15752 J. Phys. Chem.

C 2008, 112, 15752–15758

Easy Single-Step Route to Manganese Oxide Nanoparticles Embedded in Carbon and Their
Magnetic Properties

Sangaraju Shanmugam and Aharon Gedanken*

Department of Chemistry and Kanbar Laboratory for Nanomaterials at the Bar-Ilan UniVersity Center for
AdVanced Materials and Nanotechnology, Bar-Ilan UniVersity, Ramat-Gan, 52900, Israel
ReceiVed: July 13, 2008; ReVised Manuscript ReceiVed: July 29, 2008

We present a facile and simple solid-state thermolysis approach for the formation of manganese oxide
nanoparticles embedded in an amorphous carbon. This was accomplished through a single-step direct
thermolysis of cetyltrimethylammonium permanganate. The as-synhtesized products were characterized by
transmission electron microscopy (TEM), scanning electron microscopy (SEM), high-resolution transmission
electron microscopy (HRTEM), Raman microscope, X-ray diffraction (XRD), and X-ray photoelectron
spectroscopy (XPS). The product consists mainly of Mn3O4 and of MnOOH coated with carbon. The carbon
coating was observed when reaction was carried out at 400 °C and the average particle size is 9 nm. The
shape of the products can be controlled by varying parameters such as reaction temperature. As the temperature
increases from 500 to 700 °C, larger spherical particles were observed without any carbon coating. The magnetic
properties of as-synthesized products were evaluated using superconducting quantum interference devices
(SQUID). The field-dependent magnetic measurements showed that nanoparticles embedded in carbon exhibited
a high coercivity value of 10.5 kOe at 2 K. The saturation magnetization values at 2 K are 42 and 46 emu/g
for the reaction temperatures of 500 and 600 °C, respectively.

1. Introduction bath deposition, sol-gel technique, co-precipitation, and hy-

In recent years, the development of metal oxide nanoparticles
has attracted tremendous interest because of their potential
applications in catalysis, energy storage, magnetic data storage,
sensors, and biomedical application.1 Different oxides of
manganese are possible due to the existence of Mn in various
oxidation states (II, III, IV, and VII). The magnetic, structural,
and transport properties of these manganese oxides are of
considerable interest in understanding their unique properties
from a fundamental point of view.2-4 Manganese oxide and
oxyhydroxide one-dimensional nanostructured materials have
attracted a great deal of attention because of their low cost, high
natural abundance, and environmental compatibility.5 Manga-
nese oxide materials find a wide range of applications, such as
batteries, catalysts, electrochromic, and magnetic materials.6A
wide variety of morphological structures of manganese oxides,
ranging from single crystals and thin films to nanowires, nanosheets,
and nanoparticles, has been reported.7-12 Among the oxides of
manganese, Mn3O4 is known to be an effective and inexpensive
catalyst for NOx and CO reduction, which provides a powerful
method of controlling air pollution.13 Mn3O4 is also used as a
catalyst for the reduction of nitrobenzene or oxidation of methane.14
Another important application of Mn3O4 is being used as a raw
material for the production of soft magnetic materials such as
manganese zinc ferrite, which is useful for magnetic cores in
transformers for power supply.15 Manganese oxides have been used
as electrochromic materials, and intensive research work was
carried out on these materials.16-18
Mn3O4 was usually prepared by the high-temperature calcina-
tions of manganese oxides with a higher valence of manganese,
hydroxides, and hydroxyoxides at 1000 °C in air.19 Various
methods have been adapted to synthesize Mn3O4, viz., chemical
* To whom correspondence should be addressed. E-mail: gedanken@
mail.biu.ac.il.
10.1021/jp806175y CCC: $40.75  2008 American Chemical Society
Published on Web 09/13/2008
drothermal and thermal decomposition in organic solvents.20
When the hydrothermal method is used, it leads to Mn3O4
formation through hydroxide followed by partial oxidation.21
The hydrothermal method requires long reaction time, i.e., from
48 to 72 h at different temperatures and pressures. The syntheses
of carbon coating nanostructures of magnetic metal/carbon
always rely on very harsh conditions, such as arc techniques,22
catalytic chemical vapor deposition,23 magnetron and ion-beam
cosputtering, and high-temperature annealing.24 The intrinsic
high-energy consumption and expensive hardware of these
techniques are mainly responsible for the high cost of manu-
facturing magnetic nanoparticles encapsulated in carbon and thus
limit their practical applications. Very recently, the magnetic
and microstructural properties of antiferromagnetic MnO nano-
particles with ferrimagnetic Mn3O4 shells has been studied.25
Si et al. observed large coercivity for Mn3O4/MnO nanopar-
ticles.26 Among them, MnO, Mn2O3, and Mn3O4 have a wide
range of applications in catalysis and battery technologies.27
Here, we report the synthesis of manganese oxide nanopar-
ticles embedded in carbon using a single-component precursor.
The advantage of the present method is that the nanoparticle
embedded in carbon is achieved in a single step. To the best of
our knowledge, manganese oxide nanoparticles embedded in
carbon was not reported so far. The as-synthesized products
were characterized with various physicochemical techniques.
The product consists of Mn3O4/MnOOH nanoparticles with an
average size of 9 nm, and the particles are embedded in carbon,
forming sheetlike structures in two-dimensional fashions. By
varying the reaction temperature, we were able to synthesize
manganese oxide nanoparticle without any amorphous carbon.
Another aspect of the paper is the as prepared nanoparticles
exhibit higher coercive fields when compared to the reported
values.
Manganese Oxide Particles Embedded in Carbon J. Phys. Chem. C, Vol. 112, No. 40, 2008 15753

