カーボンナノチューブ化学
• 熱構造変化
• 開孔
• 内包
• エッジの化学
• その他
カーボンナノチューブの化学をカーボンナノチューブを使って行うのは、量が少なくて、困難。よって、ナノホーンで、化学研究したほうが、多くのことが分かる。
開孔方法
•酸化
(HNO3, H2SO4, H2O2, O2)
• メカニカルクラッシュ
酸素中加熱で開孔
Ar
Dry air
O2
T(target)
TimeP(keep)
Slow combustion
Quick combustionT(target)
O2
Time
Fan et al. JPCB 2006
問題:酸化処理により生じる炭素ゴミ
5nm
Hole opening by Combustion
As-grown
580oC, 10 min, O2 100%
Fan et al. JPCB 2006
解決法:炭素ゴミを取るために熱処理500oC, 2 h, 5x10-6 Torr
Fan et al. JPCB 2006
解決法:ゆっくり酸化(Slow combustion)
T(target): 550ºC
:炭素ゴミが少ない
Fan et al. JPCB 2006
開孔した事を確認する。
•比表面積、細孔容量
• TEM
• Raman スペクトル
Fan et al. JPCB 2006
Specific surface area
0 50 400 500 6000
400
800
1200
1600
Sp
ecif
ic s
urf
ace
area
(m
2/g
)
Oxidation temperature (oC)
Usual combustion
Slow combustion
N2 adsorption at 77K.
25 350 400 450 500 550 6000.0
0.1
0.2
0.3
0.4
Ad
sorp
tio
n Q
uan
tity
(g
/g)
Oxidation temperature (oC)
Xylene adsorption at r.t.
Slow combustion
BET吸着等温式(Brunauer,Emmett、Teller)
Fan et al. JPCB 2006
孔?
Holes in graphene walls
SWNHox
Ajima et al. Adv. Materials, 16 (2004) 397.
O2, 570oC, 15 minutes + HT in vac.
0
10
20
30
40
50
60
70
0-0.5 0.5-
1.0
1.0-
1.5
1.5-
2.0
2.0-
2.5
2.5-
3.0
3.0-
3.5
3.5-
4.0
4.0-
4.5
4.5-
5.0
5.0-
5.5
5.5-
6.0
Distribution of Hole Sizes.
2.3 nm
5 nm
Number of holes opened
on the tips
Number of the holes opened
on the side-walls
Hole size ( nm )
Num
ber
of h
oles
1.5 nm
0
10
70
60
50
40
30
20
0- 0.5- 1.0- 1.5- 2.0- 2.5- 3.0- 3.5- 4.0- 4.5- 5.0- 5.5-0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
Ajima et al. Adv. Materials, 16 (2004) 397.
O2, 570oC, 15 minutes
1~3 nm
HeAr
N2CH4
SF6C60
0
0.1
0.2
0.3
0.4
as …
573
623
693Probe
molecules
Pore
volu
me
Heated
temperature
Hole sizes depending on oxidation temperature
Murata et al. JPCB 2002
C60が入れる大きさの孔
5nm
400 oC 450 oC
500 oC 550 oC
Yudasaka et al
SWNTs(Laser ablation) HNO3
water
Oil bath
(~130oC、>数時間)
Trap
酸を用いた開孔硝酸
As-grwon SWNTs(Laser ablation)
硝酸処理後(120℃、4h)
Nagasama et al. CPL 2000
SWNTs(Laser ablation) HNO3
water
Oil bath
(~130oC、>数時間)
O2 (250 Torr)
420oC, 20 min.
