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Particuology
journal homepage: www.elsevier.com/locate/partic

Magnetic and electrochemical behavior of rhombohedral -Fe2 O3 nanoparticles

with (1 0 4) dominant facets
Zhong Liu a,b , Baoliang Lv a, , Dong Wu a , Yuhan Sun a,c , Yao Xu a
a

State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
Key Laboratory of Salt Lake Resources and Chemistry, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, China
c
Low Carbon Conversion Center, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201203, China
b

a r t i c l e

i n f o

Article history:
Received 22 February 2012
Received in revised form 21 May 2012
Accepted 12 June 2012
Keywords:
-Fe2 O3
Morphology
Magnetic materials
Chemical synthesis

a b s t r a c t
Uniform rhombohedral -Fe2 O3 nanoparticles, 60 nm in size, were synthesized via a triphenylphosphine-assisted hydrothermal method. Scanning electron micrograph (SEM) and transmission electron micrograph (TEM) analyses showed that the as-synthesized rhombohedral nanoparticles were
enclosed by six (1 0 4) planes. The concentration of triphenylphosphine played an important role in
morphological evolution of the -Fe2 O3 nanoparticles. The as-prepared rhombohedral nanoparticles possessed remanent magnetization Mr of 2.6 103 emu/g and coercivity HC of 2.05 Oe, both lower than
those of other -Fe2 O3 particles with similar size, indicating their potential applications as superparamagnetic precursor materials. Furthermore, these rhombohedral -Fe2 O3 nanoparticles exhibited good
sensor capability toward H2 O2 with a linear response in the concentration range of 220 mM.
2013 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of
Sciences. Published by Elsevier B.V. All rights reserved.

1. Introduction
Shape-controlled synthesis of nanocrystals with different facets
exposed is important for both fundamental studies and technological applications, because these crystals exhibit different physical
and chemical properties on the different facets. For example,
Ni(OH)2 nanocolumns with (1 0 0) facets can enhance electrochemical catalytic activity (Zhang et al., 2011), and TiO2 nanosheets with
a higher percentage of (0 0 1) facets exhibit more effective photocatalytic performance (Han, Kuang, Jin, Xie, & Zheng, 2009). As
an important and thermodynamically stable iron oxide, -Fe2 O3
has been widely used in commercial and industrial applications,
including pigments (Della et al., 2007), catalysts, purication agents
(Zhong et al., 2006), magnetic materials (Bhowmik & Saravanan,
2010), sensors (Gou, Wang, Park, Liu, & Yang, 2008), lithium ion
batteries (Zeng et al., 2008), solar energy conversion and water
splitting (Le Formal, Gratzel, & Sivula, 2010). Many efforts have
been focused on the controllable preparation of -Fe2 O3 nanoparticles with various geometries and exposed surfaces, since the
properties of the -Fe2 O3 crystals are largely determined by
the exposed surfaces. For example, dodecahedral -Fe2 O3 particles, enclosed by twelve equivalent (1 0 1) planes, show much
stronger magnetism than other nanostructures (Lv et al., 2010),

Corresponding author. Tel.: +86 351 4063121; fax: +86 351 4041153.
E-mail address: lbl604@sxicc.ac.cn (B. Lv).

