ARTICLE IN PRESS

Physica E 40 (2008) 2231–2237

www.elsevier.com/locate/physe

Electrolytic synthesis of carbon nanotubes from carbon dioxide

in molten salts and their characterization
I.A. Novoselovaa,1, N.F. Oliinyka, S.V. Volkova, A.A. Konchitsb, I.B. Yanchukb,,
V.S. Yefanovb, S.P. Kolesnikb, M.V. Karpetsc
a
Institute of General and Inorganic Chemistry, Ukrainian National Academy of Sciences, 32/34Pr. Palladina, 03680 Kyiv-142, Ukraine
b
Institute of Semiconductor Physics, Ukrainian National Academy of Sciences, 45 Pr. Nauki, 03028 Kyiv, Ukraine
c
Institute for Problems of Materials Science, Ukrainian National Academy of Sciences, 3 Krzhyzhanovsky St., 03680 Kyiv-142, Ukraine
Available online 1 November 2007

Abstract

Carbon nanotubes (CNTs) were synthesized from CO2 dissolved in molten salts using the novel electrolytic method developed by the
authors. The electrolysis were carried out under current and potential controls. To establish the actual current and potential ranges, the
electroreduction of carbon dioxide dissolved in the halide melts under an excess pressure up to 15 bar was studied by cyclic voltammetry
on glassy-carbon (GC) electrode at a temperature of 550 1C. The electrochemical–chemical–electrochemical mechanism of CO2
electroreduction was offered for explanation of the obtained results. The structure, morphology, and electronic properties of the CNTs
obtained were studied using SEM, TEM, X-ray and electron diffraction analysis, Raman and ESR spectroscopy. It was found that the
majority of the CNTs are multi-walled (MWCNTs), have curved form, and most often agglomerate into bundles. Almost all CNTs are
filled partly with electrolyte salt. Except MWCNTs the cathode product contains carbon nanofibers, nanographite, and amorphous
carbon. The dependences of CNT’s yield, their diameter, and structure peculiarities against the electrolysis regimes were established.
r 2007 Elsevier B.V. All rights reserved.

PACS: 81.07.b; 81.07.De; 81.16.Be

Keywords: Carbon nanotubes; Electrolytic synthesis; Molten salts; Carbon dioxide

1. Introduction the cathode. Unlike many other cases of electrolytic

There are a number of known methods for synthesis of
carbon nanotubes (CNTs) [1]. In contrast to other areas of
CNT research, the total number of published articles on
electrolytic CNT accounts for only a very small fraction of
total CNT publications. In 1995 Hsu et al. [2] developed a
new electrolytic method for CNT production, which was
described in detail in Ref. [3]. The main point of this
method is electrowinning of alkali (Li, Na, K) or alkaline-
earth (Mg, Ca) metals from their chloride salts on a
graphite cathode followed by the formation of carbon
tubes by the interaction of the metal being deposited with
Corresponding author. Tel.: +380 445258303; fax: +380 445258550.
E-mail addresses: iness@ionc.kar.net (I.A. Novoselova),
yanchuk@isp.kiev.ua (I.B. Yanchuk).
1
Also for correspondence. Tel.: +380 444241589; fax: +380 444243087.
production of materials where the product is deposited
from the solution onto the electrode, in the mentioned
method CNTs are prepared by converting solid graphite
(electrode) into CNTs that enter the solution phase. The
carbon cathode erodes during the electrolysis and the
electrolytic products are a mixture of CNTs and a large
proportion of carbon nanoparticles of different structures
originating from the graphite cathode. The CNTs pro-
duced are usually multi-walled (MWCNTs). The advan-
tages of electrolytic method are: apparatus simplicity;
possibility to control synthesis process by the electrolysis
modes, low energy consumption for electrolysis; use of
cheap raw materials, possibility of control of product
structures and morphologies as well as of carbon phases
doping in one step (while synthesis) by means of optimiza-
tion of electrolysis conditions and electrolytic bath
composition [3]. But the described method has several