Trap
酸化性酸を用いた開孔硝酸
開孔縁の官能基
分析方法・ 定性:IR・ 定性:TPD-MS・ 定量:TGA可視化・ 染色→TEM
開孔縁にある官能基
化学修飾に使えるもの
3h-LAOx2h-LAOx1h-LAOx
2h-Ox
3h-Ox4h-Ox
O2, 500oC
as-grown
1800 1600 1400 1200 1000
Tra
nsm
ittan
ce (a
rb. u
nits
)
Wavenumbers (cm-1)
IR spectraO
C C
O
OC
OC
CC
C OH
OC
O H
OC
OC
O
C CO
Zhang et al. ACS Nano 2007
IR assignments of functional groups on carbon surfaces
Fanning PE, Vannice MA. Carbon 1993;31:721.
• C–O in ethers (stretching) 1000–1300• Alcohols 1049–1276 3200–3640• Phenolic groups:• C–OH (stretching) 1000–1220• O–H 1160–1200 2500–3620• Carbonates; carboxyl-carbonates
1100–1500 1590–1600• C=C aromatic (stretching) 1585–1600• Quinones 1550–1680• Carboxylic acids 1120–1200 1665–1760 2500–3300• Lactones 1160–1370 1675–1790• Carboxylic anhydrides 980–1300 1740–1880• C–H (stretching) 2600–3000
TPD-MS
20 200 400 600 800 1000 Temperature (
oC)
Co
un
ts (
arb
. u
nit
s)
3h-LAOx
2h-LAOx
1h-LAOx
2h-Ox
3h-Ox
4h-Ox
O2, 500oC
as-grown
Mass 44 (CO2)
Zhang et al. ACS Nano 2007
Fanning PE, Vannice MA. Carbon
1993;31:721.
0 200 400 600 800
84
86
88
90
92
94
96
98
100
Temperature (oC)
Wei
ght
(%)
3h-LAOx
2h-LAOx
1h-LAOx
2h-Ox3h-Ox
4h-Ox
O2, 500oC
as-grown
カルボキシル基の数を推定 TGA (He)
ナノホーン1本あたりの孔(直径~2nm)の数・・・・5個程度。(多すぎる。)
Zhang et al. ACS Nano 2007
カルボキシル基の可視化Hashimoto et al. PNAS 101(2004)8527.
One Gd-atomFour Gd-atoms
Gd(CH3COO)3
を使ってキレート結合でエッジにつける。
可視化 ( Site localization)-COOH + Pt(NH3)6(OH)4
-CO-O-NH2-Pt(NH3)5(OH)4
-COO- Pt(NH3)5(OH)4 (NH4)+
Xu et al. APA 2010
As grown
Ox-H2O2 26d
Ox-H2O2 6d
ox500oC As grown
Xu et al. APA 2010
Pt 化合物付着の様子とーCOOHの有無
0.5~0.9 1~1.4 1.5~1.9 2~2.4 2.5~2.9 >30
10
20
30
40
Num
ber
Pt particle size (nm)
SWNHasPt
0.5~0.9 1~1.4 1.5~1.9 2~2.4 2.5~2.9 >30
2
4
6
8
10
12
14
16
18
20
Num
ber
Pt particle size (nm)
SWNHox500Pt
0.5-0
.91-
1.41.5
-1.9
2-2.4
2.5-2
.9 >30
10
20
30
40
50
60
70
Num
ber
Pt particle size (nm)
SWNHox-6d, Pt
0.5~0.9 1~1.4 1.5~1.9 2~2.4 2.5~2.9 >30
20
40
60
80N
um
ber
Pt particle size (nm)
SWNHox-26d, Pt
Pt complex particles: Size distribution
Xu et al. APA 2010
Ptの量を測定できる。
Ptの量からCOOH量を推定。
TGA(酸素)
0 5 10 15 20 25
0
2
4
rt-400oC
W
eig
ht
loss
(%
)
Immersion period in H2O2 (days)
Ptの量は、COOHの量と相関。Xu et al. APA 2010
内包
1.気相(昇華法)2.液相3.吸着サイト4.内包物質の反応
(C60)n@SWNT (Peapod)
C60
SWNTs
1. Open SWNT tips
by Oxidation.
