Chemical Engineering Journal 139 (2008) 208212

Electrodeposition of maghemite (-Fe2O3) nanoparticles

Hosik Park a,b , Perla Ayala a , Marc A. Deshusses a , Ashok Mulchandani a ,
Heechul Choi b , Nosang V. Myung a,
a Department of Chemical and Environmental Engineering, University of California-Riverside, Riverside, CA 92521, United States
b Department of Environmental Science and Engineering, Gwangju Institute of Science and Technology,

1 Oryong-dong, Buk-gu, Gwangju 500-712, Republic of Korea

Received 9 July 2007; received in revised form 16 October 2007; accepted 22 October 2007

Abstract
Crystalline maghemite (-Fe2 O3 ) nanoparticles were cathodically electrodeposited at room temperature from environmentally benign elec-
trolytes. The shape, size, and production rate of nanoparticles were strongly influenced by electrochemical conditions (e.g. FeCl3 concentration,
current density). X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis indicated that randomly oriented polycrystalline
maghemite nanoparticles were synthesized with the (3 1 1) and (4 4 0) peaks as the main diffraction peaks. Transmission electron microscopy
(TEM) images revealed that average particle size decreased from approximately 23 to 7 nm with increased current density. Magnetic saturation
(MS ) of maghemite nanoparticles was determined to be 66 emu g1 (66 Am2 kg1 ) at 300 K. The present maghemite nanoparticles showed a greater
As(V) adsorption compared to iron nanoparticles, which might be attributed to a higher specific surface area.
2007 Elsevier B.V. All rights reserved.

Keywords: Electrodeposition; Maghemite; Nanoparticles; Environmental remediation; As(V); Adsorption

1. Introduction Various wet chemical processes have been used to synthesize

maghemite nanoparticles including precipitation, thermolosis
Nanoparticles and one-dimensional nanostructures are the by organic metallic decomposition and carbonyl decomposi-
focus of many researchers because they often exhibit unique tion [8]. Chemical precipitation is one of the oldest and simple
properties, which cannot be achieved by their bulk counterparts techniques for the synthesis of nanoparticles [8]. In precipita-
[13]. Magnetic nanoparticles are an important class of func- tion processes, the metal precursors (e.g. FeCl3 or FeCl2 ) are
tional nanomaterials which possess unique magnetic properties. dissolved in a solvent and a precipitating agent (e.g. NH4 OH)
The potential applications of magnetic nanoparticles include fer- is added to form nanoparticles. Even though chemical precip-
rofluids for audio speakers [4], surface functionalized probes itation is simple and manufacturable, this process is difficult
for biosensors and targeted drug delivery [5], magnetic stor- to control and yields nanoparticles with a broad size distri-
age media, powder compacts for power generation, contrasting bution and irregular morphology. Thermolosis can produce
agents in magnetic resonance imaging and adsorbents for toxic monodispersed maghemite nanoparticles with good crystallinity
environmental pollutants [6]. by thermal decomposition of iron cupferron complexes in octy-
Maghemite (-Fe2 O3 ) is a ferromagnetic oxide that has been lamine and thermal decomposition of iron pentacarbonyl in
widely used as a magnetic recording material for tape drives. the presence of oleic acid, respectively [9,10]. Although ther-
In addition, maghemite nanoparticles have been utilized as fer- molosis in the presence of capping agents offers monodisperse
rofluids hyperthermia (MFM) in tumor treatment because of nanoparticles with good crystallinity, these methods operate at
good chemical stability and biocompatibility with high heat- higher temperature (100300 C) and require toxic and expen-
ing capacity in the presence of alternating magnetic fields sive precursors. These methods have limited controllability of
[6,7]. particle morphology and size causing the variation of magnetic
properties.
Electrodeposition is a promising alternative technique for
Corresponding author. Tel.: +1 951 827 7710; fax: +1 951 827 5696. fabrication of nanoparticles, because it is simple, manufac-
E-mail address: [email protected] (N.V. Myung). turable, inexpensive, fast, operates at near room temperature, and