1386-9477/$ - see front matter r 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.physe.2007.10.069
 ARTICLE IN PRESS
2232 I.A. Novoselova et al. / Physica E 40 (2008) 2231–2237
challenges: (i) cracking and destruction of graphite cathode
during electrolysis, (ii) accumulation of electrolysis pro-
ducts: chlorine gas (anode), alkaline metal (cathode), and
carbon nanomaterials (cathode) in bath. This creates
serious problems for stable and continuous performance
of electrolysis.
A novel electrolytic synthesis method for carbon nano-
material generation from ionic melts is being developed in
the Institute of General and Inorganic Chemistry [4–6].
Carbon dioxide, which is introduced in chloride melt under
an excessive pressure, is the precursor of nanoallotropes of
carbon. The process of cathodic reduction of carbon dioxide
to elemental carbon on metallic electrodes is the basis of the
proposed method. So, in this method, a new condensed
carbon phase is generated on the cathode from a liquid
molten salt phase which contains dissolved carbonic acid
gas, by electrochemical reactions. Because of the low
solubility of CO2 gas in the chloride melts the only possible
way to raise the rate of the cathode process is to generate an
excessive gas pressure. All the advantages of electrolytic
syntheses method pointed above may be completely
attributed to the developing one. It was shown that over a
wide current density and potential ranges the only cathodic
product is carbon, and the product of anodic reaction is
oxygen, i.e. an environment-friendly reaction: CO2-C+O2
is realized electrochemically. Using graphite anodes, which
react with isolated oxygen, producing carbon dioxide, this
electrolysis opens real perspective for creation of continuous
technology. The first publication concerning this method
appeared in 2004. It is still in progress.
The principal possibility of CNTs synthesis by this
method was shown in Ref. [6]. In this paper an attempt to
make detail characterization of produced carbon materials
by SEM, transmission electron microscopy (TEM), the
electron-diffraction method, X-ray phase analysis, Raman
and ESR spectroscopy, and differentiation of product
properties with electrolysis conditions was done.
2. Experiment
The principal scheme of high-temperature electrochemi-
cal cell, electrochemical apparatus, chemicals, and peculia-
rities of cathodic discharge of carbon dioxide on platinum
and golden electrodes in the melt Na,K|Cl (molar ratio
0.5:0.5) were described by the authors elsewhere [6,7].
Ternary mixture of earth metal chlorides (NaCl:KCl:CsCl,
molar ratio 0.3:0.245:0.455, melting point 480 1C) was used
as base electrolyte. Cyclic voltammetry (CV) study of CO2
discharge (cathodic and anodic) was carried out by means
of a PI-50-1 potentiostat at a rate 100 mV/s on glassy
carbon (GC) needle electrode (rod diameter 1–2 mm, area
of the electrode 0.5 cm2) as indicative one at 550 1C.
Crucibles made of GC or platinum served as the counter
electrode and melt container at the same time. The
potentials were measured versus quasi-reference elec-
trode-platinum wire (diameter 1 mm, area 5 cm2). The
peculiarities of the electrochemical behavior of this
reference electrode in the case of change of the gas phase
over the melt were described in Ref. [7].
The electrolysis was carried out in the same three-
electrode cell as that of CV measurements in the mode of
either constant cathode current or potential. In the
constant current mode, the applied current density was in
the range 0.005–0.2 A/cm2 with reference to the surface
area of the cathode before starting the electrolysis. Semi-
immersed platinum (cathode) and GC (anode) plate
electrodes (cathode area 5 cm2, anode area 10 cm2) were
used. During the electrolysis in constant current mode the
values of cell voltages and cathode potential were recorded.
In all the modes of electrolysis, platinum cathode surface
erosion was found and in some cases (always in the system
Na,K,Cs|Cl and at low current density (o0.01 A/cm2) in
the system Na,K,|Cl) there are cathode mass losses (tenths
of milligram). A powder product was either dispersed in
solidified salt or assembled on the cathode in the form of
electrolytic ‘‘pear’’ (cathode product associated by solidi-
fied melt). The deposit was separated from salts by
successive leaching with hot water. Thereafter, the pre-
cipitate was washed with distilled water by decantation
method several times and dried to a constant mass at
100–150 1C. Both fractions of cathode product were
collected and analyzed separately.
X-ray diffraction (XRD) measurements were carried out
with a DRON-UM1 diffractometer with Bragg–Brentano
geometry (R ¼ 192 mm) using Cu-Ka monochromatic
radiation. A graphite single crystal positioned on a
diffracted beam was used as a monochromator. XRD data
were treated using a PowderCell 2.4 program.
Microscopy and electron diffraction experiments were
carried out using transmission electron microscope JEM-
100CX II at 60 kV, below the threshold for knock-on
damage in CNTs. Sample preparation for TEM observa-
tion was performed by dropping a dilute acetone suspen-
sion of as-produced carbon deposit (after aqueous
