Available online at www.sciencedirect.

com

Current Applied Physics 9 (2009) 263–267

www.elsevier.com/locate/cap
www.kps.or.kr

Electronic behavior of carbon clusters/hafnium oxide

composite material
H. Matsui a, T. Kuroda a, T. Kawahara b, S. Karuppuchamy c,*, R. Kudoh a, M. Yoshihara a
a
Department of Applied Chemistry, Science and Engineering, Kinki University, 3-4-1, Kowakae, Higashiosaka, Osaka 577-8502, Japan
b
Nippon Sheet Glass Co. Ltd., 1-7, 2-Chome, Kaigan, Minatoku, Tokyo 105-8552, Japan
c
Molecular Engineering Institute, Kinki University, 11-6, Kayanomori, Iizuka, Fukuoka 820-8555, Japan

Received 12 January 2008; accepted 13 February 2008

Available online 20 February 2008

Abstract

An alternating hafnium-O-phenylene hybrid copolymer was calcined under the reduced pressure at 400–700 °C to obtain black-col-
ored materials. XRD and TEM analyses showed that the calcined materials were composed of carbon clusters with the diameters of
20 nm and hafnium oxide particles with the diameters of a few nm. ESR spectral examinations revealed that the calcined materials
formed a stable cation radical on the carbon clusters and exhibited an oxidation–reduction function. When Au particles were supported
on the material, an efficient oxidation–reduction function was found to appear.
Ó 2008 Elsevier B.V. All rights reserved.

PACS: 71.20.Rv; 71.20.Nr; 72.80.Tm; 73.63.Bd; 74.25.Jb

Keywords: Nanostructures; Composites; Electronic materials; Polymers

1. Introduction the matrix of carbon clusters. And also it is interesting to

The realization of an oxidation–reduction function with
a charge-separated multi-electron excitation under visible-
light irradiation is important for obtaining new types of
photocatalysts. Either TiO2 [1] or modified metal com-
pounds [2–7] have been expected to exhibit such an excita-
tion. We consider that the combination of carbon clusters
and nano-sized photosensitive semiconductors will lead to
the combined functions of visible-light absorption and elec-
tron transportation by means of carbon clusters and an
electron excitation by semiconductors to generate an oxi-
dation–reduction function. We have recently reported the
syntheses of metal-organic moiety hybrid copolymers [8–
12], and the calcination of the hybrid copolymers under a
reducing atmosphere gave new types of composite materi-
als involving nano-sized inorganic metal compounds in
*
Corresponding author. Tel./fax: +81 948 22 5706.
E-mail address: chamy@mol-eng.fuk.kindai.ac.jp (S. Karuppuchamy).
note that an electron transfer process varied by changing
the metal oxides. For example, calcined materials TiO2,
Nd2O3, and/or CeO2/carbon clusters obtained from Ti-,
Nd-, and/or Ce-O-phenylene hybrid copolymers showed
an electron transfer process of TiO2, Nd2O3, and/or
CeO2 particles ? carbon clusters, while Ho2O3/carbon
clusters composite material obtained from a Ho-O-pheny-
lene-O hybrid copolymer showed an electron transfer pro-
cess of carbon clusters ? Ho2O3 particles [13–15]. A
sufficient explanation for the change of electron transfer
process depends on the metal oxides is not possible to given
at present. However, it was found that CeO2/carbon clus-
ters/Ho2O3 particles loaded with Pt particles showed an
electron transfer process of CeO2 ? carbon clusters ?
Ho2O3 ? Pt which could decompose water to H2 and O2
with a ratio of 2 under whole visible-light irradiation [15].
These findings strongly indicate that the combination of
metal oxides and carbon clusters exhibiting different elec-
tron transfer modes is important for achieving a really