Figure 1. (a, b) TEM images of product, showing the sheetlike morphology and consist of nanoparticles; (c) HRTEM image, showing lattice
fringes of manganese oxide particles. An arrow shows the carbon.

TABLE 1: Reaction Parameters, Product Morphology and Magnetic Properties of Manganese Oxide Nanoparticles
reacn params
expt no. (temp, time, atmosphere) C (wt %) product morphology size of crystals (nm) M (emu/g) coercivity (kOe)
1 400 °C, 3 h, argon 13.4 sheetlike 9 15 10.5
2 500 °C, 3 h, argon 0.05 chains with sperhical spheres 100-250 42 10.14
3 600 °C, 3 h, argon chains with spherical spheres 200-400 46 11.42

2. Experimental Section amorphous carbon film, and then drying under air. High-
resolution scanning electron microscopy (HRSEM) of the
Preparation of the Precursor. The precursor cetyltrimethy-
obtained product was carried out on a JEOL-JSM 840 scanning
lammonium permanganate was prepared by using an aqueous
electron microscope operating at 10 kV. The X-ray diffraction
solution of potassium permanganate (KMnO4, 0.01 M) and
measurements were carried out with a Bruker AXSD Advance
cetyltrimethylammomium bromide (CTAB, 0.01 M). The ratio
powder X-ray diffractometer with a Cu KR (λ ) 1.5418 Å)
between the cation and anion is 1:1. An aqueous solution of
radiation source. The diffraction measurements were collected
CTAB was added drop by drop to the KMnO4 solution with
from 20 to 80° at a speed of 1.2°/min. The elemental analysis
vigorous stirring.28 A purple gel was formed and was aged in
of the sample was carried out by an Eager C, H, N, S analyzer.
air overnight, filtered, and washed with water several times. The
An Olympus BX41 (Jobin Yvon Horiba) Raman spectrometer
C, H, N analysis reveals that the ratio between the cation to
was employed, using the 514.5 nm line of an Ar laser as the
anion is 1. The theoretical carbon content in the starting material
excitation source to analyze the nature of the carbon present in
is 56.6 wt %the, and observed carbon content is 54.2 wt %.
the products. The X-ray photoelectron spectroscopy (XPS)
The synthesis of Mn3O4 structures has been carried out in a
measurements was carried out using JEOL JPS-900, in an
single-stage furnace with precisely controlled temperatures. Fine
ultrahigh-vacuum (UHV), axis HS monochromatized Mg KR
dry powder of cetyltrimethylammonium permanganate was used
cathode source, at 75-150 W, using a low-energy electron flood
as the single-component precursor. For a typical synthesis, the
gun for charge neutralization. Survey and high-resolution
precursor was directly placed in a quartz boat and kept at the
individual metal emissions were taken at a medium resolution,
center of a quartz tube, which was placed inside a tubular
with a pass energy of 50 eV and a step of 1 eV.
furnace. The temperature was raised 20 °C/min in the presence
Magnetic Measurements. Magnetic properties of powder
of argon gas. Thermolysis was carried out at 400 °C for 3 h,
samples were analyzed with a Quantum Design MPMS-7.
and thereafter the furnace was cooled to room temperature.
Detailed magnetic measurements, zero-field-cooled (ZFC) and
Argon flow was maintained throughout the experiment. The as-
field-cooled (FC) magnetization vs temperature under field, and
synthesized product obtained in the quartz boat was used for
magnetic hysteresis loops at several temperatures have been
characterization and magnetic studies. The yield of brownish-
carried out in order to study the magnetic properties of the as-
black product is 0.16 g which corresponds to 55% relative to
synthesized manganese oxide nanoparticles. The saturation
the starting material. Similar experiments were carried out at
different temperatures (500, and 600 °C) and different duration