and tetrakaidecahedral -Fe2 O3 nanoparticles which are bound by

(0 1 2), (1 0 2) and (0 0 1) facets, lose ferromagnetism at temperatures lower than the Morin transition temperature (Tm ) (Yin et al.,
2010). In order to prepare -Fe2 O3 nanocrystals with different morphologies and exposed facets, the choice of appropriate adsorption
ions or ligands was most important. Usually, organic polymers
which are soluble under normal temperature and pressure, are
chosen as adsorption and dispersing reagents for the preparation
of -Fe2 O3 with different morphologies, such as tetrabutylammonium bromide (TBAB), polyvinylpyrrolidone (PVP) (Geng, Ma, &
You, 2008) and sodium carboxymethyl cellulose (CMC) (Yin et al.,
2010). The inuences of organic compounds and oxygen vinyl
polymers on -Fe2 O3 particle morphologies were systematically
investigated by Kandori etc. (Kandori, Hori, & Ishikawa, 2006;
Kandori, Hayashi, Matsukawa, Fukusumi, & Morisada, 2010). Meanwhile, inorganic anions with selective adsorption capability were
also used to change the growth behavior of -Fe2 O3 particles, e.g.,
Wang obtained dendritic -Fe2 O3 micro-pines with growth along
six crystallographically equivalent [1 0 0] directions in the presence
of CN (Cao et al., 2005). Jia et al. (2008) described the shape of Fe2 O3 nanorings as mainly regulated by the adsorption of H2 PO4
on faces parallel to the [0 0 1] direction during nanocrystal growth,
and the hollow structure as given by the preferential dissolution
of -Fe2 O3 along the [0 0 1] direction due to the strong coordination of So2
. Lv, Xu, Wu, & Sun (2011) synthesized single-crystal
4
-Fe2 O3 hexagonal nanorings by using F specially adsorbed onto
the (1 0 0) plane, and SCN -induced oriented dissolution along the

1674-2001/$ see front matter 2013 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

http://dx.doi.org/10.1016/j.partic.2012.06.016

Please cite this article in press as: Liu, Z., et al. Magnetic and electrochemical behavior of rhombohedral -Fe2 O3 nanoparticles with
(1 0 4) dominant facets. Particuology (2013), http://dx.doi.org/10.1016/j.partic.2012.06.016

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[0 0 1] direction. The magnetic property of the above mentioned

(1 0 0), (0 0 1), (1 0 1) and (1 0 2) planes were tested, and the inuence of adsorption ions or ligands on the above low surface-energy
facet were investigated. However, few reports referred to adsorption of ions or ligands which inuence -Fe2 O3 morphologies on
the (1 0 4) facet, and special magnetic property and sensing capacity of rhombohedral -Fe2 O3 which only exposed (1 0 4) facet was
not still reported.
In the present work, uniform rhombohedral -Fe2 O3 particles
(60 nm) which exposed only the (1 0 4) facets were successively
synthesized by a simple hydrothermal route, and its magnetic
properties and sensing capacity were investigated. At high temperature and pressure, triphenylphosphine obviously had the
coordination and dispersion effect for the formation of -Fe2 O3
particles. The as-synthesized -Fe2 O3 showed not only lower
remanent magnetization and coercivity than others reported in the
literature (Cao et al., 2006; Gao, Liang, Yang, & Sun, 2009), but also
had good sensor capability toward H2 O2 with a linear response in
certain specic range of concentration.

Fig. 1. XRD patterns of the product formed with 10 mol% triphenylphosphine.

3. Results and discussion

2. Experimental
All chemicals were analytical grade and used without further
purication. A typical experiment was as follows: 9.0 102 mM
triphenylphosphine was added to an 80 mL aqueous solution of
9.0 101 mM FeCl3 6H2 O under stirring, while keeping the molar
ratio of triphenylphosphine to Fe3+ at 10%. The solution was
subsequently transferred into a 100 mL autoclave, sealed, and
maintained at 220 C for 24 h. Then, the autoclave was cooled
gradually to room temperature. The red precipitates were collected by centrifugation, and then washed with deionized water
and ethanol in an ultrasonic bath. The cycle was repeated three
times, and nally the product was dried in a desiccator at 60 C
for 4 h. Morphological comparative experiments were similar to
the procedure described above, except for the molar ratio of triphenylphosphine to Fe3+ which was changed from 0% to 2.5%, 5%,
and 20%.
X-ray powder diffraction (XRD) spectra of the products were
acquired by a Philips XPert PRO SUPER X-ray diffractometer equipped with graphite-monochromatized Cu K radiation
Morphologies of the samples were examined by
( = 1.5418 A).
scanning electron microscopy (SEM, X-650) and transmission electron micrograph (TEM, Hitachi H-600). Selected area electron
diffraction (SAED) patterns were obtained on a high-resolution
transmission electron microscope (HRTEM, JEOL-2010). Magnetic
hysteresis loops of the samples were measured at room temperature by a superconducting quantum interference device (SQUID,
MPMS-XL5). Electrochemical response was measured at room
temperature with a conventional three-electrode system and an
electrochemical workstation (CHI760A, USA). All the potentials
were referred to a saturated calomel electrode (SCE). A platinum
plate was used as the counter electrode. Modied glassy carbon
(GC) electrode (3 mm in diameter) was used as the working electrode. The GC electrodes were polished with aqueous slurries of
alumina powder (down to 0.05 m), and then carefully rinsed with
bidistilled water in an ultrasonic bath for 5 min Before modication, 0.5 mL of Naon lm alcohol solution (1%, v/v) and 1 mg of
as-prepared -Fe2 O3 particles were mixed to form a suspension
by sonication. Then, this 50 L suspension was cast onto the surface of the pretreated GC electrode, and the solvent was allowed to
evaporate at room temperature, leaving the as-prepared -Fe2 O3
immobilized coating onto the GC electrode surface. By bubbling
high-purity nitrogen, the phosphate buffer solution (PBS, pH 7.2)
was made thoroughly anaerobically.