1567-1739/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.cap.2008.02.006
264 H. Matsui et al. / Current Applied Physics 9 (2009) 263–267
Scheme 1. Synthesis of copolymer I.
effective water photodecomposition catalyst. The authors
have thus been examining for clarifying the electron trans-
fer features of combinations of various metal oxides/
carbon clusters composite materials.
Recently, we have reported the formation and elec-
tronic behavior of such composite materials from several
metal-organic moiety hybrid copolymers [16–22]. In the
present study, as one of a series of carbon clusters/
nano-sized inorganic metal compound composite materi-
als, we describe the electronic nature of calcined material
from alternating hafnium-O-phenylene hybrid copolymer
I (Scheme 1).
2. Experimental
2.1. Reagents
Commercially available hafnium n-butoxide, 1,4-hydro-
quinone, anhydrous THF, ferrocenium hexafluorophos-
phate, triethylamine, tin chloride, and gold chloride were
used.
2.2. Synthesis of copolymer I
A mixture of hafnium n-butoxide (0.17 ml, 0.5 mmol)
and 1,4-hydroquinone (0.11 g, 1.0 mmol) in anhydrous
THF was refluxed under an argon atmosphere for 3 h. Pre-
cipitate formed was washed with anhydrous THF using a
Soxhlet extractor and dried at 100 °C under vacuum to
obtain copolymer I.
2.3. Calcination of copolymer I
Copolymer I (0.5 g) in a porcelain crucible was heated
under reduced pressure with a heating rate of 5 °C/min
and kept for 1 h at 400, 500, 600, and 700 °C using an elec-
tric furnace, Denken KDF-75, to obtain calcined materials
Ic-400, Ic-500, Ic-600, and Ic-700, respectively.
2.4. Au-loading on calcined material Ic-600
Calcined material Ic-600 (0.5 g) was immersed in
1.0 wt% tin chloride aqueous solution (100 ml) for two
minutes and washed twice with distilled water. Then, the
material was immersed in 0.1 wt% gold chloride solution
(100 ml) for two minutes and washed twice with distilled
water and dried under vacuum.
2.5. Apparatus
The TG-DTA analyses of copolymer I was performed
using Rigaku TG-DTA-MS 8010. Elemental analyses were
performed for C and H using Yanaco MT-6 and for Hf by
inductively coupled plasma atomic emission spectroscopy
(ICP-AES) using Shimadzu ICPS-7500. X-ray diffraction
(XRD) spectra were taken using Rigaku Mini Flex. Trans-
mission electron microscopy (TEM) measurements were
carried out using Jeol JEM-3010 microscope. Electron spin
resonance (ESR) spectra were taken using Jeol JES-TE200
spectrometer. X-ray photospectroscopy (XPS) spectra were
measured using Shimadzu U-4000 spectrometer.
3. Results and discussion
The results of elemental analyses of copolymer I was
shown in Table 1. The Hf/C6H4 molar ratio in I was calcu-
lated from the observed hafnium and carbon contents to be
2.05, which is almost equal to the expected ratio of 2, indi-
cating the formation of a nearly alternating hafnium–phe-
nylene unit. The TG-DTA measurement of copolymer I
with a heating rate of 5 °C/min under a nitrogen atmo-
sphere (Fig. 1) showed an endothermic reaction below
400 °C due to the evaporation of volatile components, a
weight decrease with an exothermic reaction at 400–
700 °C due to the formation of carbon clusters, and an
endothermic reaction above 700 °C possibly due to the
growth of inorganic metal compound phase. Thus, copoly-
mer I was calcined under reduced pressure with a heating
rate of 5 °C/min for 1 h at 400–700 °C.
The ICP and elemental analyses of the materials (Table
1) showed that increase in calcination temperature
decreased the hydrogen contents and increased both haf-
