࡿ໬Ꮫ཯ᛂ࠿ࡽ┤᥋㟁Ẽ࢚ࢿࣝࢠ࣮ࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡿࠋ୧ᴟඹ࡟཯ᛂࢆ㐍⾜ࡉࡏࡿࡓࡵ࡟ⓑ㔠ゐ፹ࡀ⏝࠸ࡽࢀ࡚࠸ࡿࠋ୰࡛ࡶṇᴟࡢ㓟⣲㑏ඖ཯ᛂ㻔ORR: Oxygen Reduction Reaction㻕ࡣ཯ᛂ㏿ᗘࡀ㐜࠸ࡓࡵ࡟ከ㔞ࡢゐ፹ࢆᚲせ࡜ࡋࠊᕼᑡ࡛㧗౯࡞ⓑ㔠ࡢ౑⏝ࡀ PEFC ᬑཬࡢ᭱኱ࡢጉࡆ࡜࡞ࡗ࡚࠸ࡿࠋࡉࡽ࡟ⓑ㔠ࡣࠊPEFCసື᫬ࡢᙉ㓟ᛶୗ࡛㛗ᮇ㛫౑⏝ࡍࡿ࡜ࠊຎ໬ࡋ࡚ࡋࡲ࠺ࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡇࢀࡽࡢၥ㢟ࢆゎỴࡍࡿࡓࡵ࡟ࡣࠊ㠀ⓑ㔠⣔ゐ፹ࡢ㛤Ⓨ◊✲ࡀᚲ㡲࡛࠶ࡿࠋࡑࡢࡼ࠺࡞୰ࠊ㧗࠸㓟⣲㑏ඖάᛶࢆ♧ࡍⅣ⣲ᮦᩱࡀ㏆ᖺᩘከࡃሗ࿌ࡉࢀࠊᮇᚅࡀ㞟ࡲࡗ࡚࠸ࡿ[1-4]ࠋࡇࢀࡽࡢⅣ⣲ᮦᩱࡣཎᩱ࡟㑄⛣㔠ᒓࢆྵࡴࡶࡢࡀከ࠸ࡀࠊྜᡂࣉࣟࢭࢫ࡟࠾࠸࡚㔠ᒓࢆ㝖ཤࡋࡓᚋࡶ㧗࠸άᛶࢆ♧ࡍࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋⅣ⣲⏤᮶࡛࠶ࡿࡓࡵ࡟㈨※㔞ࡀ㇏ᐩ࡛Ᏻ౯࡛࠶ࡿࡇ࡜࠿ࡽࠊPEFC ᮏ᱁ᬑཬᮇ࡟࠾ࡅࡿⓑ㔠௦᭰ゐ፹࡜ࡋ࡚᭷ຊどࡉࢀ࡚࠸ࡿࠋⓑ㔠ࡢᛶ⬟࡟༉ᩛࡍࡿ㠀ⓑ㔠⣔ゐ፹ࢆᐇ⌧ࡍࡿ࡟ࡣࠊࡑࡢᣦ㔪࡜࡞ࡿ㠀ⓑ㔠⣔ゐ፹ࡢ㓟⣲㑏ඖάᛶ࣓࢝ࢽࢬ࣒ࢆゎ᫂ࡍࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࠋⅣ⣲ᮦᩱゐ፹࡟࠾ࡅࡿάᛶ୰ᚰ࡜ࡋ࡚ࠊsp2 ࢿࢵࢺ࣮࣡ࢡ࡟㉳ᅉࡍࡿⅣ⣲ࡢࢼࣀᵓ㐀[5,6]ࠊⅣ⣲ࢧ࢖ࢺ࡟ࢻ࣮ࣉࡉࢀࡓ❅⣲[7,8]ࠊⅣ⣲࣭❅⣲࡜ΰᡂࡋࡓ㑄⛣㔠ᒓࡢ」ྜయ[9,10]ࡀೃ⿵࡜ࡋ࡚⪃࠼ࡽࢀ࡚࠸ࡿࡀࠊⅣ⣲ᮦᩱゐ፹࡟࠾ࡅࡿ ORR Ⓨ⌧ᶵᵓࡣᮍࡔ᫂ࡽ࠿࡟࡞ࡗ࡚࠾ࡽࡎ㆟ㄽࡢ᭱୰࡟࠶ࡿ[11]ࠋάᛶ୰ᚰࡢ୰࡛ࡶ㑄⛣㔠ᒓ࡟㛵ࡋ࡚ࡣ஧✀㢮ࡢᐤ୚ࡀᥦ᱌ࡉࢀ࡚࠸ࡿࠋ୍ࡘࡣ」ྜయࡀ┤᥋ⓗ࡞άᛶ୰ᚰ࡜࡞ࡗ࡚࠸ࡿ࡜࠸࠺ࡶࡢࠊࡶ࠺