Fig. 1 shows the XRD patterns of the product synthesized by

the typical experiment, showing that the characteristic peaks are
consistent with the standard data of rhombohedral -Fe2 O3 (JCPDS
33-0664). The strong and sharp diffraction peaks mean high crystallinity of the products.
The size and morphology of the rhombohedral -Fe2 O3 particles
obtained at 10 mol% triphenylphosphine were examined by SEM
and TEM (Fig. 2). Fig. 2(a) shows the sample containing more than
80% of rhombohedral nanoparticles with narrow size distribution.
Three kinds of particles could be identied in Fig. 2(b)(d). Fig. 2(b)
shows rhombic particles with an obtuse angle of about 115 and
an edge of about 60 nm. Fig. 2(c) shows hexagonal particles with
equal edge lengths. Fig. 2(d) illustrates a situation apparently different from both Fig. 2(b) and 2(c). Actually, only one kind of particles
exists in these images, i.e. rhombohedral. Apparently three kinds
of particles are present in the TEM images because of their different orientations, as shown in the corresponding insets. Similar
phenomena can also be found in the literature, for instance, nanodisks of Cu and CuS (Puntes, Zanchet, Erdonmez, & Alivisatos,
2002; Sigman et al., 2003). On the basis of the above SEM and TEM
analyses, the -Fe2 O3 particles in Fig. 2(a) are all rhombohedral.
Their surfaces were covered by six identical rhombi with obtuse
angles, each about 115 , and edge lengths, each about 60 nm.
HRTEM was used to provide more information about the
microstructure and morphology of the rhombohedral -Fe2 O3 particles. Fig. 3 presents the HRTEM images from different directions.
Fig. 3(a) shows the TEM image of a typical rhombohedral -Fe2 O3
particle and its corresponding SAED pattern (inset of Fig. 3(a)). The
diffraction spots can be attributed to (1 1 0), (0 1 4), (1 0 4) planes
and/or their equivalent planes under the incident electron beam
along the [4 4 1] direction. Besides, the sharp diffraction spots also
reveal the single crystalline nature of the synthesized particles.
Fig. 3(b) displays the HRTEM image of the rounded corner of the
rhombohedral particle. The lattice spacings are 0.251 nm, 0.269 nm
and 0.269 nm, which agree well with the (1 1 0), (1 0 4) and (0 1 4)
planes, respectively. The angle in the bottom of particle is near
115.8 (Fig. 3(a)), which is very close to the angle between (1 0 4)
and (0 1 4) crystal planes (115.2 ). The angle value and particle edge
image conrm that the side facets are parallel to the (1 0 4) and
(0 1 4) crystal planes, which t well with the results from the SAED
pattern (inset of Fig. 3(a)). Fig. 3(c) and 3(e) are the TEM images
of the single rhombohedral particle, and Fig. 3(d) and 3(f) are the
HRTEM images (insets are their corresponding FFT patterns) taken

