Niᢸᣢࢮ࢜ࣛ࢖ࢺ㗪ᆺⅣ⣲࡟࠾ࡅࡿỈ⣲྾ⶶᣲືࡢin situ XAFSゎᯒすཎ ὒ▱1ࠊ୸ᒣ ⣧21ᮾ໭኱Ꮫࠊ2኱㜰ᕷ❧ᕤᴗ◊✲ᡤ

1. ࡣࡌࡵ࡟ࣉ㛫ࡢࢹ࣮ࢱࡢᩚྜᛶࡀஈࡋ࠸ࡇ࡜ࠊղPtࡸPd࡞࡝㧗2014ᖺࡼࡾ⇞ᩱ㟁ụ⮬ື㌴㸦FCV㸧ࡢ㈍኎ࡀ㛤ጞ౯࡞㔠ᒓࢆ⏝࠸࡚࠸ࡿࡇ࡜ࠊࡢ2Ⅼࡀ኱ࡁ࡞ၥ㢟࡜ࡉࢀࡓࡀࠊ⌧≧࡛ࡣFCVࡀᦚ㍕ࡍࡿỈ⣲㈓ⶶᐜჾࡣ㉸࡞ࡗ࡚࠸ࡿࠋᡃࠎࡢࢢ࣮ࣝࣉ࡛ࡣࡇࢀࡽࡢၥ㢟ࢆゎỴ㧗ᅽ㸦70 MPa㸧ࡢ࢞ࢫ࡛࣎ࣥ࣋࠶ࡾࠊᐜ㔞࡜㔜㔞ࡢࡍ࡭ࡃࠊࢫࣆ࣮ࣝ࢜ࣂ࣮࡟ࡼࡿỈ⣲㈓ⶶ࣓࢝ࢽࢬ࣒ࡢ