nium and carbon contents, suggesting that the carboniza-
tion of copolymer I proceeded. The XRD measurement
of the materials (Fig. 2) showed peaks at 2h = 31°, 51°
Table 1
Elemental analyses of copolymer I and calcined materials
Material Found (%)
Hf C H
I 32.6 27.6 2.82
Ic-400 38.1 33.4 2.45
Ic-500 40.6 32.9 1.78
Ic-600 41.9 32.5 1.31
Ic-700 46.9 33.2 1.12
 H. Matsui et al. / Current Applied Physics 9 (2009) 263–267
Fig. 1. TG-DTA analysis of copolymer I.
Fig. 2. X-ray diffraction of calcined materials.
Fig. 3. TEM images of Ic-600 and Ic-700.
and 60° due to HfO2. The TEM images of Ic-600 and Ic-
700 (Fig. 3) showed the presence of ultrafine particles with
the diameters of a few nm, possibly of HfO2, in the matrix
of carbon clusters with the diameters of ca. 20 nm. The CP/
265
MAS 13C NMR spectra of Ic-600 showed peaks at 128 and
180 ppm due to carbon atoms, which are at lower magnetic
fields than those of copolymer I (117 and 150 ppm). The
ESCA spectra measurement of Ic-600 showed the peak of
4d5/2 orbital of hafnium atom at 214.985 eV, which was
lower than that in copolymer I (216.260 eV), suggesting a
lower electron density in Ic-600 than in I. These results
indicate that nano-sized hafnium oxide is formed in the
electronically negative carbon clusters.
The electronic natures of the calcined materials were
examined. UV–Vis spectra of the materials showed absorp-
tion bands over the entire range of wavelengths with high
intensities (Fig. 4). ESR spectra measurements (Fig. 5)
indicated that every material showed a peak at 337 mT
Fig. 4. UV–Vis spectra of copolymer I and calcined materials Ic’s. Spectra
were taken by using the diffusion reflecting method. f(R) is a coefficient of
diffusion reflecting which is calculated by the following equation:
f(R) = {1 R(k)}2/2R(k), where R(k) = is the reflection rate of the sample.
Fig. 5. ESR spectra of copolymer I and calcined materials Ic’s. Spectra
were taken by using 1 mg of sample. Measurement conditions: C. Field
337.00 mT, power 1.00 mW, sweep width 5 mT, modulation width 0.5 mT,
time constant 0.1 s, temp. room temp.
266 H. Matsui et al. / Current Applied Physics 9 (2009) 263–267
(g = 2.0032) due to a free electron, and the intensities were
in the decreasing order Ic-600 > Ic-500 > Ic-400 > Ic-700 >
I. Our understanding is that an electron transfer between
the metal components and the phenylene group for I or
the carbon clusters for Ic’s took place to form a free
electron on the carbon components. The peak intensity of
Ic-600 at 337 mT was considerably higher than that of
copolymer I, suggesting that the calcination treatment
enhanced the degree of charge separation.
The ESR peak intensity of Ic-600 was found to
increase with the addition of an oxidant (ferrocenium
hexafluorophosphate) and to decrease with the addition
of a reductant (triethylamine) (Fig. 6), indicating that
Fig. 6. ESR spectra of Ic-600 in the presence of oxidant and reductant.
Spectra were taken by using 1 mg of sample. Measurement conditions: C.
Field 337.00 mT, power 1.00 mW, sweep width 5 mT, modulation width
0.5 mT, time constant 0.1 s, temp. room temp.
Fig. 7. ESR spectra of Ic-600
Au in the presence of oxidant and reductant.
Spectra were taken by using 1 mg of sample. Measurement conditions: C.
Field 337.00 mT, power 1.00 mW, sweep width 5 mT, modulation width
0.5 mT, time constant 0.1 s, temp. room temp.
Scheme 2. Plausible electron transfer process.
the peak signal is due to a cationic radical formation
on the carbon clusters by an electron acceptation for haf-
nium oxide. In other words, hafnium oxide act as a