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Fig. 2. SEM (a) and TEM ((b)(d)) images of rhombohedral -Fe2 O3 particles obtained with 10 mol% triphenylphosphine.

from the regions annotated with d and f in Fig. 3(c) and 3(e).
In Fig. 3(d), the lattice spacings are 0.362 nm and 0.268 nm, corresponding respectively to (0 1 2) and (1 0 4) planes and/or their

equivalent planes under the incident electron beam along [4 2 1]

direction. In Fig. 3(f), three sets of clear lattice fringes with interplanar distance of 0.252 nm are observed, which can be indexed to
the (1 1 0) planes and/or to their equivalent planes. According to
the above HRTEM analysis, the surface parallel to the background
should be the (1 1 4) plane on the basis of reciprocity law, which is
in good agreement with the results obtained by using TEM and AFM
techniques (Rodriguez et al., 2007). That is to say, the rhombohedra particles have three equivalent planes and these three facets all
belong to the {1 0 4} family. The model of rhombohedral -Fe2 O3
particles viewed from the above different orientations is illustrated
by Fig. 3(g), in which [4 4 1] is parallel to two (1 0 4) planes and
is parallel to one (1 0 4) plane.
[4 2 1]
In the -Fe2 O3 shape evolution process, the ratio of ligands
to precursor played the most important role (Wang, Min, & Yu,
2007). To better understand the formation and shape evolution
processes of the synthesized rhombohedral -Fe2 O3 nanoparticles, different molar ratios of triphenylphosphine to Fe3+ ions
were investigated. The morphologies of the corresponding products were investigated by SEM and TEM as shown in Fig. 4. Without
adding triphenylphosphine, the morphology of particles was that
of an irregular sphere with large particle size distribution (Fig. 4(a)
and 4(b)). With 2.5 mol% of triphenylphosphine, well dispersed
spherical particles were obtained (Fig. 4(c) and 4(d)), with particle size of around 60 nm. With increasing triphenylphosphine to
5 mol%, the shape of the product changed from sphere to irregular
polyhedron (Fig. 4(e) and 4(f)). Fig. 2(a) shows a typical SEM image
of -Fe2 O3 particles, which was obtained by increasing the amount
of triphenylphosphine to 10 mol%, showing uniform rhombohedral
-Fe2 O3 nanoparticles with a narrow size distribution. By further
increasing the amount of triphenylphosphine to 20 mol% (Fig. 4(g)
and 4(h)), the particle shape remained rhombohedral though the

particle size became nonuniform. Fig. 5 shows XRD patterns that

provide further information on particle crystallinity and phase
composition. All the diffraction peaks in Fig. 5 are readily indexed
to -Fe2 O3 (JCPDS 33-0664), indicating that triphenylphosphine
has slight inuence on crystallinity and phase for reaction temperatures up to 220 C.
On the basis of the above SEM and TEM results, it can be concluded that the shape and size of -Fe2 O3 nanoparticles varied
obviously with the concentration of triphenylphosphine. It is well
known that the triphenylphosphine molecule has a phosphorus
atom and three benzene rings. The phosphorus atom can provide
isolated pair of electrons to coordinate with positive ions. The
surface of -Fe2 O3 particles is covered by adsorbed hydroxyls in
solution, and the (1 0 4) plane possesses the highest hydroxyl density of 5.3 nm2 , including singly, doubly and triply coordinated
hydroxyl groups (Cornell & Schwertman, 2003). When rhombohedral -Fe2 O3 nanoparticles are synthesized in acid solution
(pH = 2.7), these hydroxyls are protonated becoming most active
to adsorb phosphorus atom. The adsorption capacity and density is larger on the (1 0 4) plane than others, thus restraining the
crystal growth on (1 0 4) planes and leading to particle surface
enclosed by {1 0 4} family facets. Besides, when triphenylphosphine was adsorbed on the surface of -Fe2 O3 particles, the effect
of steric hindrance and electron cloud on the three benzene rings
will prevent crystal from getting close to each other, thus leading
to the synthesis of well dispersed rhombohedral -Fe2 O3 nanoparticles. Between adsorption and dispersion, the main effect changed
from adsorption to dispersion with increasing triphenylphosphine,
and the morphology of particles was transformed from aggregated particles to regular nanocrystals. The above analysis reveals
that particle shape depends strongly on the adsorption of triphenylphosphine on -Fe2 O3 particles.
Because of the role of anisotropy on magnetism, the size and
shape of magnetic materials are crucial in affecting their magnetic behavior (Song & Zhang, 2004). It is worthy to note that