washing) onto copper grid whose amorphous carbon film
was first prepared by dissolving the underlying Formvar in
chloroform. To reduce agglomeration, the dilute suspen-
sion was subjected to ultrasonic dispersion for 10 min.
Raman spectra were recorded at room temperature in the
‘‘backscattering’’ configuration using a double monochro-
mator, a cooling phototube, and discrete lines from Ar laser.
For analysis all spectra were fitted with Gaussian lines.
ESR measurements were carried out in the temperature
range 20–300 K using X-band (nffi9.4 GHz) ESR spectro-
meter Radiopan SE/X-2244 with 100 kHz modulation of
magnetic field. Estimated accuracy of g-value measurement
was 72  104.
3. Results and discussion
3.1. Electrochemical measurements
CV study gives information about current and potential
regions of electrochemical reactions occurring at electrodes,
 ARTICLE IN PRESS
I.A. Novoselova et al. / Physica E 40 (2008) 2231–2237
mechanism, and kinetics peculiarities of electrode pro-
cesses. There are two waves with limiting currents and
half-wave potentials, E1/2: (A) E1/2 ¼ 0.73 (0.43) V,
and (B) E1/2 ¼ 0.98 (0.68) V vs. platinum–oxygen, Pt,
2
1
2O2|O (platinum-carbonate, Pt, CO2+12O2| CO2 3 ) refer-
ence electrodes are observed on the forward cathodic sweep
(Fig. 1(a)). In this part of voltammetric curve, the results at
three indicator electrodes (GC, Pt, and Au) in both studied
electrolytes agree. On the reverse cathodic sweep, two
waves, (C) and (D) are observed as in the case of platinum
electrode. But in contrast to the platinum electrode, the
wave (C) appears at GC electrode already at the reversal
potential after the first cathodic wave (B), and its potential
does not depend on the reversal potential. When the
reversal potential increases in the negative direction, only
an increase of the wave current is observed (Fig. 1(b),
curves 4–6). As far as the wave (D) is concerned,
investigations with different polarization directions (first
to the anodic and then to the cathodic region) showed that
it is observed and does not practically change either in
current or potential on all curves (curves 1–4). If the reverse
sweep is performed after the cathodic wave (B) potential,
the (D) wave potential shifts in the negative direction
(Fig. 1(b), curves 5 and 6). Thus, the wave (D) on the
curves 5 and 6 results from oxidation processes that occur
both in the case of anodic polarization of GC electrode and
in the case of oxidation of the cathodic product. It should
be noted that in the case of anodic polarization of the
Fig. 1. Voltammograms of Na,K,Cs|Cl melt on GC electrode at 550 1C
saturated with CO2 under excess pressure (atm): (a) 1—0, 2—5, 3—10, 4,
(b) –15; potential scan rate 0.1 V/s.
2233
freshly prepared surface of GC electrode (held in the melt
without applied potential for not less than 0.5 h),
the voltammogram exhibited extra waves (E) and (F)
(Fig. 1(b), curve 1). These waves are not observed once
more on repeated sweep after 5 min. They are apparently
due to the oxidation of functional groups adsorbed on the
surface of GC electrode. Based on the data obtained the
electrochemical–chemical–electrochemical (ECE) mechan-
ism of CO2 electroreduction was suggested:
First stage: (Wave A) Reduction of CO2 to CO2
2 radical:
CO2 þ 2e ¼ CO2
2 . (1)
Second stage: Chemical formation of carbon monoxide:
CO2 2
2 ! CO þ O . (2)
Third stage: (Wave B) Irreversible electroreduction of CO
to elementary carbon:
CO þ 2e ! C þ O2 . (3)
At the same time, carbon dioxide acts as acceptor of
oxide anions, and the overall cathode reaction may be
represented as
 2
C 3CO2 þ 4e ! C þ 2CO3 . (4)
Carbonate-ion discharge takes place at the anode to
produce carbon dioxide and oxygen:
2CO2 
3 ! 2CO2 þ O2 þ 4e . (5)
The overall electrode reaction is
CO2 ¼ C þ O2 . (6)
Before starting the electrolysis the cyclic voltammograms
were recorded on plate Pt working electrodes for a much
better control of cathodic potential. Applied cathodic
potentials and current densities did not reach the values
needed for cathodic discharge of the base electrolyte—
isolation of alkali metal. Fig. 2(a) presents the typical I–E
curves and regions of applied cathode current densities and
potentials where cathode processes of electrolysis pro-
ceeded. Cathode and anode potentials–time relations
(Fig. 2(b)) showed stable performance of electrolysis with
slightly decreasing of potential values during the early time
of electrolysis. This phenomenon is believed to result from
the rise of the cell resistance due to the formation of a new
solid carbon phase on cathode.
3.2. Product characterization
There are two main aspects of analysis of the electrolytic
product: (1) identifying and studying properties of the
various forms of the electrolytic carbon and (2) the
proportional content of each. CNT concentration in mixed
carbon materials was measured by TEM and the result
provides an approximate volume proportion. Because the
measurement strongly depends on how the microscope
sample is prepared and who carries out the measurement,
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2234 I.A. Novoselova et al. / Physica E 40 (2008) 2231–2237