୍ࡘࡣⅣ⣲ᵓ㐀ࡢⓎ㐩ࡢゐ፹࡜ࡋ࡚స⏝ࡍࡿ࡜࠸࠺ࡶࡢ࡛࠶ࡿ[12]ࠋ๓⪅ࡣ໬ྜ≀ࡔࡀᚋ⪅ࡣከࡃࡢሙྜࠊࡑࡢ໬Ꮫ≧ែࡣ㔠ᒓ࡛࠶ࡿࠋࡼࡗ࡚ࠊⅣ⣲ᮦᩱゐ፹࡟࠾ࡅࡿ㑄⛣㔠ᒓࡢ໬Ꮫ≧ែࢆྠᐃࡍࡿࡇ࡜࡛༊ูࡀྍ⬟࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋࡑࡇ࡛ࠊᮏ◊✲ࡣⅣ⣲ᮦᩱゐ፹࡟࠾ࡅࡿ㑄⛣㔠ᒓࡢ ORR άᛶ࡟ᑐࡍࡿᙺ๭ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࠊCo ࣇࢱࣟࢩ࢔ࢽࣥ㻔Pc㻕ཬࡧ FePc ࢆཎᩱ࡟ྵࡴⅣ⣲ᮦᩱゐ፹࡟࠾ࡅࡿ㑄⛣㔠ᒓࡢ㟁Ꮚᵓ㐀ࢆ X ⥺྾཰➃ᚤ⣽ᵓ㐀㻔XANES㻕࡟ࡼࡾㄪ࡭ࡓࠋ
CoPc ࡜ FePc ࡣ┤᥋ⓗ࡞άᛶ୰ᚰ࡜⪃࠼ࡽࢀ࡚࠸ࡿ TM-N4㻔TM:㑄⛣㔠ᒓ㻕ᵓ㐀ࢆ᭷ࡋ࡚࠸ࡿࠋⅣ⣲ᮦᩱゐ፹ࡢ㔠ᒓࡢᙺ๭ࢆゎ᫂ࡍࢀࡤࠊ㠀ⓑ㔠ゐ፹ࡢᮦᩱ᥈⣴ࠊゐ፹ྜᡂᡭἲࡢ᭱㐺໬࡟኱࠸࡟ᙺ❧ࡘ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊ㓟⣲㑏ඖ཯ᛂࡢάᛶⅬࡀゎ᫂ࡍࢀࡤࠊྜᡂࡋࡓゐ፹ࡢຠᯝⓗ࡞ᢸᣢ᪉ἲ࡞࡝ࡢ᭱㐺໬࡟ᙺ❧ࡘࡇ࡜ࡀண᝿ࡉࢀࡿࠋᐇ㦂㸸Ⅳ⣲ᮦᩱゐ፹ࡣࠊCoPc ࡜ FePc ࡑࢀࡒࢀࢆࣇ࢙ࣀ࣮ࣝᶞ⬡࡜ΰྜࡋࡓࡶࡢࢆ 1000 oCࠊ800 oC ࡛↝ᡂࡋ࡚స〇ࡋࡓࠋ㑄⛣㔠ᒓࢆྲྀࡾ㝖ࡃࡓࡵࡢ㓟ฎ⌮ࡣሷ㓟࡟ࡼࡾ⾜ࡗࡓࠋヨᩱࡢホ౯ࡣࠊ㟁Ẽ໬Ꮫ≉ᛶࢆᅇ㌿ࢹ࢕ࢫࢡ㟁ᴟ㻔RRDE㻕 ᐃ࡛ࠊᒁᡤᵓ㐀ほ ࢆ㏱㐣㟁Ꮚ㢧ᚤ㙾㻔TEM㻕 ᐃ࡟ࡼࡾ⾜ࡗࡓࠋXANES ᐃࡣ⺯ගἲࢆ⏝࠸࡚ᐊ ࡛⾜ࡗࡓࠋ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸
ᅗ 1 ࡟ CoPc ⏤᮶Ⅳ⣲ᮦᩱゐ፹࡟࠾ࡅࡿ Co K XANES ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋ㓟ฎ⌮ࡢ๓ᚋ࡛ẚ㍑
ࡍࡿ࡜ࠊ໬Ꮫ≧ែ࡟኱ࡁ࡞ኚ໬ࡀ࡞࠸ࡇ࡜ࡀぢ࡚ྲྀࢀࡿࠋࡇࢀࡣ㓟ฎ⌮࡟ࡼࡗ࡚໬Ꮫ≧ែ࡟ࡼࡽࡎ඲యⓗ࡟ Co ࡀ㝖ཤࡉࢀࡓࡇ࡜ࢆ♧၀ࡍࡿࠋᅗ 1㻔a㻕࡟ࡣẚ㍑ࡢࡓࡵᵝࠎ࡞ Co ໬ྜ≀ࡢࢫ࣌ࢡࢺ
ࣝࢆ㍕ࡏ࡚࠸ࡿࠋࡇࡇ࡛ẚ㍑ࡋ࡚࠸ࡿࡢࡣࠊCo 㔠ᒓ, CoPc, Co3O4, CoO, LaCoO3 ࡛࠶ࡿࠋCoPc ⏤᮶Ⅳ⣲ᮦᩱゐ፹ࡢࢫ࣌ࢡࢺࣝ࡟≉ᚩⓗ࡞ᵓ㐀ࡣࠊCo 㔠ᒓࡸ㓟໬ Co ࡟ぢࡽࢀࡿࠋࡑࡇ࡛ࠊࡇࢀࡽࡢࢫ࣌ࢡࢺࣝࢆ⏝࠸࡚ᡂศศ㞳ࢆ⾜ࡗࡓࠋ⤖ᯝࢆᅗ 1㻔b㻕ཬࡧ 1㻔c㻕࡟ࠊࡑࢀࡒࢀࡢᡂศẚࢆ⾲ 1 ࡟♧ࡍࠋゎᯒ⤖ᯝࡣࠊ⣙ 8 ๭ࡢ Co ࡀ㔠ᒓ≧ែ࡟࠶ࡿࡇ࡜ࢆ♧၀ࡋࡓࠋᅗ 2 ࡟ FePc ⏤᮶Ⅳ⣲ᮦᩱゐ፹࡟࠾ࡅࡿ Fe K XANES ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋCoPc ⏤᮶Ⅳ⣲ᮦᩱゐ፹࡜ྠᵝ࡟ࠊࢫ࣌ࢡࢺࣝࡢᙧ≧ࡀ㓟ฎ⌮࡟ࡣ౫Ꮡࡋ࡞࠿ࡗࡓࡇ࡜࠿ࡽࠊ㓟ฎ⌮࡟ࡼࡗ࡚໬Ꮫ≧ែ࡟ࡼࡽࡎ඲యⓗ࡟ Fe ࡀྲྀࡾ㝖࠿ࢀ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋᅗ 2㻔a㻕࡟ࡣẚ㍑ࡢࡓࡵ࡟ࠊ
Fe 㔠ᒓ, FePc,
Fe3C [13], FeO, Fe2O3, Fe3O4 ࡢࢫ࣌ࢡࢺࣝࢆ㍕ࡏ࡚࠸ࡿࠋࡇࢀࡽࢆ⏝࠸࡚ᡂศศ㞳ࢆ⾜ࡗࡓ⤖ᯝࢆᅗ 2㻔b㻕ཬࡧ 2㻔c㻕࡟ࠊᡂศẚࢆ⾲ 2 ࡟♧ࡍࠋFePc ⏤᮶Ⅳ⣲ᮦᩱゐ፹࡟࠾࠸࡚ࠊ⣙༙ศࡢ Fe ࡣ Fe3C
≧ែ࡟࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ
100