పῶࡀồࡵࡽࢀ࡚࠸ࡿ[1]ࠋࡲࡓࠊ㉸㧗ᅽ࡟⪏࠼ࡿᙉᗘゎ᫂࡜ࠊᏳ౯࡞Niࢆ฼⏝ࡋࡓ᪂ࡋ࠸Ỉ⣲྾ⶶᮦᩱࡢ㛤ࢆ☜ಖࡍࡿࡓࡵ኱㔞ࡢⅣ⣲⧄⥔ࡀ౑⏝ࡉࢀ࡚࠾ࡾࢥ

Ⓨࢆ⾜ࡗ࡚࠸ࡿࠋࡑࡢ᳨ウࡢ୰࡛᭱㏆ࠊ1 nm௨ୗࡢࢫࢺࡀ㧗࠸ࡇ࡜ࡶၥ㢟࡛࠶ࡿࠋࡇࢀࡽࡢၥ㢟ࢆゎỴࡍ

ᚤᑠ࡞Niࢡࣛࢫࢱ࣮ࢆ㧗ศᩓᢸᣢࡋࡓࢮ࢜ࣛ࢖ࢺ㗪ࡿ࡟ࡣࠊỈ⣲྾ⶶᮦᩱࢆ฼⏝ࡋ࣎ࣥ࣋ᅽຊࢆ35 MPa

ᆺⅣ⣲㸦ZTC㸧ࢆ㛤ⓎࡋࠊPtᢸᣢZTC࡟༉ᩛࡍࡿ࡯࡝ࣞ࣋ࣝࡲ࡛పῶࡉࡏࡿࡇ࡜ࡀᮃࡲࡋ࠸ࠋỈ⣲྾ⶶᮦᩱࡢỈ⣲ࢫࣆ࣮ࣝ࢜ࣂ࣮㈓ⶶ㔞ࢆ♧ࡍࡇ࡜ࢆぢฟࡋࡓࠋࡣ୍⯡࡟ࠊỈ⣲྾ⶶྜ㔠ࠊ໬ᏛỈ⣲໬≀ࠊ≀⌮྾╔⣔ࡇࡢࡼ࠺࡞ᣲືࡣᚑ᮶࠿ࡽሗ࿌ࡉࢀ࡚࠸ࡿNiᢸᣢⅣᮦᩱࡢ3✀㢮࡟኱ࡁࡃศ㢮࡛ࡁࡿࠋࡇࡢ୰࡛ࠊ≀⌮྾⣲࡜ࡣ᫂ࡽ࠿࡟␗࡞ࡗ࡚࠾ࡾࠊᴟࡵ࡚⯆࿡῝࠸ࠋࡑࡇ╔⣔ࡢᮦᩱࡣỈ⣲ᨺฟ࡟ຍ⇕ࡀ୙せࠊࢧ࢖ࢡࣝ≉ᛶ࡟࡛ᮏ◊✲࡛ࡣࠊ⇕ศゎ࡟ࡼࡿNiࢡࣛࢫࢱ࣮ࡢⓎ⏕㐣⛬ඃࢀࡿ࡞࡝኱ࡁ࡞฼Ⅼࡀ࠶ࡿࡀࠊ㈓ⶶ㔞ࡀᐊ ࡛1㹼2࠾ࡼࡧNiࢡࣛࢫࢱ࣮ᢸᣢZTCࡢỈ⣲྾╔ᣲືࢆࠊinwt%࡜ప࠸ࡇ࡜ࡀ᭱኱ࡢḞⅬ࡛࠶ࡿࠋࡑࡇ࡛㏆ᖺᮇᚅsituࡢXAFS ᐃ࡟ࡼࡾゎᯒࡋࡓࠋࡉࢀ࡚࠸ࡿࡢࡀࠊ≀⌮྾╔࡟ຍ࠼࡚ࢫࣆ࣮ࣝ࢜ࣂ࣮ࡋࡓཎᏊ≧Ỉ⣲ࢆ㈓ⶶࡍࡿ᪂ࡋ࠸Ỉ⣲㈓ⶶ᪉ᘧ࡛࠶ࡿ[2]ࠋ

2. ᐇ㦂ࡇࡢࠕ≀⌮྾╔㸩ࢫࣆ࣮ࣝ࢜ࣂ࣮ࠖ࡟ࡼࡿỈ⣲྾ⶶ࡟

ヨᩱࡢㄪ〇᪉ἲࢆᅗ 1 ࡟♧ࡍࠋNi ࡢ༢య࡜ࡋ࡚⏝㛵ࡋ࡚ࡣࠊୡ⏺୰࠿ࡽከࡃࡢㄽᩥࡀⓎ⾲ࡉࢀ࡚࠸ࡿࡀࠊ

࠸ࡓࡢࡣࠊBET ẚ⾲㠃✚ࡀ 3800 m2/g ࡢ ZTC[3]࡛࠶

ձ࣓࢝ࢽࢬ࣒ࡀゎ᫂ࡉࢀ࡚࠾ࡽࡎࠊ␗࡞ࡿ◊✲ࢢ࣮ࣝ

ࡿࠋNi ࡣᅗ 1 ࡟♧ࡍ 2 ㏻ࡾࡢ᪉ἲ࡛ㄪ〇ࡋࡓࠋࡲࡎ

Ni(NO)2䞉6H2O
Nickel nitrate (NN)Wang and Yang,
J. Phys. Chem. C,
112 (2008) 12486.