Fig. 2. Cyclic voltammograms (a) on plate Pt electrode before electrolysis and cathode (anode) potential–time relations of constant current electrolysis in
molten Na,K,Cs|Cl-CO2 (15 atm) system at 550 1C at current densities (A/cm2): 0.004 (2,3); 0.01 (1,4).

Table 1
Electrolysis conditions of the obtained samples

Sample Electrolytic bath Electrolysis parameters and characteristics

composition
CO2 pressure Temperature (1C) Duration (h) Deposition rate of CNT content
(atm) product (g/A h) (vol%)

Cathode fraction NaCl–KCl 10 750 5 0.060 40

Electrolyte NaCl–KCl–CsCl 15 550 2 0.576 5
fraction

errors in the TEM and SEM result are high. Based on SEM
(results are not presented in this paper) and TEM
estimations the produced electrolytic carbon nanomaterials
contain CNTs in the range 5–40 vol% depending on the
electrolysis conditions and electrolytic bath composition.
For a detailed characterization two samples obtained at
various electrolysis regimes and electrolytic bathes were
investigated (Table 1). Fig. 3. TEM images of nanotubes and nanoparticles prepared in molten
Na,K|Cl-CO2(10 atm) system at 750 1C.
3.2.1. TEM and electron diffraction study
Typical morphologies of the electrolytic nanotubes and
nanoparticles are demonstrated in Figs. 3 and 4, showing majority of which are multi-walled and have curved form
various sampled areas. The patterns show that all the (structural defects). Most often CNTs agglomerate into
products produced in the Na,K|Cl melt contain CNTs, the bundles (Figs. 4(a), (g), and (h)), and more rarely are
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I.A. Novoselova et al. / Physica E 40 (2008) 2231–2237 2235

