ARTICLE IN PRESS

Journal of Magnetism and Magnetic Materials 308 (2007) 10–14

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Mercury-based cobalt magnetic fluids and cobalt nanoparticles

R. Massart, B. Rasolonjatovo, S. Neveu, V. Cabuil
Université Pierre et Marie Curie—Paris 6, UMR 7612, LI2C, Colloı¨des inorganique, 4 place Jussieu, Paris F-75232, France
Received 11 October 2005; received in revised form 7 April 2006
Available online 24 May 2006

Abstract

This paper describes the synthesis of a magnetic and conducting liquid consisting of cobalt nanoparticles dispersed in mercury. The
magnetic nanoparticles are obtained in one step by the electroreduction of a cobalt(II) solution on mercury. These particles are then
extracted using an organic solution of surfactant in order to obtain a ferrofluid based on cobalt nanoparticles.
r 2006 Elsevier B.V. All rights reserved.

PACS: 75.50.Mm; 75.50.Tt; 82.70.D

Keywords: Ferrofluid; Nanoparticle; Magnetic

1. Introduction cobalt atoms produced by electrolysis coalesce and metallic

Cobalt nanoparticles have been produced by several
methods, such as dioctyl cobalt carbonyl decomposition
[1–3], hydrogen reduction of cobalt chloride in the gas
phase [4] and reduction in reverse micelles [5]. As an
alternative physical method, metal particles have been
dispersed into mercury. Nanoparticles are prepared in
aqueous solutions of metal cations, either by chemical
reduction using sodium borohydride (NaBH4) [6] or by
electrolysis on a mercury cathode. Luborsky [7] was the
first to prepare iron on mercury. Later, two groups were
interested in solutions of iron, cobalt, nickel or alloy
particles in mercury, Charles and coworkers in UK [8,9]
and Fedonenko and coworkers in Russia [10].
Recently, the electrochemical reduction of iron oxide
nanoparticles on mercury has been described [11,12]. The
maghemite nanoparticles, once reduced, are incorporated
into mercury and a magnetic conducting liquid is obtained.
This method has been adapted here in order to obtain
cobalt nanoparticles using the electrolytic reduction of
Co(II) species on a mercury cathode.
In contrast to most metals, which form alloys with
mercury, cobalt atoms are not soluble in mercury; indeed,
aggregates are formed. At the Hg–Co interface, an interfacial
potential occurs because of the difference between the Fermi
levels of the two metals (mercury and cobalt). The electron
work function of cobalt (5 eV [13,14]) is higher than that of
mercury (4.5 eV [9,15]). This means that negatively charged
cobalt aggregates in positively charged mercury cavities. The
cobalt nanoparticles are spontaneously dispersed in mercury
and their surface negative charges prevent aggregation
because of electrostatic repulsion.
In all these works, when the cathodic reduction is
performed in acidic medium, hydrogen is formed in preference
to metal, because the redox potential E Hþ =H2 is higher than
the redox potential E M2þ =M . Therefore, the pH is a key
parameter in achieving the electroreduction of cobalt(II) ion
on a mercury cathode. Fig. 1 shows the variation of E Hþ =H2
and E Co2þ =Co as a function of pH. Above pH 4.6, metallic
cobalt is produced more easily than hydrogen
ðE Co2þ =Co 4E Hþ =H2 Þ; although in acidic medium, the solvent
is reduced before cobalt(II). In this work, the electrolysis was
performed in a citrate buffer at pH 6.5.
2. Experimental

Corresponding author. Tel.: +33 1 44 27 27 57; fax: +33 1 44 27 36 75. The electrolysis was performed using a generator (Delta
E-mail address: neveu@ccr.jussieu.fr (S. Neveu). Electronika, Power Supply E030-1) under constant stirring