2. Expose to C60 Vapor
at 400 oC.
Hirahara et al. Phys. Rev. Lett. 85, 5384, 1999
Heat treatment at 1200 oC
C60@SWNT
Double-wall carbon nanotubes
Bandow et al. Chem. Phys. Lett. 337, 48, 2001
C60@SWNTs Double-walled carbon nanotubes
Nano-Condensation
Incorporation in liquid phase at room temperature.
CNT, SWNHGuest
molecules
Solvents
strong
weak
Nano-precipitation
Nano-Extraction
Nano-Titration, etc.
Affinity
balance
CNTsGuest
molecules
Solvents
Affinity
balance
Yudasaka et al. Chem. Phys. Lett. 2003.
Yuge et al, J. Phys. Chem. B 2005.
Filtration paper
TEM gridSolution
NTs, NHs
Nano-Condensation
Incorporation Methods:Non-equilibrium methods of C60 in
Liquid Phase at Room Temperature
M.Yudasaka et al., Chem. Phys. Lett., 380, 42 (2003).
Filter paper
TEM grid
C60 + Toluene
SWNT
or SWNH
Ajima et al. Adv. Materials, 16 (2004) 397.
5 nm
M.Yudasaka et al., Chem. Phys. Lett.,
380, 42 (2003).
C60 @ SWNTsC60 @ SWNHs
Ajima et al. Adv. Materials, 16 (2004) 397.
Incorporation Methods:Non-equilibrium methods of C60 in
Liquid Phase at Room Temperature
M.Yudasaka et al., Chem. Phys. Lett., 380, 42 (2003).
Nano-Extraction
C60 + EtOH + SWNT/ SWNH5 nm
Ajima et al. Adv. Materials, 16 (2004) 397.
Incorporation of ZnPc into SWNHs (NHox)
Dried in
N2 flow
at r. t.
Filtration,
and washing
with ethanol
SWNHox was
dispersed in DMSO-
Ethanol solution of
ZnPc
SWNHox was
immersed in
ZnPc-DMSO –
EtOH for 24 h
ZnPc@NHox
NHox
ZnPc-DMSO
24 h
Zhang et al PNAS 2008
10 nm
TEM image of ZnPc-SWNHox
COOH
COOH
Zhang et al PNAS 2008
Chemical Modification of ZnPc-SWNHox with BSA protein
ZnPc
~40 wt.%
Temperature (oC)
Wei
gh
t (%
)
TGA results
in O2
The content of ZnPc in SWNHox did not
change after modification with BSA.20 nm
ZnPc-SWNH-BSA
20 nm
ZnPc-SWNHox
BSA
~20 %
0 200 400 600 800 10000
20
40
60
80
100
Zhang et al PNAS 2008
C
Zn O
元素マッピング(EELS)Zhang et al PNAS 2008
Cisplatin (CDDP)@SWNHox
•Abundant incorporation :
CDDP 50 wt%
•Slow release : 4days
10 nm 2 nm
CDDP
clusters
CDDP+H2OCDDP@
SWNHox
Ajima, et al. ACS Nano 2008
Molecular structure confirmation for CDDP
in CDDP@SWNHox
EELS
Cl and C mapping
Z-contrast image
Pt: Bright spots
STEM image
Pt
Pt
Cl
Cl
H3N
H3NICP analysis Pt:Cl= 1:2
CDDP
Ajima, et al. ACS Nano 2008
内包量の評価は、金属(あるいは、SとかFとか)がない場合は簡単ではない。
5 nm
5 nm
10 nm2 nm
C60
TEM images of
C60@SWNHox prepared by
nano-precipitation (b and c),
and C60 crystal (indicated by
arrow) deposited on as-grown
SWNHs (d). TEM image of
residue obtained by stopping
TG measurement of 15%-
C60@SWNHox at 500C,
indicating most of C60 was
eliminated by combustion with
O2 (e).