1385-8947/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2007.10.025
 H. Park et al. / Chemical Engineering Journal 139 (2008) 208212 209

its ability to control composition, crystallinity, and properties of using a magnetic property measurement system (MPMS, Quan-
the deposit by adjusting deposition conditions. tum Design) at room temperature with applied magnetic field up
Iron oxide thin films were both cathodically and anodically to 4 kOe.
electrodeposited [1119]. In the case of anodic formation of iron
oxides, the different phases of the iron oxidesoxyhydroxides 2.2. As(V) remediation
thin films were obtained by adjusting deposition potentials and
solution composition [11]. Zotti et al. [17] reported the cathodic As(V) stock solutions (1000 mg L1 ) were prepared using
electrodeposition of amorphous Fe2 O3 thin films by reduction analytical-grade Na2 HAsO4 7H2 O (Sigma Aldrich Chemical
of Fe (III) perchlorate in oxygenated acetonitrile where ferric Co.) and diluted as needed. 1 M HCl or NaOH solutions were
ions reduced with dissolved oxygen to form amorphous Fe2 O3 . used for pH adjustment. All experiments were performed in
Amorphous Fe2 O3 thin films were later converted to -Fe2 O3 0.01 M NaCl background solution.
(i.e. hematite) thin films after heat treatment. Schrebler et al. As(V) remediation with using maghemite nanoparticles
[18] electrodeposited amorphous and nanocrystalline -Fe2 O3 was conducted by reacting 1 mg L1 As (V) in 0.01 M NaCl
(i.e. hematite) thin films from electrolytes containing 5 mM with varying maghemite nanoparticles concentrations (0.10,
FeCl3 + 1M H2 O2 + 5 mM KF + 0.1 M KCl at 50 C. The reduc- 0.5, 0.75, and 1.00 g L1 ). For these experiments, maghemite
tion of hydrogen peroxide at the cathode caused an increase in nanoparticles were synthesized at 500 mA cm2 in 0.01 M FeCl3
local pH on the surface of the cathode which later directed the electrolytes as described in the previous section. At predeter-
surface precipitation of Fe(OH)3 . Ferric hydroxides were later mined times, tests tubes in which experiments were conducted
transformed to Fe2 O3 by the thermal annealing in air. Favier et al. were centrifuged, the supernatant was filtered through a 0.22 m
synthesized amorphous maghemite nanoparticles by anodic dis- pore PVDF filter, and analyzed by for total arsenic by atomic
solution of a sacrificial Fe anode, followed by chemical reaction adsorption spectroscopy (AAS).
in an organic medium [19].
In this work, we demonstrated a simple method for the 3. Results and discussion
electrochemical deposition of crystalline maghemite (-Fe2 O3 )
nanoparticles by cathodic reaction at room temperature in Fig. 1 shows the dependence of the production rate on the
environmentally benign aqueous electrolytes. In addition, we current density and FeCl3 concentrations. As expected, the pro-
demonstrate the ability to control the particle size, morphol- duction rate linearly increased with increasing current density.
ogy and production rate by adjusting the deposition conditions. The maximum production rate was observed at 0.05 M FeCl3
Furthermore, electrodeposited maghemite nanoparticles were and as the concentration of FeCl3 was increased to 0.10 M, the
applied to remediate As(V) in aqueous solutions. production rate decreased might be attribution to the increase in
side reactions including ferric ions to ferrous ions and ferrous
2. Experimental ions to metallic iron.
Since iron oxide nanoparticles were electrodeposited in natu-
2.1. Electrochemical synthesis and characterization rally aerated solution, two competitive electrochemical reactions
may occur at the cathode. Dissolved oxygen can be reduced and
Maghemite nanoparticles were cathodically electrodeposited then combines with ferric ions to form Fe2 O3 which is insoluble
from electrolytes with various FeCl3 concentrations (i.e. 0.01, (Eq. (1)). However, this process is probably limited by dissolved
0.05, and 0.10 M of FeCl3 ) under gavalnostatic control at 20 C.
The electrochemical cell was a 150 ml glass jar with a working
volume of 100 ml, an open to the atmosphere. Steel rods served
as both the cathode and anode. The surface area of cathode was
fixed at 4 cm2 . The pH of solution was adjusted to 2 by adding
HCl or NaOH. The current densities were varied from 150 to
2000 mA cm2 . All reagents used in this study were reagent
grade. Ultrapure water was used in preparation of solutions
(Milli-Q Academic, Millipore). Resistivity of ultrapure water
was 18.2 M cm at 25 C and concentration range of TOC was
510 ppb level.
To determine the phase and composition of nanoparticles, X-
ray photoelectron spectroscopy (XPS) analysis was performed
using a Physical Electronics 5500/5600 ESCA system with
monochromatic Al K radiation (1486.7 eV) as the X-ray source.
The crystal structure of nanoparticles was determined using X-
ray diffraction with a Miniflex diffractometer by Rigaku Corp
using Cu K radiation. The size and morphology of nanopar-
ticles were characterized by transmission electron microscopy Fig. 1. Dependence of the maghemite nanoparticle production rate on the
(TEM). The magnetic properties of nanoparticles were measured applied current density and the FeCl3 concentration.
210 H. Park et al. / Chemical Engineering Journal 139 (2008) 208212