periods. The carbon content in the products was determined by
using C, H, and N elemental analysis. A comparison of product
morphology, reaction parameters, and carbon content is pre-
sented in Table 1.
Structural Characterization. The particle morphology was
studied with transmission electron microscopy on a JEOL-JEM
100 SX microscope, working at 80 kV accelerating voltage,
and a JEOL-2010 high-resolution transmission electron micros-
copy (HRTEM) instrument with an accelerating voltage of 200
kV. Samples for TEM and HRTEM were prepared by ultrasoni-
cally dispersing the products into absolute ethanol, then placing
a drop of this suspension onto a copper grid coated with an Figure 2. EDAX spectrum of the product obtained at 400 °C.
15754 J. Phys. Chem. C, Vol. 112, No. 40, 2008
Figure 3. (a) HRTEM image, showing lattice fringes of Mn3O4 and
MnOOH. (b) HRTEM image, depicting amorphous carbon on the
surface of manganese oxide particles. The dotted arrows show the
carbon layers.
Figure 4. Raman spectrum of product obtained at 400 °C, showing
the presence of disordered graphitic carbon.
magnetization and coercivity filed values were obtained from
the hysteresis loops measured up to to a field of 6 T at 300, 10,
Shanmugam and Gedanken
Figure 5. XRD pattern of the product obtained at 400 °C.
and 5 K. The temperature dependence of the magnetization was
monitored by ZFC and FC experiments. The ZFC curve was
generated by first cooling the system in a zero field. Then the
field was applied (100 Oe), and magnetization was measured
while the temperature was increased to 300 K. The FC curve
was obtained in a similar way except that the sample was cooled
in an applied field of 100 Oe.
3. Results and Discussion
The morphology of the product synthesized at 400 °C is
shown in Figure 1. A typical TEM image shows that the product
exhibits sheetlike shape. A closer look at the sheet indicates
that the sheet consists of spherical-shaped nanoparticles. The
TEM image shows that the nanoparticles are embedded in
carbon, which is highlighted with an arrow in Figure 1b. The
average size of the particles is 9 ( 1 nm. The higher
magnification of the image shows lattice fringes, indicating the
particles are crystalline (Figure 1c). The EDAX analysis of the
sheet shows the presence of Mn, O, and C without any other
impurities (Figure 2). The carbon content in the product was
determined by using C, H, and N elemental analysis. The
contents of C, H, and N were found to be 13.4, 0.6, and 0.6 wt
%, respectively. The HRTEM image of the product indicates
that the particles are arranged in such a way that the particles
are in close contact with other particles (Figure 3a). The well-
resolved lattice fringes with a d-spacing value of 0.491 nm
correspond to the (101) plane of cubic Mn3O4 (JCPDS 024-
0734). The image also shows particles with a lattice distance
of 0.378 nm, which is corresponding to the γ-MnOOH (110)
plane. From Figure 3b, it is clear that the disordered carbon
coating on the Mn3O4 particle is evidenced (highlighted with
arrows). The thickness of the carbon coating is around 4 nm.
Figure 3b also reveals that the nature of carbon is disordered
layers, corresponding to the nongraphitic, coallike lattice planes
of the carbon, as the thermolysis reaction was carried out at
400 °C.
The nature and type of carbon present in the product is
analyzed by Raman spectroscopy. The product exhibits two
broad peaks at 1328 and 1602 cm-1 (Figure 4). The band at
1328 cm-1 corresponds to the D peak arising from the breathing
motion of sp2 rings, and the band at 1602 cm-1 is a G band.
The ratio between the D and G bands is found to correlate to
Manganese Oxide Particles Embedded in Carbon J. Phys. Chem. C, Vol. 112, No. 40, 2008 15755