Ni(NO)2

Ni

Ni

Ni(NO)2

Liquid phaseadsorption in acetone

ZTC

Ni(NO)2

ZTC-NN(l)Thermal reduction
at 300 ºC, 1 hin H2 stream

Ni

Ni

ZTC-NN(l)R

Ni

Ni

Nickelocene (NC)
Vapor adsorption
at 60 ºC, 12 hZTC-NC(v)Thermal reduction
at 300 ºC, 1 hunder vacuum

Ni

NiZTC-NC(v)Rᅗ 1ヨᩱࡢㄪ〇᪉ἲ ୖẁ ◪㓟ࢽࢵࢣࣝࢆཎᩱ࡜ࡍࡿᚑ᮶ࡢ Ni ᢸᣢⅣ⣲ㄪ〇ἲ࡟ࡼࡿ Ni ࢼࣀ⢏Ꮚᢸᣢ ZTC ࡢㄪ〇ࢫ࣮࣒࢟[4] ୗẁ ࢽࢵࢣࣟࢭࣥࢆཎᩱ࡜ࡍࡿ᪂つ Ni ࢡࣛࢫࢱ࣮ᢸᣢ ZTC ࡢㄪ〇ࢫ࣮࣒࢟
ᚑ᮶ࡢㄪ〇ἲ࡛࠶ࡿ◪㓟ࢽࢵࢣࣝࢆཎᩱ࡜ࡍࡿ᪉ἲ[4]ᢸᣢࡉࢀ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋXRDࡸTEMほᐹࡼࡾࠊ࡟࡚ࠊNi ࢼࣀ⢏Ꮚᢸᣢ ZTC㸦ZTC-NN(l)R㸧ࢆㄪ〇ࡇࡢヨᩱࡣ࠾ࡼࡑ2㹼6 nmࡢ⢏Ꮚ≧Ni✀ࡀᢸᣢࡉࢀࡋࡓ㸦ᅗ 1, ୖẁ㸧ࠋ๓㥑య࡛࠶ࡿ◪㓟ࢽࢵࢣࣝᢸᣢ࡚࠸ࡿࡇ࡜ࡣ௨๓ࡢ⤖ᯝ࠿ࡽศ࠿ࡗ࡚࠸ࡿࡢ࡛ࠊ௒ᅇ

ZTC ࡣ ZTC-NN(l)࡜⾲グࡍࡿࠋࡉࡽ࡟ࠊᡃࠎࡀ⊂⮬ࡢ⤖ᯝ࠿ࡽᢸᣢࡉࢀ࡚࠸ࡿࡢࡣNiࢼࣀ⢏Ꮚ࡛࠶ࡿ࡜࡟㛤Ⓨࡋࡓ᪂つࣉࣟࢭࢫ࡟ࡼࡾࠊNi ࢡࣛࢫࢱ࣮ᢸᣢ☜ㄆࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋࡲࡓࠊ௨๓ࡢᐇ㦂⤖ᯝࡼࡾࠊZTC ࢆㄪ〇ࡋࡓ㸦ᅗ 1, ୗẁ㸧ࠋ๓㥑య࡛࠶ࡿࢽࢵࢣ

ZTC-NN(l)Rࡣ࠶ࡲࡾỈ⣲ࢆ໬Ꮫ྾╔ࡏࡎࢫࣆ࣮ࣝ࢜

ࣟࢭࣥᢸᣢ ZTC ࡣ ZTC-NC(v)࡜⾲グࡍࡿࠋࡑࢀࡒࢀ

ࣂ࣮㈓ⶶ㔞ࡶṤ࡝↓࠸ࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗ࡚࠸ࡿࠋ୍ࡢ๓㥑యヨᩱ⢊ᮎࢆ BN ࡜ΰྜࡋࠊᅽ⦰ᡂᆺࡋ࡚࣌᪉࡛ࠊ⢏ᚄࡀ⣙50 nmࡢNiࢼࣀ⢏Ꮚࡣࠊ⾲㠃࡟Ꮡᅾࡍࣞࢵࢺ࡜ࡋࠊin situ ຍ⇕ࢭࣝࡢ୰࡟⨨ࡁࠊX ⥺྾཰ᚤ