C60/asSWNHC60@SWNHox
C60@SWNHox
500℃ TGA reside
Yuge et al. JPCB 2005
200 400 600 800 10000
50
100
0.0
0.3
0.6
Temperature (C)
Wei
ght
(%)
Deriv. W
eight (%
/C)
SWNHox
1% (0.01 g/g)
3% (0.03 g/g)
10% (0.11 g/g)
15% (0.18 g/g)
40% (0.67 g/g)
C60@SWNHox
Raman spectra
Yuge et al. JPCB 2005
200 400 600 800 1000
0
20
40
60
80
100
as-grown SWNHs
40%-C60
/SWNH (as-grown)
Temperature (ºC)
Weig
ht
(%)
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
Deriv
. Weig
ht (%
/ºC)
C60@as-SWNH
Raman spectra
0
200
400
10 15 20 25 300
500
1000
1500
0
2000
4000
6000
Inte
nsit
y (
arb
. u
nit
s)
2 theta (degree)
0%
15%
40%
60% -C60@SWNHox
15%-C60/as-SWNH
C60(1
11)
(22
0)
(311)
(22
2)
(33
1)
(42
0)
XRD
Yuge et al. JPCB 2005
1000 1200 1400 1600 1800
0.2
0.4
0.6
0.8
1.0
In
ten
sit
y (
arb
. u
nit
s)
Raman shift (cm-1)
1466 cm-1
C60@SWNHox-tol
C60@SWNHox
(TGA residue)
15%-C60@SWNHox
SWNHox
Raman spectra
1400 1420 1440 1460 1480 1500 1520 1540
0.15
0.20
0.25
0.30
0.35
0.40
Inte
nsi
ty (
arb
. u
nit
s)
Raman shift (cm-1)
15%-C60@SWNHox
3%-C60@SWNHox
40%-C60@SWNHox
15%-C60/as-SWNHs
40%-C60/as-SWNHs
Raman spectra
1420 1440 1460 1480 1500
0.14
0.15
0.16
0.17
0.18
T= 120 min
T= 90 min
T= 60 min
In
ten
sity
(arb
. u
nit
s)
Raman shift (cm-1)
T= 30 min
Raman spectra
(レーザー照射によるC60ラマンピーク
強度の減衰。SWNHox内部にあ
ると減衰速度は遅くなる。)
15%-C60@SWNHox
Starting quantity of C60
in the initial mixture of
C60, SWNHox, and
toluene
% 1 3 10 15 40 60
g/g 0.01 0.03 0.11 0.18 0.67 1.50
vol/vol 0.02 0.05 0.17 0.28 1.06 1.65
Ratio of incorporated
C60 and SWNHox in the
end products of
C60@SWNHox
g/g 0 0.03 0.09 0.11 0.22 **
vol/vol 0 0.05 0.15 0.19 0.36 **
In calculating C60 quantities in units of vol/vol, the density of the C60 crystal (1.68 g cm-3)
and the pore volume of the inside space of the SWNHox (0.36 ml g-1)13 were applied.
カギになる元素がいない場合には、量の計測が容易ではない。
SWNH外部にはC60がいないことを確認。 TGAからC60量を見積もった。
内包量は、仕込み量で制御できる。
Hashimoto, A. et al.,
Proc. Natl. Acad. Sci. USA, (2004).
5 nm1. Stirring of NHox and Gd(OAc)3・4H2O
in EtOH for 24 hrs at r.t.
2. Filtration
3. Sonication in EtOH for 20 sec
4. Filtration
5. Vacuum drying
Gd(III)-NHox
Equilibrium methods for preparingGd-acetates@SWNHox
NHoxGd(III)
-NHox
Nano-
windowGd
acetates
SWNHox and Gd(OAc)3・4H2O are
immersed in EtOH at room temperature.