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doi:10.1016/j.jmmm.2006.04.024
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R. Massart et al. / Journal of Magnetism and Magnetic Materials 308 (2007) 10–14 11

lasting at least 5 h. At the cathode, a platinum rod was in
volume of the aqueous solution: 300 mL,
contact with the mercury. The anode consisted of a
medium: Ammonium citrate (0.3 mol L1), citric acid
platinum plate. The setup is described in Fig. 2. (0.3 mol L1), ammonium chloride (0.1 mol L1), pH ¼ 6.5,
The electrolysis was performed either in a homo-
electrolysis duration: 7.5 h.
geneous medium (sodium citrate or ammonium citrate;
Co2+ ions being dissolved as complexes) or in a hetero- 2.1. Coulometry
geneous medium (sodium hydroxide; Co(II) being
precipitated as Co(OH)2). In this way, a magnetic phase During the electrolysis, the current decreases with time
consisting of cobalt nanoparticles in mercury could be (Fig. 3). The amount of electricity consumed during
R
obtained. the electrolysis ( idt ¼ 1410 C) corresponds to the
As an example, the results described below were formation of 7.3  103 mol of cobalt.
obtained in the case of an electrolysis performed in a
homogeneous medium. 2.2. Optical spectrophotometry
The amount of cobalt incorporated in mercury was
determined by two different methods during the electrolysis When the electrolyte solution is a cobalt citrate complex,
in a homogeneous phase with the following experimental its absorbance is proportional to the cobalt concentration
conditions: according to the BeerLambert law (at l ¼ 506 nm,
characteristic wavelength of the cobalt complex). The

mass of mercury: 307.5 g, difference between the absorbance before and at the end

initial amount of cobalt (CoCl2): 0.026 mole, of the electrolysis is due to the disappearance of Co(II) in
solution, and therefore, due to the formation of metallic
cobalt. The amount of metallic cobalt calculated by means
E of this method is equal to 6.3  103 mol of cobalt. This
value is close to the value found by coulometry. These two
H+ methods give similar amounts of metallic cobalt. In the
0V
Co2+ Co(OH)2 following calculations, a mean value equal to
(E2)
6.8  103 mol of cobalt will be used.
-0.28V
H2 2.3. Magnetic characterization
Co
The magnetic measurements were performed using a
(E3) Foner device [16]. A typical magnetization curve for cobalt
(E1) dissolved in mercury is shown in Fig. 4. The curve obtained
4.7 6.9
pH by increasing the field follows the Langevin law [17]. For
an ideal monodisperse solution of nanoparticles (diameter
Fig. 1. Standard redox potential–pH diagram: E1 ¼ E Hþ =H2 ¼ 0.06 pH, D), the magnetization M is given by
E2 ¼ E Co2þ =Co ¼ 0.29 V (for pHo6.9); E3 ¼ E Co2þ =Co ¼ 0.124–0.06 pH 


(for pH46.9). mB kT
M ¼ M s ctnh  ,
kT mB
where Ms ¼ msf is the saturation magnetization of the
solution, ms the saturation magnetization of the
magnetic material, f the volume fraction of cobalt, T the
absolute temperature, k the Boltzmann constant, B the

0.5

0.4

0.3
i (A)

0.2

0.1

0
0 2 4 6 8
t (hours)

Fig. 2. Experimental setup. Fig. 3. Decrease of the intensity in function of time.

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12 R. Massart et al. / Journal of Magnetism and Magnetic Materials 308 (2007) 10–14

Fig. 4. Magnetization curve of the magnetic conducting liquid.

magnetic induction and m ¼ ms ðpD3 =6Þ is the magnetic Table 1

moment of the particles. Magnetic liquids are never Results of the tests with different combinations of surfactants and solvents
monodisperse and a log-normal distribution P(D) is for extraction of the cobalt magnetic nanoparticles
usually assumed [18]: Surfactant Quantity Solvent Result


1 ln2 ðD=D0 Þ Oleic acid 0.7 mL Cyclohexane Black Magnetic
PðDÞ ¼ pffiffiffiffiffiffi exp  , Powder (BMP)
Ds 2p 2s2
5 mL Cyclohexane N
where s is the standard deviation and D0 the mean value 0.7 mL Toluene N
of D. 0.6 mL Hexane N
0.6 mL Kerosene N
Because the volume fraction of particles in the magnetic
phase is always low (o0.05), the analysis of the shape of AOT 0.8 g Cyclohexane BMP
the Langevin curve allows the determination of the 3g Cylohexane BMP
1g Toluene BMP
parameters of the particles’ size distribution [19]. The
mean diameter D0 ranges between 4.7 and 6 nm and the Octanoic acid 0.7 mL Cyclohexane N
standard deviation s is of the order of 0.3. 0.6 mL Toluene N
A slight residual magnetization was observed after N ¼ Nothing.
decreasing the field, probably due to the formation of
chains induced by the aggregation of the nanoparticles
under the magnetic field. This residual magnetization
disappeared when the sample was stirred. 4. Extraction of the cobalt magnetic nanoparticles