oxygen concentration. Another possible reaction is via hydrogen

gas evolution (Eq. (2a)) which may cause an increase in local pH
on the surface of cathode. This promotes the formation of ferric
hydroxides (Eq. (2b)). Ferric hydroxides later convert to form
Fe2 O3 (Eq. (2c)). The overall reaction is shown in Eq. (2d). It
was experimentally observed that there was a significant amount
of hydrogen gas evolution during electrodeposition. This and
the low dissolved oxygen concentration in solution suggest that
Reaction 2 is the dominant electrodeposition reaction pathway
to form Fe2 O3 .
Reaction 1

4Fe3+ + 3O2 + 12e 2Fe2 O3 (1)

Reaction 2

Fig. 3. X-ray diffraction patterns of the maghemite nanoparticles. Maghemite

nanoparticles were synthesized at 500 mA cm2 in 0.01 M FeCl3 .

Fig. 3 shows the X-ray diffraction patterns of the maghemite

nanoparticles prepared at different current densities. Indepen-
dent of the current density, nanoparticles were randomly oriented
XPS spectrums and X-ray diffraction patterns were collected polycrystalline with two main diffraction peaks at (3 1 1) and
to determine the phase, composition, and crystallinity of iron (4 4 0). However, the X-ray diffraction intensity of (3 1 1) and
oxide nanoparticles. Fig. 2 shows the XPS spectrum of iron (4 4 0) slightly decreased and increased with increasing current
oxide nanoparticles deposited at 500 mA cm2 in 0.01 M FeCl3 . densities, respectively, indicating the slight changes in crystal
As shown in Fig. 2, the position of the Fe (2p3/2 ) and Fe (2p1/2 ) structure as a function of current density.
peaks were at 711.1 and 724.9 eV, respectively, which is similar Transmission electron microscopy (TEM) was utilized to
to bulk counterpart (i.e. Fe (2p3/2 ) at 711 eV and Fe (2p1/2 ) at investigate the shape and size dependence of maghemite
725 eV) [20,22]. From the XPS analysis, the atomic ratio of nanostructures as functions of current density and electrolyte
iron and oxygen was also determined to be approximately 2:3, compositions (Fig. 4). The shape and size of nanoparticles were
verifying the formation of Fe2 O3 . Unlike bulk hematite, which strongly influenced by electrolyte composition and applied cur-
has two distinct Fe (2p3/2 ) peaks, one narrow Fe (2p3/2 ) peak was rent density. For example, dendritic maghemite nanostructures
observed that matched maghemite [21-23]. In addition, C1 S and with approximately 8001200 nm thick trunks and 50210 nm
O1 S were observed at 285.4 and 530.4 eV, respectively. These thick branches were synthesized at 150 mA cm2 in 0.01 M
results suggested that electrodeposited iron oxide nanoparticles FeCl3 (Fig. 4a). However, as the concentration and current den-
are maghemite. sity increased, spherical shaped nanoparticles were observed
(Fig. 4bi). In all cases, the size of nanoparticles decreased
with increased current density (Fig. 5), though this was most
pronounced at 0.01 M FeCl3 for which the average size of the
nanoparticles decreased from 23 to 7 nm with increasing the
current density from 500 to 2000 mA cm2 . The change in mor-