Gd(OAc) ・0.5H2O
( From TG-MS and IR )
(Gd(OAc)3 ・4H2O was changed.)
吸着サイト
Inter-SWNH pore
0.1 ml/g
Intra-SWNH pore I
0.2 ml/g
Intra-SWNH pore II
0.2 ml/g
100 200 3000.0
0.1
0.2
Temperature (oC)
∂(w
eig
ht)
/∂T
(%
/oC
)Desorption of
xylene and benzene CH3
CH3
Single-wall carbon nanohorns
1 nm
20 nm
0 100 200 300 400 500 600
0.00
0.05
0.10
0.15
0.20
0.25
Temperature at
maximum of
DW curve
(T(desorb))
Temperature (oC)
Wei
ght
(%)
Der
iv. W
eight
(%/o
C)
0 100 200 300 400 500 60070
75
80
85
90
95
100
Desorptionquantity
(DQ)
dry air
NHoxXylene@NHox
1 hour 0 ~ 21 days
xylene,
Temperature (oC)
CH3
CH3
Fan CPL 2004Yudasaka et al. JPCB 2005
0 100 200 500 600
70
80
90
100
0 100 200 500 600
0.0
0.1
0.2
Wei
gh
t (%
)D
eriv
. W
eig
ht
(%/o
C)
Temperature (oC)
Temperature (oC)
21 days
11
7
0
1
2
21 days
11
7
0
12
0 100 200 500 60070
80
90
100
As-grown
350
450580
600
Temperature (oC)
Wei
gh
t (%
)
0 100 200 500 6000.0
0.1
0.2
As-grown
350450
550oC580600
Temperature (oC)
Der
iv.
Wei
gh
t(%
/oC
)
550oC
Xylene adsorption quantity depended on hole-opening temperatures.
Adsorbed xylene was released slowly.CH3
CH3
0 5 10 15 200
5
10
15
20
25
0
50
100
150
DQ
(%
)
T(d
esorb
) (oC
)
Period(air) (days)Tox (oC)
DQ
(%
)
T(d
esorb
) (oC
)
0 30300 400 500 6000
5
10
15
20
25
0
20
40
60
80
100
Xylene adsorption quantity depended on hole-opening temperatures.
Adsorbed xylene was released slowly.CH3
CH3
XY
Z
0.2
0.1
0.0
0.1
0.0
0.1
0.0
0.1
0.0
0.05
0.0
0.05
0.0
0 100 200 300 400
Temperature (oC)
Der
iv, W
eight
(%oC
-1)
Tox: 600oC
580oC
550oC
450oC
350oC
As-grown
Der
iv. W
eight
(%oC
-1)
Temperature (oC)
Periods left in
dry air for 21 days
11 days
2 days
0 dayX Y
Z
0 100 200 3000.0
0.1
0.2
0.0
0.1
0.2
0.0
0.1
0.2
0.0
0.1
0.2
Xylene adsorption quantity depended on hole-opening temperatures.
Adsorbed xylene was released slowly. CH3
CH3
0 10 200
10
2040
80
120
160
200
0 10 20 0 10 20
Periods in air (days)
T(desorb)
FWHM
Quantity
X YZ
T(d
eso
rb)(
oC
), F
WH
M(o
C),
Qu
anti
ty (
g/1
00
g)
X Y Z
T(desorb)
FWHM
Quantity
Tox (oC)0 200 400 600
0
10
60
80
100
120
140
160
180
0 200 400 6000 200400600
Z
Y
X
燃焼で消滅強く吸着放出しにくい
CH3
CH3
燃焼で消滅しない弱く吸着放出しやすい
燃焼で消滅しない強く吸着放出しにくい
0 30 300 400 500 6000
2
4
6
8
10
12
14
0
20
40
60
80
100
Tox (oC)
DQ
(%)
T(d
esorb
) (oC
)
0 2 4 6 8 10 12 14 16 18 20 220
5
10
15
20
25
0
20
40
60
80
100
120
140
160
DQ
(%)
T(d
esorb
) (oC
)
Period(air) (days)
Benzene adsorption quantity depended on hole-opening temperatures.