reduction site and the carbon clusters acts as an oxida-
tion site. Next, the surface of Ic-600 was modified with
Au particles by a nonelectron-plating method to obtain
Au-loaded Ic-600 (Ic-600
Au). The addition of the oxi-
dant to Ic-600
Au greatly increased the ESR peak inten-
sity, and the intensity decreased with the addition of the
reductant (Fig. 7), indicating that Au particles supported
on the reduction site of Ic-600 effectively gather electrons
to cause effective charge separation, thus forming both
oxidation and reduction sites (Scheme 2). Here, the
remaining question is why the electron transfer between
carbon clusters and HfO2 particles was observed for only
in Ic-600. We propose an idea that the reducing atmo-
sphere during the calcinations treatment may form either
donor level in HfO2 due to O-defect or a partial HfO2–
carbon bonding to affect the ability of electron transfer.
4. Conclusions
We have thus succeeded in realizing an oxidation–reduc-
tion function in the carbon cluster–hafnium oxide compos-
ite material. We believe that similar function must be
achieved by the combination of carbon clusters and many
other semiconductors, and the materials will be widely use-
ful in many fields including electronic, magnetic, and opti-
cal devices, oxidation and/or reduction catalysts, organic
synthesis catalysts, an artificial photosynthesis catalysts,
solar cells, and so on.
References
[1] A. Kudo, A. Nagane, I. Tsuji, H. Kato, Chem. Lett. 31 (2002) 882.
[2] A. Kasahara, K. Nukunizu, T. Takata, J.N. Kondo, M. Hara, H.
Kobayashi, K. Domen, J. Phys. Chem. 107 (2003) 791.
[3] H. Kato, M. Hori, R. Konta, Y. Shimodaira, A. Kudo, Chem. Lett.
33 (2004) 1348.
[4] V.R. Reddy, D.W. Hwang, J.S. Lee, Catal. Lett. 90 (2003) 39.
[5] A. Kudo, K. Domen, K. Maruya, T. Onishi, Bull. Chem. Soc. Jpn. 61
(1988) 1535.
 H. Matsui et al. / Current Applied Physics 9 (2009) 263–267
[6] C.T.K. Thaminimulla, T. Takata, M. hara, J.N. Kondo, K. Domen,
J. Catal. 196 (2000) 362.
[7] G.N. Schrauzer, T.D. Guth, J. Am. Chem. Soc. 26 (1977) 7189.
[8] M. Yoshihara, T. Shino, K. Otsuki, H. Matsui, S. Ohshiro, J. Mater.
Sci. Lett. 21 (2002) 1051.
[9] M. Uda, R. Kudo, H. Matsui, M. Yoshihara, J. Macromol. Sci. 40
(2003) 731.
[10] A. Okada, A. Katayama, H. Matsui, S. Ito, M. Yoshihara, J. Jpn.
Soc. Colour Mater. 77 (2004) 253.
[11] H. Matsui, T. Kawahara, Y. Inui, M. Yoshihara, J. Macromol. Sci.
A42 (2005) 783.
[12] H. Matsui, T. Kawahara, M. Mishima, M. Yoshihara, Polym. J. 37
(2005) 656.
[13] H. Matsui, K. Otsuki, E. Kunimitsu, H. Kajita, T. Kawahara,
M. Yoshihara, Electrochemistry 73 (2005) 959.
[14] T. Furukawa, H. Matsui, T. Kawahara, A. Okada, Y. Seguchi,
M. Yoshihara, Mater. Technol. 23 (2005) 348.
267
[15] H. Matsui, K. Otsuki, H. Yamada, T. Kawahara, M. Yoshihara,
J. Colloid Interface Sci. 297 (2006) 672.
[16] H. Matsui, S. Yamamoto, T. Sasai, S. Karuppuchamy, M. Yoshihara,
Electrochemistry 75 (2007) 345.
[17] H. Matsui, T. Kuroda, K. Otsuki, K. Yokoyama, T. Kawahara,
S. Karuppuchamy, M. Yoshihara, TANSO 222 (2006) 114.
[18] H. Matsui, S. Yamamoto, Y. Izawa, S. Karuppuchamy, M. Yoshi-
hara, Mater. Chem. Phys. 103 (2007) 127.
[19] S. Yamamoto, H. Matsui, S. Ishiyama, S. Karuppuchamy,
M. Yoshihara, Mater. Sci. Eng., B 135 (2006) 120.
[20] T. Furukawa, H. Matsui, H. Hasegawa, S. Karuppuchamy,
M. Yoshihara, Solid State Commun. 142 (2007) 99.
[21] T. Kawahara, H. Miyazaki, S. Karuppuchamy, H. Matsui, M. Ito,
M. Yoshihara, Vacuum 81 (2007) 680.
[22] T. Kawahara, T. Kuroda, H. Matsui, M. Mishima, S. Karuppuch-
amy, Y. Seguchi, M. Yoshihara, J. Mater. Sci. 42 (2007)
3708.