100 (b)(a)
Co K
XANES0+0+

Co Dh2+-100

Co3O43+Co , Co50

Co Oh3+

Co Oh

Co Oh

CoO
LaCoO37680 7700 7720 7740 7760 7780

Photon Energy (eV)-2002+3+

Co Oh
As-grown
Acid-washed

Acid-washed
Fitted0+CoCo Dh
2+503+FePc

0Fe3C

100 (c)FeO

Acid-washed
FittedFe metal
FePc
Fe3C
FeO
Fe2O3
Fe3O450

Co , Co
2+Co Oh

Fe2O33+

Co Oh-300

07680

As-grown
FittedFe metal
FePc
Fe3C
FeO
Fe2O3
Fe3O4

Fe metal-100

0100 (c)2+3+

Co , Co
2+50-200

2+100 (b)

(a)
Fe K
XANES

0Co DhIntensity (arb. units)

2+CoPc2+

Co

0
Co metal

As-grown
FittedCo

Intensity (arb. units)

Intensity (arb. units)1007700

77207740

As-grown
Acid-washed
0Fe3O47080 7100 7120 7140 7160 7180

7760

Photon Energy (eV)7100

Photon Energy (eV)ᅗ 1. CoPc ⏤᮶Ⅳ⣲ᮦᩱゐ፹ࡢ Co K XANES ࢫ࣌ࢡࢺࣝ.
㻔a㻕 Co ໬ྜ≀࡜ࡢẚ㍑ࠊ㻔b㻕, 㻔c㻕 ᡂศศ㞳

712071407160

Photon Energy (eV)ᅗ 2. FePc ⏤᮶Ⅳ⣲ᮦᩱゐ፹ࡢ Fe K XANESࢫ࣌ࢡࢺࣝ.
㻔a㻕 Fe ໬ྜ≀࡜ࡢẚ㍑ࠊ㻔b㻕, 㻔c㻕 ᡂศศ㞳⾲ 1. CoPc Ⅳ⣲ゐ፹࡟࠾ࡅࡿ Co ࡢᡂศẚ
CoPc catalysts
As-grown
Acid-washed

Co metal
82 %
85 %

CoPc
5%6%

CoO
13 %9%

Co3O4~0%~0%

LaCoO3~0%~0%⾲ 2. FePc Ⅳ⣲ゐ፹࡟࠾ࡅࡿ Fe ࡢᡂศẚ
FePc catalysts
As-grown
Acid-washedFe metal
18 %
19 %