Fig. 4. TEM images and electron diffraction patterns (c, f, l) of various electrolytic carbon products produced in the systems Na,K|Cl-CO2(10 atm)
(a, b, d, e, g, h, j) and Na,K,Cs|Cl-CO2(15 atm) (k) by constant current electrolysis at 750 and 550 1C, respectively.

arranged as individual tubes (Figs. 4(b), (d), and (j)). As a
rule, a separate bundle consists of CNTs of the same
diameter. The outer diameter of CNTs varies from 5 to
250 nm, while the internal diameter—from 2 to 140 nm.
Almost all CNTs are filled partly with electrolyte salt.
When the current density increases, the CNT diameter
decreases (although every product obtained at the used
current densities has CNTs of different diameters). At the
same time, the carbon product yield and the proportion of
CNTs in the total mass of this product increase. The part
of CNTs in the carbon materials obtained in the system
Na,K,Cs|Cl is about 5 vol% and a large quantity of
amorphous carbon is observed (Fig. 4(k)). Such peculia-
rities of structural carbon phase’s ratios in the product,
synthesized in the ternary melt eutectic, presumably, are
related to the fact that the synthesis temperature was
200 1C below that in the double chloride system. Appar-
ently electrocrystallization of amorphous carbon is a
energy-preferable process at a temperature of 550 1C. It
should be noted that in other widely used synthesis
methods of CNTs (laser evaporation, arc discharge,
chemical vapor (pyrolytic) decomposition) the synthesis
temperature for the maximal yield of CNT is fixed at
temperatures, which are higher than 700 1C. As follows
from TEM and electron diffraction patterns carbon
materials contain also metallic phases, g-Fe, and Pt
(Figs. 4(e), (f), (k), and (l)).
3.2.2. XRD analysis
The XRD data reveal that in all products synthesized in
the system Na,K|Cl-CO2 (10 atm) there are two halos on
the XRD pattern recorded in the regions 2Y (Cu): from 151
to 321 with the center at 26.51; (2) from 381 to 481 with the
center at 421 (Fig. 5(a)). The presence of the first halo
testifies the availability of graphitized planes (0 0 2) with
dE2.37–2.71 A1. The XRD data show also maxima of a
face-centered cubic (FCC) lattice based on Fe (austenite).
The lattice, in addition to Fe, can consist of nickel and
chromium as well. The origin of the above FCC phase is
explained by a non-controlling interaction of a reactor
material and a crucible holder (stainless steel and
nichrome) with a carbon-contained phase formed. During
the prolonged electrolysis (up to 5 h) it is possible to reach
oxidization of reactor walls and to put a sinter into the
alloy. Oxidized components of the reactor material were
dissolved in a chloride liquid melt and then they (together
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2236 I.A. Novoselova et al. / Physica E 40 (2008) 2231–2237

used. It is confirmed by erosion of platinum electrode

surface and its mass loses after electrolysis in this system.

3.2.3. Raman spectroscopy

In Raman spectra of the samples two broad and clearly
separated D and asymmetric G peaks were observed. The
parameters of these peaks (G peak located around
1580 cm1, ID/IG1.2) and the shoulder at the higher
frequency of G peaks testify to the presence of nanoscale
sp2-hybridized carbon clusters as well as MWCNTs in the
synthesized products.