Figure 6. XPS spectra of the product synthesized at 400 °C; (a) survey scan; (b) Mn 2p core level; (c) C 1s and (d) O1s spectra.

Figure 7. (a) Temperature-dependent hysteresis loops of manganese oxide synthesized at 400 °C and (b) ZFC and FC magnetization curves under
an applied field of 100 Oe.

the nature of carbon.29 The measured ID/IG ratio is found to be
1.1, suggesting that the carbon exists in a more disordered
graphitic form (amorphous). A typical XRD pattern of the
product is shown in Figure 5. The XRD peaks can be indexed
to the tetragonal Hausmannite phase of Mn3O4 with a ) 0.576
nm and c ) 0.946 nm in accordance with JCPDS No.24-0734.
The XRD pattern also shows additional patterns, which cor-
respond to the γ-MnOOH phase.
The composition and oxidation state of the product prepared
at 400 °C was further analysized by the XPS spectroscopy. The
XPS survey spectrum shows the sheet consists of Mn, O, and
C elements (Figure 6a). The concentration of C is found to be
15%, which is in good agreement with elemental analysis results.
The high-resolution spectrum of Mn 2p is given in Figure 6b.
The obtained binding energy (BE) values of Mn 2p3/2 and 2p1/2
are 641.0 and 652.7 eV, respectively. The spin-orbit splitting
is the difference between BE values of Mn 2p3/2 and Mn 2p1/2
levels. The observed spin-orbit splitting is 11.7 eV, same as
in manganese oxides. 30 The BE of the Mn 2p3/2 (641.0 eV)
and spin-orbit splitting (11.7) is well-matched with the reported
value of Mn3O4. The discrimination between MnOOH and
Mn3O4 is difficult from the Mn 2p values, because, in both cases,
manganese exists in the +3 oxidation state. Figure 6c shows a
broad asymmetric peak, and the peak has been deconvoluted
15756 J. Phys. Chem. C, Vol. 112, No. 40, 2008
Figure 8. SEM images of product obtained at (a) 500 and (b) 600 °C; (c,d) TEM images of product formed at 600 °C.
into three symmetric peaks, C1, C2, and C3 (284.2, 286.4, and
288.0 eV). The peak C1 (284.4 eV) originates from the from
C-C and C-H forms of sp2 carbon, while the peaks at 286.4
(major), and 288.0 eV can be assigned to sp3-hybridized carbon
atoms bonded with one or two oxygen atoms, respectively.31
When the electronegative oxygen atoms are bonded to the
carbon, a positive charge is induced on the carbon atom. Hence,
they can be assigned to alcoholic, ether (C-O) and ketone, or
aldehyde (>CdO). These observations suggest that the carbon
present in the product is amorphous carbon. The oxygen spectra
also give two peaks (O1 and O2) after a deconvulation (Figure
6d). The peak (O1) at 529.6 eV can be attributed to oxygen
(O2-) in the lattice of Mn-O-Mn,32 whereas the peak (O2) at
531.1 eV can be considered to pertain to oxygen in OH groups
present in MnOOH. The Mn/O2- atomic ratio is in agreement
with the theoretical values calculated from the bulk composition.
The magnetic studies of Mn3O4 nanoparticles embedded in
amorphous carbon were investigated using superconducting
quantum interference devices (SQUID) at 300, 10, and 2 K.
The hysteresis loops measured at different temperatures are
shown in Figure 7a. The room-temperature magnetization study
shows the Mn3O4 is paramagnetic, and at low (42 K) temper-
ature Mn3O4 exhibits ferromagnetic behavior. The saturated
magnetization value is 15 emu/g, and remanence is 5.5 emu/g
at 10 K. The remanence ratio (Mr/Ms) of Mn3O4 nanoparticles