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Fig. 3. (a), (c) and (e), TEM images of a single -Fe2 O3 particle; (b), (d) and (f), HRTEM images of the labeled corners, as shown in (a), (c) and (e), oriented along the [4 4 1],
and [0 0 1] axes; insets of (a), (d) and (f), the corresponding SAED patterns and FFT patterns; and (g), the model of a single rhombohedral -Fe2 O3 particle.
[4 2 1]

the particles in Fig. 2(a) and Fig. 4(c) have similar size (60 nm)
but possess different shapes, while the particles in Fig. 2(a) and
Fig. 4(g) show similar shape (rhombohedral) but different size.
Therefore, magnetic hysteresis measurements of these three typical -Fe2 O3 particles were carried out to investigate the effects of
particle size and shape on the -Fe2 O3 magnetic properties (Fig. 6).
Curves ac in Fig. 6 represent the hysteresis loops of spherical,
rhombohedral and nonuniform rhombohedral -Fe2 O3 particles at
room temperature, while their morphologies were already shown
in Fig. 4(c), Fig. 2(a), and Fig. 4(g), respectively. In these curves,
three samples show weakly ferromagnetic behavior, and maximum magnetization is not reached up to saturation in the applied
magnetic eld. The magnetizations at the maximum applied magnetic eld of 1 T, Mmax , are 0.45, 0.48, and 0.47 emu/g, respectively.

The remanences of the three samples are 0.11, 2.60 103 and
1.10 102 emu/g, and the corresponding coercivities are 549.60,
2.05 and 13.87 Oe (see table inside Fig. 5), respectively. The uniform rhombohedral -Fe2 O3 nanoparticles enclosed by the (1 0 4)
planes exhibit lower coercivity than bulk -Fe2 O3 (0.11 emu/g) or
smaller -Fe2 O3 nanoparticles (8.70 103 emu/g) at 300 K (Lian
et al., 2009), indicating that rhombohedral -Fe2 O3 could be a
potential precursor for preparing superparamagnetic -Fe2 O3 particles. Coercivity is known to depend on several possible factors,
including crystallinity, size, structure, surface disorder, morphologies, etc. The lower coercivity of rhombohedral -Fe2 O3 particles
may be attributed to the six equivalent exposed (1 0 4) plane surfaces, which make their surface anisotropy smaller than that for
spherical and irregular rhombohedral particles (Song & Zhang,

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Fig. 4. SEM ((a), (c), (e), (g)) and TEM ((b), (d), (f), (h)) images of products synthesized using different amounts of triphenylphosphine: (a) and (b) 0 mol%, (c) and (d) 2.5 mol%,
(e) and (f) 5 mol%, (g) and (h) 20 mol%.

2004). Moreover, well dispersed particles have more single domain

than multidomain, thus decreasing their remanence and coercivity
(Wang & Gao, 2009).
The sensor properties of as-synthesized rhombohedral -Fe2 O3
particles were also investigated. Traditionally, hydrogen peroxide is analyzed with enzyme-modied electrodes. However, the
instability of these electrodes remains a major problem, which
is believed to be caused by the breaching of enzymes from the
electrode surface and the poisoning or loss of activity of the immobilized enzymes (Shao, Shan, Wong, & Lee, 2005). As the most
stable iron oxide, -Fe2 O3 is potentially more suitable for detecting hydrogen peroxide in a physiological system (pH 7.2) (Gong,
Wang, Zhao, & Song, 2008). Curves ad in Fig. 7(A) show the cyclic
voltammograms of a bare GC electrode, and a spherical -Fe2 O3
(Fig. 4(c)), nonuniform rhombohedral -Fe2 O3 (Fig. 4(g)), and the