phology and size with the increase in current density might
be attributed to the (1) higher nucleation rate; (2) shift reac-
tion control from kinetic control to mass transfer control; and
(3) non-uniform electric field cause by nanostructure formation
at the electrode surface. At relatively high deposition current
density (e.g.150 mA cm2 in 0.01 M FeCl3 ), the local current
density at the electrode is not uniform because of the higher
electrical field at the edge of the growing deposit, which favors
the nucleation at the tip of the deposit. These conditions can
lead to the formation of dendrites. When the deposition current
density is very high (e.g. >500 mA cm2 ), powdered deposits
(i.e. micro or nanoparticles) are formed on the cathode due to
Fig. 2. XPS spectra of the electrodeposited maghemite nanoparticles. the high nucleation rate. The deposit morphology shifts from
Maghemite nanoparticles were synthesized at 500 mA cm2 in 0.01 M FeCl3 . dendritic to powdery deposits similar to other electrodeposi-
 H. Park et al. / Chemical Engineering Journal 139 (2008) 208212 211

Fig. 4. TEM images of maghemite nanoparticles: current densities were (ac) 150 mA cm2 ; (df) 500 mA cm2 ; (gi) 2000 mA cm2 ; electrolyte compositions
were (a, d, g) 0.01 M FeCl3 , (b. e, h) 0.05 M FeCl3 , (c, f, i) 0.10 M FeCl3 .

tion systems [24]. These results clearly demonstrate that the Lastly, the adsorption capacity of the nanoparticles was deter-
shape and size of maghemite nanoparticles can be controlled mined using arsenate (As(V)) as a model pollutant. As shown in
by adjusting electrolyte compositions and deposition current Fig. 7, As(V) was rapidly removed from solution and reached
density. an equilibrium within 520 min of exposure to the maghemite
Fig. 6 shows the B-H loop of maghemite nanoparticles nanoparticles. Arsenic adsorption followed a pseudo first order
at 300 K. The magnetic saturation (MS ) and coercivity (HC ) reaction as follows:
were determined to be 66 emu g1 (Am2 kg1 ) and 59 Oe d[Astot ]
(4.7 103 A m1 ), respectively. Both MS and HC were simi- Rate = = kobs [-Fe2 O3 ] (3)
dt
lar to maghemite nanoparticles synthesized by DC thermal arc
plasma method and solvothermal reduction method [22,25]. where [Astot ] is the soluble arsenic concentration (mg L1 ), [-
Fe2 O3 ] is the concentration of maghemite nanoparticles (g L1 ),
and kobs is the pseudo first order rate constant (min1 ). The

Fig. 5. Average maghemite nanoparticles diameter as a function of the applied

current density and the concentration of FeCl3 . The error bars show one standard
deviation. Fig. 6. B-H loop of maghemite nanostructures (500 mA cm2 , 0.01 M FeCl3 ).
212 H. Park et al. / Chemical Engineering Journal 139 (2008) 208212

Acknowledgement

This work was supported by the Korea Science and

Engineering Foundation (KOSEF) grant (no. M10500000-
12806J000012810) through the National Research Laboratory
Program by the Korea government (MOST) and University of
California Toxic Substances Research & Teaching Program
(UC TSR & TP).

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