ࡿNiཎᏊ1ಶ࡟ᑐࡋ࡯ࡰ1ಶࡢỈ⣲ཎᏊࢆ໬Ꮫ྾╔ࡍ⣽ᵓ㐀ゎᯒ㸦XAFS, BL11㸧࡟࡚ Ni K-edge ࢫ࣌ࢡࢺࡿࡇ࡜ࡀ࡛ࡁࡿࠋ௨ୖࡢ⤖ᯝࡼࡾࠊ⢏ᚄࡀᑠࡉ࠸Niࣝࡢ ᐃࢆ⾜ࡗࡓࠋḟ࡟ࠊZTC-NN(l)ࡢሙྜࡣ H2 㞺ࢼࣀ⢏ᏊࡣⅣ⣲ࡢᢸయຠᯝ࡟ࡼࡗ࡚ࡑࡢỈ⣲໬Ꮫ྾ᅖẼ࡟࡚ࠊZTC-NC(v)ࡢሙྜࡣ He 㞺ᅖẼ࡟࡚ࡑࢀࡒ╔≉ᛶࡀ኱ᖜ࡟పୗࡋ࡚࠸ࡿྍ⬟ᛶࡀ♧၀ࡉࢀࡓࠋ

ࢀ 300°C ࡲ࡛ຍ⇕ࡋ1 h ಖᣢࡍࡿࡇ࡜࡛Ni ๓㥑యࢆ ୍᪉ࠊ
ᅗ3 ࡟ࢽࢵࢣࣟࢭࣥࢆᢸᣢࡋࡓZTC ࡢ in situ㑏ඖࡋ࡚άᛶ࡞ Ni ✀࡟ኚ໬ࡉࡏࡓࠋᐊ ࡲ࡛෭༷ࡍXAFS ศᯒࡢ⤖ᯝࢆ♧ࡍࠋ⯆࿡῝࠸ࡇ࡜࡟ࠊࢽࢵࢣࣟ

ࡿࡇ࡜࡛ࠊࡑࢀࡒࢀ ZTC-NN(l)RࠊZTC-NC(v)R ࡜ࢭࣥࢆ༢࡟ᢸᣢࡋࡓࡔࡅࡢ ZTC-NC(v)ࡢẁ㝵࡛ࠊNi

࡞ࡗࡓヨᩱࢆ෌ࡧ XAFS ࡛ศᯒࡋࡓࠋࡣඖࡢࢽࢵࢣࣟࢭࣥࡼࡾࡶ㓟໬ࡉࢀ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋXANES ࢫ࣌ࢡࢺࣝ㸦ᅗ 3a㸧ࡢ Ni ࢚ࢵࢪࡣ㓟

3. ⤖ᯝ࡜⪃ᐹ໬ࢽࢵࢣࣝ㸦NiO㸧࡜࡯ࡰྠ࡛ࣞ࣋ࣝ࠶ࡿࡀࠊືᚄᵓ

ᅗ2࡟ࠊ◪㓟ࢽࢵࢣࣝࢆᢸᣢࡋࡓZTCࡢ in situ㐀㛵ᩘ㸦ᅗ 3b㸧ࡣ NiO ࡜ࡣ඲ࡃ␗࡞ࡗ࡚࠸ࡿࡓࡵࠊXAFS㸦Ni K-edge㸧ศᯒࡢ⤖ᯝࢆ♧ࡍࠋ◪㓟ࢽࢵࢣ

ZTC-NC(v)୰ࡢ Ni ࡣ≉Ṧ࡞㓟໬≧ែ࡟࠶ࡿࡇ࡜ࡀุࣝࢆ༢࡟ᢸᣢࡋࡓẁ㝵࡛࠶ࡿZTC-NN(l)ࡣࠊXANES᫂ࡋࡓࠋࡲࡓࡇࢀࢆ 300°C ࡛⇕ฎ⌮ࡋ࡚ㄪ〇ࡋࡓࢫ࣌ࢡࢺࣝ㸦ᅗ2a㸧ࠊືᚄᵓ㐀㛵ᩘ㸦ᅗ2b㸧ඹ࡟Ni