3.2.4. ESR spectroscopy

ESR spectra of the samples 1 and 2 at room temperature
are similar and consist of two overlapping lines, namely a
narrow line (g ¼ 2.002, DHppffi25 G) and a broad one
(gffi2.3, DHppffi1.3 kG), integral intensities of which differ
approximately by 3 orders of magnitude (Fig. 6). The
narrow lines in both samples have an asymmetrical Dyson
shape (insert in Fig. 6) that is typical for ESR signals
originating from delocalized spins in conducting materials.
As the temperature decreases, the value of Hres for
narrow line in both samples remains constant (Fig. 7,
circles). At the same time the linewidth decreases gradually
up to DHppffi3–7 G (depending on the specific sample) as

Fig. 5. XRD patterns of samples 1 and 2. Miller index are presented for
the peaks of austenite (face-centered cubic lattice based on g-Fe) (a), and
Pt (b). *Centers of a halo.

with carbon dioxide) were reduced on the cathode. This Fig. 6. ESR spectra of the samples 1 and 2. Insert shows an asymmetrical
fact is confirmed by a presence of the austenite phase in Dyson shape of narrow ESR line. T ¼ 295 K.
carbon products derived on the cathode and in the
electrolyte volume. The relative quantity of the FCC and
carbon phases was determined in every specimen using
ratios of intensities of the first halo and the first [1 1 1] line
of austenite. The ratio changed in different specimens and
it was within the range 0.5–2. At the 1:1 ratio, as the
microscopy data revealed, the carbon product contained
the maximum content of carbon tubes, up to 40 vol%.
The typical XRD pattern of cathodic product powders
produced in the system Na,K,Cs|Cl-CO2 (15 atm), T ¼
550 1C (sample 2) is characterized by the presence of all Pt
peaks with a symmetrical halo in the region 2Y ¼ 19–321
with the center at 26.51 (Fig. 5(b)). The origin of Pt in
cathode product apparently is connected with ejection of
cathode material by isolating carbon as a result of Fig. 7. The temperature dependencies of resonance field Hres values for
interaction between them when small current densities are narrow (circles) and broad (squares) lines (Sample 2).
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I.A. Novoselova et al. / Physica E 40 (2008) 2231–2237
one can expect in the case of the Elliott–Yafet mechanism
dominating the ESR line broadening in delocalized spin
systems [8]. The nature of this line in our samples is due to
either delocalized charges in CNTs [9] or nanoclusters of
amorphous carbon [10]. The contribution of the carbon
nanoclusters can dominate for sample 2 with a smaller
percentage of nanotubes.
For the broad lines observed in both samples (Fig. 6) the
magnitude of the resonance field Hres decreases gradually
(Fig. 7, squares) while the linewidth increases when the
temperature decreases. Such a behavior is typical for
superparamagnetic systems [11], evidencing the presence of
nanosize magnetic particles in our samples. According to
X-ray data these nanoparticles are due to Fe or Pt content
in samples 1 and 2, respectively (ferromagnetic behavior of
the noble metal nanoclusters was ascertained recently
[12,13]).
4. Conclusion
Electroreduction of carbon dioxide dissolved in molten
salts to carbon can be taken as the basis of high-
temperature electrochemical synthesis (HTES) of various
nanoscaled carbon particles of different structures and
morphologies. The possibility to produce MWCNTs by
this method with content up to 40 vol% in the cathode
product has been shown. The MWCNTs have curved form
and most often agglomerate into bundles. Almost all CNTs
are filled partly with the electrolyte salt.
It was found by the methods of XRD, TEM, and ESR
that the produced framework carbon phases contain
metallic impurities that have nanoscale size. The origin of
metallic phases is (1) the residual admixtures of steel
reactor (g-Fe) and (2) cathodic material (Pt). Metallic
impurities are fixed by TEM as inside and on the ends of
the carbon tubes. The augmentation of tube percentage in
the overall volume of the carbon product was detected in
the samples where austenite phase was fixed. Both Fe and
2237
Pt metallic impurities are present as nanosize particles and
demonstrate superparamagnetic properties.
Thus, metallic phase acts as a catalyst for the generation
of nanotubes in the electrolytic synthesis method from
molten salts.
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