FePc
12 %
14 %

Fe3C
47 %
44 %

FeO
4%4%

Fe2O36%6%

Fe3O4
13 %
13 %

CoPc ཬࡧ FePc ⏤᮶Ⅳ⣲ᮦᩱゐ፹ࡣ㓟ฎ⌮࡟ࡼࡗ࡚ࡑࡢ㓟⣲㑏ඖ㟁఩ࡣኚ໬ࡋ࡚࠸࡞࠿ࡗࡓࠋ㓟ฎ⌮࡟ࡼࡾ㑄⛣㔠ᒓࡀ㝖ཤࡉࢀࡓࡇ࡜㻔㔞ࡢῶᑡࡣග㟁Ꮚศග࡛☜ㄆ㻕ࢆ⪃៖ࡍࢀࡤࠊヨᩱ୰࡟Ꮡᅾࡍࡿ㑄⛣㔠ᒓࡣ┤᥋ⓗ࡞άᛶ୰ᚰ࡛ࡣ࡞࠸࡜ண᝿ࡉࢀࡿࠋ୍᪉࡛ࠊࡇࢀࡲ࡛࡟㔠ᒓᚤ⢏Ꮚࡀ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡢᡂ㛗࡟㛵ࡋ࡚ゐ፹࡜ࡋ࡚ാࡃࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿ[14, 15]ࠋ࣮࢝࣎ࣥࢼ
ࣀࢳ࣮ࣗࣈࡢᡂ㛗 ᗘ㻔㹼1250 oC㻕௨ୗ࡛↝ᡂࡋࡓሙྜࠊ㔠ᒓᚤ⢏Ꮚࡀከᩘࡢࢢࣛࣇ࢓࢖ࢺᒙ࡟ᅖ
ࡲࢀࡿࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿ[16]ࠋࡲࡓ Fe3C ᚤ⢏Ꮚࡶ Fe 㔠ᒓᚤ⢏Ꮚ࡜ྠᵝ࡟࣮࢝࣎ࣥࢼࣀࢳࣗ
࣮ࣈࡢᡂ㛗࡟ᑐࡍࡿゐ፹࡜࡞ࡿࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿ[17]ࠋ௨ୖࡢሗ࿌ࢆ⪃៖ࡍࢀࡤࠊTMPc ⏤᮶Ⅳ⣲ᮦᩱゐ፹࡟࠾࠸࡚ࠊ㑄⛣㔠ᒓࡣάᛶ࡞Ⅳ⣲ᵓ㐀ࢆసࡿࡇ࡜࡟㈉⊩ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ௒ᚋࡢㄢ㢟㸸Ⅳ⣲ᵓ㐀࡜㔠ᒓࡢ໬Ꮫ≧ែࡢ㛵㐃ᛶࢆ♧၀ࡋࡓࡀࠊࡇࢀ࡟㛵ࡍࡿᐇ㦂ⓗ࡞᳨ドࡀᚲせ࡛࠶ࡿࠋ౛࠼ࡤࠊ↝ᡂ ᗘࢆኚ࠼ࡓヨᩱ࡟࠾࠸࡚ࠊⅣ⣲࡜㔠ᒓࡢ㟁Ꮚᵓ㐀ࢆㄪ࡭࡚ẚ㍑ࡍࡿࡇ࡜࡛ࠊⅣ⣲ᵓ㐀ࡢⓎ㐩࡜㑄⛣㔠ᒓࡢ㔠ᒓ໬ࡢ㛫࡟࡝ࡢᵝ࡞┦㛵ࡀ࠶ࡿ࠿ࢆㄪ࡭ࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡲࡓࠊάᛶ࡜ࡶẚ㍑ࡍࢀࡤࠊάᛶⅬ࡟ࡘ࠸࡚ࡢ▱ぢࡀᚓࡽࢀࡿ࡜ண᝿ࡉࢀࡿࠋࡇࢀ࡟ࡼࡾࠊࡼࡾᛶ⬟ࡢ㧗࠸Ⅳ⣲ᮦᩱゐ፹ࡢస〇ࡀྍ⬟࡟࡞ࡿࡇ࡜ࢆᮇᚅࡍࡿࠋཧ⪃ᩥ⊩㸸[1] K. Gong, D. Du, Z. Xia, M. Durstock, and L. Dai, Science 323, 760 㻔2009㻕.
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