ZTC-NC(v)R ࡣ Ni ࢚ࢵࢪࡢ࢚ࢿࣝࢠ࣮ࡀప࢚ࢿࣝࡢࣃࢱ࣮ࣥࡀ◪㓟ࢽࢵࢣࣝ㸦6Ỉ࿴≀㸧࡜࡯ࡰྠࡌ࡛

ࢠ࣮ഃ࡟ࢩࣇࢺࡋ࡚࠾ࡾࠊNi ࡀ㑏ඖࡉࢀ࡚࠸ࡿࡇ࡜

࠶ࡾࠊNiࡣ◪㓟ࢽࢵࢣࣝࡢ≧ែ࡛ZTC࡟ᢸᣢࡉࢀ࡚࠸ࡀࢃ࠿ࡿࠋࡋ࠿ࡋࠊࡑࡢ≧ែࡣ Ni ⟩࡜ࡶࢽࢵࢣࣟࢭࡿ ࡇ ࡜ ࡀ ࢃ ࠿ ࡿ ࠋ ࡇ ࢀ ࢆ 300°C ࡛ ⇕ ศ ゎ ࡋ ࡓࣥ࡜ࡶ␗࡞ࡿࠋືᚄᵓ㐀㛵ᩘ࡛ࡣࠊ➨஧㏆᥋ཎᏊࡀṤ

ZTC-NN(l)R࡛ࡣࠊNi K-edgeࡢ఩⨨ࡀNi⟩࡜࡯ࡰྠ࡝Ꮡᅾࡋ࡞࠸ࡇ࡜࠿ࡽࠊNi ✀ࡣจ㞟ࡍࡿࡇ࡜࡞ࡃ༢ࡌ࡟࡞ࡾ㸦ᅗ2a㸧ࠊࡲࡓືᚄᵓ㐀㛵ᩘࡶNi foil࡜㏆࠸⊂࡛ᢸయୖࡢ࡝ࡇ࠿ࡢࢧ࢖ࢺ࡟྾╔ࡍࡿࡼ࠺࡞ᙧ࡛

ࣃࢱ࣮ࣥ࡟ኚ໬ࡋ࡚࠸ࡿࡇ࡜࠿ࡽࠊNiࡣ㔠ᒓࡢ≧ែ࡛Ꮡᅾࡋ࡚࠸ࡿ࡜᥎

(a)ࡉࢀࡿࠋ௨๓ࡢ⤖ᯝ࠿ࡽࠊ(b)
Ni foil (㽢0.7)

Ni foil

ZTC-NN(l)R
NiO (㽢0.7)
ZTC-NN(l)NiO

Ni(NO3)2䞉6H2O
8320

8330

8340

8350

Energy (eV)

8360

8370

01

23

4

56R (ύ)ᅗ 2. ◪㓟ࢽࢵࢣࣝࢆᢸᣢࡋࡓ ZTC ࡢ in situ XAFS㸦Ni K-edge㸧ศᯒ.ࡢ⤖ᯝ. (a) XANES ࢫ࣌ࢡࢺࣝ, (b) ືᚄᵓ㐀㛵ᩘ.

(a)

(b)
Ni metal
ZTC-NC(v)Nickelocene(NC)

ZTC-NC(v)R

Ni metal (㽢0.2)

ZTC-NC(v)RNiO (㽢0.2)

NC

NiO
ZTC-NC(v)

8320

8330

8340

8350

8360

8370

01Energy (eV)

23R (ύ)456

ᅗ3. ࢽࢵࢣࣟࢭࣥࢆᢸᣢࡋࡓZTCࡢin situ XAFS㸦Ni K-edge㸧ศᯒ.ࡢ⤖ᯝ. (a) XANESࢫ࣌ࢡࢺࣝ, (b) ືᚄᵓ㐀㛵ᩘ.