regular rhombohedral -Fe2 O3 (Fig. 2(a)) modied GC electrode in

phosphate buffered saline (PBS, pH 7.2) in the presence of 8 mM
H2 O2 . Nearly no reductive peak is observed at the GC electrode,
while a small increased reductive peak is obtained at the spherical and nonuniform -Fe2 O3 modied GC electrode, and reductive
peak increases obviously at the rhombohedral -Fe2 O3 modied
GC electrode. Thus, the rhombohedral -Fe2 O3 modied GC electrode exhibits good response at 0.5 V for reduction of H2 O2 ,
suggesting that the -Fe2 O3 is catalytic to the reduction of H2 O2 .
Fig. 7(B) shows the typical amperometric responses of the bare GC
electrode, and the spherical -Fe2 O3 (Fig. 4(c)), irregular -Fe2 O3
(Fig. 4(g)), and rhombohedral -Fe2 O3 (Fig. 2(a)) modied GC electrode to the successive addition of H2 O2 at an applied potential

Fig. 5. XRD patterns of particles formed with different amount of triphenylphosphine, from 0 mol% to 20 mol%.

Fig. 6. Magnetization loops for synthesized -Fe2 O3 particles with different morphologies: (a) spherical, (b) rhombohedral and (c) nonuniform rhombohedral.

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with a linear response in the concentration range of 220 mM, indicating its potential application as a superparamagnetic precursor
material and chemical sensor.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (No. 21003147), Natural Science Foundation of
Shanxi (2011011007-3) and the State Key Laboratory of Coal Conversion (SKLCC) in-house project (No. 2011BWZ005).
References

Fig. 7. (A) Cyclic voltammograms of a bare GC electrode (a), and a spherical -Fe2 O3
(b), irregular -Fe2 O3 (c), and the rhombohedral -Fe2 O3 (d) particles modied GC
electrode in PBS (pH 7.2) in the presence of 8 mM H2 O2 . Scan rate = 50 mV/s. (B)
Amperometric response of the bare GC electrode (a), spherical -Fe2 O3 (b), irregular
-Fe2 O3 (c), and rhombohedral -Fe2 O3 (d) modied GC electrode with successive
additions of H2 O2 from 2 mM to 30 mM in PBS (pH 7.2) at an applied potential of
0.5 V (vs. SCE) (inset: its corresponding calibration plot for curve d).

of 0.5 V, which is the potential of the peak of the H2 O2 reduction.

The rhombohedral -Fe2 O3 sensor presents a linear response to
H2 O2 concentration in the range of 220 mM, with a correlation
coefcient of R2 = 0.997. These results show that the rhombohedral
-Fe2 O3 functions as a sensitive electrocatalyst for H2 O2 detection,
mainly owing to their well dispersion and the unique network of
interconnected pores on the exposed (1 0 4) plane surfaces of the
electrode. It also implies that the H2 O2 concentration in this wide
range can be found out in this curve by the current detected.
4. Conclusions
Rhombohedral -Fe2 O3 nanoparticles with a narrow size
distribution (60 nm) and each enclosed by six equivalent (1 0 4)
planes were synthesized. The inuence of triphenylphosphine on
the morphologies of the -Fe2 O3 nanocrystals and their magnetic
properties were studied. Triphenylphosphine acted as a coordinating and structure-directing agent in the synthesis process.
The uniform rhombohedral particles showed lower remanent
magnetization Mr and coercivity HC than other -Fe2 O3 products
of similar size, and exhibited good sensor capability toward H2 O2

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Please cite this article in press as: Liu, Z., et al. Magnetic and electrochemical behavior of rhombohedral -Fe2 O3 nanoparticles with
(1 0 4) dominant facets. Particuology (2013), http://dx.doi.org/10.1016/j.partic.2012.06.016