The aim of this extraction was to retrieve the cobalt

3. Results
The amount of cobalt (6.8  103 mol) corresponds to
a volume fraction of cobalt in mercury (f) equal to
1.96  103. The saturation magnetization is Ms ¼ 2.1 kA m1.
The specific magnetization of the cobalt nanoparticles is
ms ¼ Ms/f ¼ 1070 kA m1. This value is lower than that of
solid cobalt (1400 kA m1). This decrease, often observed
in the case of ferromagnetic nanoparticles, is probably due
to a poorly crystallized structure and an effect of the
surface disorder on the magnetic contribution.
Placed in a magnetic field gradient, a phase separation is
induced. The magnetic cobalt particles concentrate them-
selves in the high field. Thus, a concentrated magnetic
liquid phase can be obtained with high-saturation magne-
tization (Ms ¼ 20 kA m1, f ¼ 0.02).
Similar results were observed when the electrolysis was
performed in a heterogeneous medium (sodium hydroxide).
nanoparticles from the mercury using an organic solvent
and a surfactant by mechanical stirring for several days.
When the extraction was performed without surfactant and
without precautions against oxidation, the extracted
particles were black and nonmagnetic. These particles were
identified by X-ray diffraction as a mixture of cobalt oxide
(Co3O4) and cobalt hydroxide (Co(OH)2).
In contrast, when the stirring was performed in the
presence of surfactant under inert gas, black magnetic
nanoparticles were recovered. Several combinations of
surfactant (oleic acid, octanoic acid or bis(2-ethylhexyl)-
sulfosuccinate (AOT)) and solvent (cyclohexane, hexane or
toluene) have been tested. Ten grams of magnetic mercury
(volume fraction of cobalt equal to 0.015) and 10 mL of
solvent were used in each test. The results are listed in
Table 1.
The best combinations are the mixtures consisting of
oleic acid–cyclohexane and AOTcyclohexane or toluene.
 ARTICLE IN PRESS
R. Massart et al. / Journal of Magnetism and Magnetic Materials 308 (2007) 10–14 13

In these cases, black magnetic nanoparticles were obtained.
These particles were washed several times with acetone and
alcohol, and then dried.
Fig. 5 shows the black magnetic nanoparticles observed
by transmission electron microscopy. The particles are
polydisperse with a mean diameter of the order of 4.5 nm.
Their crystallographic structure is compared with the
JCPDS data: the characteristic peaks of the hexagonal
close-packed cobalt (Co hc) ((1 0 0), (0 0 2), (1 0 1)) are
observed (Fig. 6). A supplementary peak (3 1 1) is
attributed to cobalt oxide, Co3O4. It seems that the cobalt
nanoparticles are covered by an oxide shell that protects
them against increased oxidation. Therefore, these black
magnetic particles are stable in air and stay magnetic with
exposure time.

5. Conclusion

The electroreduction of Co(II) species on a mercury

cathode results in a conducting magnetic fluid consisting of
cobalt nanoparticles dispersed in mercury. The latter phase
can be considered as a container for cobalt nanoparticles
that can be extracted using suitable solventsurfactant
association. Solid cobalt particles thus synthesized are very
stable against oxidation.
50nm
Acknowledgments
(a)
The authors are greatly indebted to Fabienne Warmont
30 (SIARE, electronic microscopy, University Pierre et Marie
Curie) for the transmission electron microscopy pictures,
25 Fréquence
and Ammy Elfakir and Jean-Paul Souron (LCS, UMR
Fit

20
7574, University Pierre et Marie Curie) for the X-ray
diffraction patterns.
15
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