is found to be 0.36. The interesting features of hysteresis loops
are as follows: (i) The sample does not saturate at a magnetic
field of 5 T, which means the particles have a large anisotropy
field, and the anisotropy is directly related to the saturation;
hence, the unsaturation of the hysteresis loop implies the
presence of ferromagnetic or antiferromagnetic fractions at low
temp. (ii) The coercive field Hc (HR + HL)/2) of the product is
very large at 10 K (6.5 kOe), much higher than the reported
Shanmugam and Gedanken
value for nanocrystalline Mn3O4 particles, and also at 2 K the
coercivity found to be 10.5 kOe. Buckelew et al. observed 8.8
kOe coercivity at 2 K for Mn3O4 particles synthesized by
hydrolysis of K2[Mn2(CN)6].33 We have thus obtained a large
coercivity, which is much larger than the values of 2.8 kOe for
bulk samples,34 3.5 kOe for thin films,35 and 5.7 kOe for
nanowires.36 To avoid dynamic coercivity, we have collected
the hysteresis very slowly. Another important observation is
that the hysteresis loop shifts in both horizontal and vertical
directions even in the absence of cooling field. The horizontal
hysteresis loop shift at 10 and 2 K are 1.0 and 4.8 kOe,
respectively, in the negative direction in the field axis. The origin
of such high coercivity may be ascribed to the effect of shape
anisotropy of Mn3O4 nanoparticles and also due to the interfacial
interaction between the antiferromagnetic (γ-MnOOH) and
ferromagnetic (Mn3O4) phases, which results in the hysteresis
loops shift. In our product, the nanoparticles are fixed in
amorphous carbon, and therefore preferential orientation of the
magnetic easy axis could also possible.
In our study, the presence of second-phase MnOOH antifer-
romagnetic components could be responsible for such vertical
and horizontal loop shifts. In fact, due to the large anisotropy
of Mn3O4, KMn3O4 ) 1.4 × 106 erg/cm3 is expected to display
a small exchange bias that is only observable for very small
nanoparticles.34 Larger anisotropy results in greater exchange
bias effect, since if a system has larger anisotropy, Mn3O4 will
have greater pinning effect over the other phase with lesser
anisotropy, which creates difficulty in magnetization reversal
and hence larger exchange bias.
The temperature-dependent magnetization studies measured
under zero-field-cooled and field-cooled processes from 5 to
300 K in a 100 Oe probe field are shown in Figure 7b. At room
temperature Mn3O4 exhibits paramagnetic and ferromagnetic
Manganese Oxide Particles Embedded in Carbon
Figure 9. (a) Temperature-dependent hysteresis loops of manganese
oxide synthesized at 500 °C. The inset shows the variation of coercivity
(Hc) vs temperature (T). (b) ZFC and FC magnetization curves under
an applied field of 100 Oe.
nature at low temperature (about 42 K). In our product, from
the ZFC curve (filled symbols), an apparent transition from
paramagnetic to ferromagnetic behavior was observed at 41.5
K, which is known to be the blocking temperature of Mn3O4.
The observed blocking temperature is consistent with the
literature values.37
The thermolysis temperatures play an important role in the
morphology of the product. We carried out the reactions at 500
and 600 °C, and the XRD results indicate that as the reaction
temperature increases, the second-phase intensity, γ-MnOOH,
decreased. The morphology of these products was measured