Yudasaka et al. JPCB 2005
0.0
0.1
0 50 100 150 200 250 300
0.0
0.1
0.0
0.10.0
0.10.0
0.10.0
0.1
0.0
0.1
Temperture (oC)
Deri
v.
of
weig
ht (%
/oC
)
YZ
Tox 620oC
600
580
550
450
350
As-grown
0 100 200 300
0.00
0.05
0.00
0.05
0.00
0.05
0.00
0.05
0.10
0 day
4 days
1 day
Temperture (oC)
Der
iv. of
wei
ght
(%/o
C)
YZ
Periods left in dry air.
16 days
Benzene adsorption quantity depended on hole-opening temperatures.
Yudasaka et al. JPCB 2005
0 200 400 6000 200 400 600
0
10
50
100
150
0 5 10 15
0246
50
100
150
200
0 5 10 15
T(d
eao
rb)
(oC
), F
WH
M (
oC
) Q
uan
tity
(g
/SW
NH
ox
10
0 g
)
Y
Z
T(desorb)
FWHM
Quantity
Period (air) (days)
Tox (oC)
Y Z
T(desorb)
FWHM
Quantity
Z
Y
X
消滅しやすい強く吸着放出しにくい
消滅しない弱く吸着放出しやすい
消滅しない強く吸着放出しにくい
Xサイトからの放出がない!
Yudasaka et al. JPCB 2005
sites X Y Z
Xylene/SWNHox
Desorption quantity
(mole/SWNHox(100g))0.17 0.11 0.046
Desorption temp (oC) 75 120 170
sites Y Z
Benzene/SWNHox
Desorption quantity
(mole/SWNHox(100g))Not detected 0.12 0.026
Desorption temp (oC) Not detected 80-110 130-190
0.17
mole/SWNHox(100g)
Yudasaka et al. JPCB 2005
K. Ajima, et al. Adv. Mater. 2004, 16, 397–401.
C60 molecules (0.7 nm) were preferentially incorporated at sites of NHox with diameters of 1−2 nm.
2 nm
1.2 nm 1.2 nm 1.6 nm 1.9 nm
Relation between number of C60 molecules and local
diameters of NHox
0
5
10
15
20
25
30
35
0.5-
0.9
1.0-
1.4
1.5-
1.9
2.0-
2.4
2.5-
2.9
3.0-
3.4
3.5-
3.9
4.0-
Local diameter: 2r (nm)
Num
ber
of
inco
rpo
rate
dC
60
mo
lecu
le
S. Okada et al., Phys. Rev. B 2003, 67, 205411–
205415.
1.2 1.3 1.4 1.5 1.6 1.7
1.8
ΔE
(eV
/Fulle
rene)
SWNT diameter (nm)
(1.5 nmf)C60@SWNTs
C70@SWNT
s
Stability of peapod depends on diameter of SWNTsC60 encapsulation in nanospaces by van der Waals force
(1.5 nmf)
Quantum Effects on Hydrogen Isotope
Adsorption on Single-Wall Carbon Nanohorns
Tanaka et al. JACS 2005
Quantum effects cause the density of adsorbed H2 inside the
SWNH to be 8-26% smaller than that of D2
Nanowindow-Regulated Specific Capacitance of
Supercapacitor Electrodes of Single-Wall Carbon
Nanohorns
Yang et al.
JACS 2006CAN アセトニトリル,
PC プロピレンカーボネート
H2SO4/H2O < Et4NBF4/ACN <
Et4NBF4/PC (Et4N+â7ACN, 1.30 nm; BF4
-â9ACN, 1.16 nm; Et4N+â
4PC, 1.35 nm; BF4
-â8PC, 1.40 nm).
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