ZTC-NC(v)R ࡣᐊ ࡛ࡶỈ⣲ࢆゎ㞳྾╔ࡋࠊ࡞࠾࠿ࡘhydrogen/deuteriumࢫࣆ࣮ࣝ࢜ࣂ࣮㈓ⶶ࡛ࡁࡿࡇ࡜ࡀࢃ࠿ࡗ࡚࠸ࡿࠋ௒ᅇ

zeolite-templated carbon", J. Phys. Chem. C, 118,

ࡢ ᐃ࡟ࡼࡾࠊᚑ᮶࡜ࡣ␗࡞ࡿᙧែࡢ Ni ✀ࡢ≧ែࡀ

9551-9559, (2014).

ࡇ࠺࠸ࡗࡓ≉␗ⓗ࡞Ỉ⣲྾ⶶ≉ᛶࢆⓎ⌧ࡋ࡚࠸ࡿࡇ

[3]࡜ࡀ♧၀ࡉࢀࡓࠋ

Uchiyama, T. Kaburagi, A. Ikura, J. Katamura, T.

spilloveron

Pt-loaded

H. Nishihara, P.-X. Hou, L.-X. Li, M. Ito, M.

Kawarada, K. Mizuuchi, T. Kyotani, "High-pressure

5. ࡲ࡜ࡵhydrogen storage in zeolite-templated carbon", J. Phys.

㧗ẚ⾲㠃✚࡞つ๎ᛶ࣑ࢡࣟከᏍᛶⅣ⣲࡛࠶ࡿࢮ࢜

Chem. C, 113, 3189-3196, (2009).

ࣛ࢖ࢺ㗪ᆺⅣ⣲㸦ZTC㸧࡟ࢽࢵࢣࣟࢭࣥࢆẼ┦⵨╔࡛

[4]ᢸᣢࡋࠊࡇࢀࢆ 300°C ࡛⇕ศゎࡍࡿࡇ࡜࡛ㄪ〇ࡋࡓ

properties of carbons doped with ruthenium, platinum,Ni ᢸᣢ ZTC ࡢ≉␗ⓗ࡞Ỉ⣲྾╔ᣲືࢆ⌮ゎࡍࡿࡓࡵࠊ

and nickel nanoparticles", J. Phys. Chem. C, 112,ࡑࡢ⇕ศゎᣲື࠾ࡼࡧỈ⣲྾╔ᣲືࢆ in situ ࡢ12486-12494, (2008).

XAFS㸦Ni K-edge㸧 ᐃ࡟࡚ヲ⣽࡟ศᯒࡋࡓࠋࡑࡢ⤖ᯝࠊࢽࢵࢣࣟࢭࣥࡀ ZTC ࡟ᢸᣢࡉࢀࡓẁ㝵࡛ࠊNiࡣ≉Ṧ࡞㓟໬≧ែ࡟ኚ໬ࡍࡿࡇ࡜ࠊ300°C ࡢ⇕ฎ⌮࡟ࡼࡾ⏕ᡂࡍࡿỈ⣲྾╔⬟ࡢ㧗࠸≧ែ࡟࠾࠸࡚ࠊNi ࡣⱝᖸࡢ㑏ඖ≧ែ࡟࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋᚑ᮶ࡢ
Ni ᢸᣢⅣ⣲࡜ࡣ᫂ࡽ࠿࡟␗࡞ࡿᣲືࢆ♧ࡋ࡚࠾ࡾࠊỈ⣲໬Ꮫ྾╔࡟㧗άᛶ࡞᪂ࡓ࡞ Ni ࡢᙧែࢆぢฟࡋࡓࠋཧ⪃ᩥ⊩[1]

H.

Nishihara,T.

Kyotani,"Templatednanocarbons for energy storage", Adv. Mater., 24,4473-4498, (2012).
[2] H. Nishihara, S. Ittisanronnachai, H. Itoi, L.-X. Li,
K. Suzuki, U. Nagashima, H. Ogawa, T. Kyotani, M.
Ito,"Experimentalandtheoreticalstudiesof

L. F. Wang, R. T. Yang, "Hydrogen storage