with SEM and TEM, and the results are shown in Figure 8.
The products obtained at 500 and 600 °C exhibit the particles
with spherical shape without any carbon on the surface. When
the reaction temperature increases, the particle size also
increases, giving rise to bigger particles sizes. It can be seen
from the image that the product consists of spherical spheres
forming chains. The size of the individual sphere is about 100
nm. The length of the chains varies from 2 to 5 µm (Figure 8).
The fusion of adjacent spheres is manifested as sharing the
substructure. The linear alignment of several subunits was
evident inside some microspheres. The further association of
spheres led to higher levels of hierarchical structures. A typical
TEM image of microsphere chains is shown in Figure 8c. It is
clear from the image that the joining of adjacent microspheres
J. Phys. Chem. C, Vol. 112, No. 40, 2008 15757
is through the fusion process. The HRTEM image of the sphere
is shows well-resolved fringes with a d-spacing value of 0.265
nm, corresponding to the (303) plane of cubic Mn3O4 (Figure
8d).
To compare the magnetic properties of product obtained at
400 °C, we prepared manganese oxide nanoparticles without
carbon; this was accomplished by increasing the reaction
temperature. It was observed that when the reaction was carried
out at higher temperatures (500 and 600 °C), the resulting
products consist of Mn3O4 without any carbon (see Table 1).
The magnetic studies of products synthesized at 500 and 600
°C were measured, and the obtained results were given in Table
1. The saturation magnetization values at 2 K are 42 and 46
emu/g for 500 and 600 °C, respectively (Figure 9a). The high
magnetization values observed for Mn3O4 particles obtained at
500 and 600 °C could be attributed to the large particle size
and the shape of the products when compared to Mn3O4-400,
where the particle size is 9 nm, and also to high coercivities of
10.1 and, 11.4 kOe for samples prepared at 500 and 600 °C,
respectively. For samples prepared at 500 and 600 °C systems,
the hysteresis loop shifts are 0.96 and 1.1 kOe, respectively, in
the negative direction on the field axis at 2 K. The blocking
temperature of the product obtained at 500 °C is found to be
42 K (Figure 9b).
4. Conclusions
In summary, by a one-step solid-state thermolysis of the
cetyltrimethylammonium permanganate, we have successfully
synthesized manganese oxide nanoparticles embedded in amor-
phous carbon. The formation of such Mn3O4-MnOOH nano-
particles embeded in carbon was derived by the presence of an
organic structure-directing agent. The product mainly consists
of Mn3O4 along with γ-MnOOH nanoparticles embedded in
amorphous carbon. The average size of the particle is 9 nm for
the sample prepared at 400 °C. The products obtained at 500
and 600 °C exhibit particles with spherical shape without any
carbon around, and the sizes of the particles are in the range of
200-400 nm. The magnetic properties of Mn3O4-MnOOH
nanoparticles exhibit a coercivity value of 10.5 kOe, and the
blocking temperature is 41.5 K. These nanoparticles showed
loop shift (exchange bias) due to the coupling of the weakly
anisotropic MnOOH antiferromagnetic with highly anisotropic
Mn3O4 ferromagnetic particles. The magnetization values of the
products obtained at 500 and 600 °C are in the range of 42-45
emu/g.
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