Accepted Manuscript

Magnetite Fe3O4 nanoparticles and hematite α-Fe2O3 uniform oblique hexago-

nal microdisks, drum-like particles and spindles and their magnetic properties

Gang Xu, Lingling Li, Zhihong Tao, Yi Zhang, He Tian, Xiao Wei, Ge Shen,
Gaorong Han

PII: S0925-8388(14)02799-6
DOI: http://dx.doi.org/10.1016/j.jallcom.2014.11.140
Reference: JALCOM 32694

To appear in: Journal of Alloys and Compounds

Received Date: 13 September 2014

Revised Date: 20 November 2014
Accepted Date: 21 November 2014

Please cite this article as: G. Xu, L. Li, Z. Tao, Y. Zhang, H. Tian, X. Wei, G. Shen, G. Han, Magnetite Fe3O4
nanoparticles and hematite α-Fe2O3 uniform oblique hexagonal microdisks, drum-like particles and spindles and
their magnetic properties, Journal of Alloys and Compounds (2014), doi: http://dx.doi.org/10.1016/j.jallcom.
2014.11.140

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Magnetite Fe3O4 nanoparticles and hematite α-Fe2O3 uniform oblique hexagonal
microdisks, drum-like particles and spindles and their magnetic properties

Gang Xu,* Lingling Li, Zhihong Tao, Yi Zhang, He Tian, Xiao Wei,* Ge Shen, Gaorong Han
State Key Laboratory of Silicon Materials and Department of Materials Science and Engineering,
Zhejiang University, Hangzhou 310027, China

Abstract: Magnetite Fe3O4 nanoparticles and uniform hematite (α-Fe2O3) oblique hexagonal
microdisks, drum-like particles, and spindles have been synthesized via a facile hydrothermal
reaction route, in which the mixture solvents of ethylene glycol (EG) and water are used as
reaction medium. The phase, size, shape and growth orientation of the synthesized iron oxide
crystals were characterized by powder X-ray diffraction and electron microscopy. When the
reaction medium is almost composed of EG, a lot of Fe3+ ions reduce to Fe2+ ions due to the effect
of EG, resulting in the magnetite Fe3O4 nanoparticles. As the volume ratio of EG/water in the
reaction medium is lower than 30:10, the reductive ability of EG is too low to reduce the Fe3+ ions
to Fe2+ ions, leading to the hematite α-Fe2O3 crystals. Moreover, since the adsorption of EG on the
crystals, the shape of the obtained hematite α-Fe2O3 crystals evolves from oblique hexagonal
microdisks to drum-like particles, and spindles due to the decrease of EG in the mixture reaction
medium solvent. The magnetic properties of the magnetite Fe3O4 nanoparticles and hematite
α-Fe2O3 uniform microcrystals were also investigated by measuring the magnetic hysteresis loops.
Keywords Hematite α-Fe2O3; Oxide materials; Magnetic properties; Scanning electron
microscopy
1. Introduction
Over the past decade, the interests on the nanostructured materials have expanded into
controlling the shape of the nanocrystals and understanding the correlations between the materials
properties and their shapes, because it has been confirmed that the shape of the nanocrystals can
be as vital as size for determining the uniqueness and novelty of materials properties [1-5]. In
consequence, a number of polyhedral-shaped crystals, including oxides and noble metals, have
been reported [6-10]. Iron oxide is an important transition metal oxide and usually exists in nature
in three phases of magnetite (Fe3O4), maghemite (γ-Fe2O3) and hematite (α-Fe2O3). Because of
the instinctive environment-friendly feature and profound performances, iron oxide materials have
been extensively studied in diverse fields including catalysis [11,12], environment protection [13],
gas sensors [14,15] magnetic storage media [16], and clinical diagnosis and treatment [17]. In
order to pursue the excellent performance, many efforts have also been carried out on the
synthesis and properties of the iron oxide nanostructures with well-defined morphologies, such as
nanocrystals [18], polyhedrons [10,14], cubes [14], spindles [19,20], rods/wires [21,22], tubes [23]
and flakes [13]. However, it is still a big challenge to develop a simple and reliable synthetic
method for controlling the morphology of the iron oxide nanoparticles.
Hydrothermal technique is an aqueous-based precipitation route. Because the nucleation and
growth can be controlled over by tuning the hydrothermal conditions, such as reaction medium
solvents, precursors, mineralizers, modifiers, during temperature and time, hydrothermal
technique is widely employed to synthesize the functional nanostructures with specific shapes
[24-26]. In the past few years a lot of uniform α-Fe2O3 nanocrystals with a variety of specific
shapes and morphologies have been realized via hydrothermal routes in virtue of the preferential
adsorption of the modifiers. For examples, quasi-cubic α-Fe2O3 nanocrystals were hydrothermally
synthesized with the assistance of poly-vinyl pyrrolidone (PVP) as a surfactant [12]. Because of
the exposition of {11-20} planes, the obtained quasi-cubic α-Fe2O3 nanocrystals express excellent
catalytic performance in the oxidation of CO. Under the modification effect of cetyltrimethyl
ammonium bromide (CTAB), α-Fe2O3 nanorods with polyhedral configuration were obtained via
a facile hydrothermal route [27]. Yang and his co-workers in virtue of the selective adhesion of
carboxyl methyl cellulose (CMC) on the facets to alter the crystal habits significantly have
successfully realized the synthesis of well-shaped polyhedral single-crystalline α-Fe2O3 particles
by the hydrothermal method [14]. Because of the contribution of the high-index facets, the
obtained polyhedral α-Fe2O3 particles exhibit outstanding gas-sensing performance over ethanol.
Recently, Chen and his co-worker [28] reported that by dint of the preferential adsorption of
ethanol molecules on (0001) planes, hexagonal α-Fe2O3 nanoplates with (0001) planes as basal
surfaces and (10-12) planes as side surfaces have been successfully grown via a simple
ethanol-thermal route in the presence of trace water under the effect of acetate sodium as
mineralizer.
Ethylene glycol (EG) is an organic solvent. Two hydroxyls are involved in the molecule of EG.
Thus, same as the ethanol, EG easily adsorbs on the surfaces of the crystals by hydrogen-bonding
to alter the nucleation and crystal growth behavior. In our more recent works, single-crystalline
SrTiO3 nanosheets [25] and monodispersed LiFePO4 nanoparticles [29] have been hydrothermally
achieved with EG as reaction medium solvent in the presence of trace water. In the present work,
we propose a facile and simple hydrothermal reaction route to realize the shape-controlled
synthesis of α-Fe2O3 crystals from oblique hexagonal microdisks to drum-like particles and
spindles by simply tuning the volume ratio of EG and water in the used reaction medium solvent.
With the basis of the experimental results, a possible phase- and morphology-evolution
mechanism of magnetite and hematite nano-/microcrystals was preliminarily proposed.
2. Experimental procedures
All chemicals are of analytical grade and were used as purchased without any further
purification. Hydrated iron nitrate (Fe(NO3)3·9H2O) and potassium hydroxide (KOH) were
purchase from Shanghai Reagent Chemical Factory (Shanghai, China), and ethylene glycol (EG)
from Hangzhou Changzheng Chemical Reagent Ltd (Hangzhou, China). Distilled water was used
throughout the experiment.
The hydrothermal reaction was carried out in a homemade Teflon-lined stainless-steel autoclave.
In a typical experimental procedure, Fe(NO3)3·9H2O (4.85 g) was dissolved in mixture solvent (40
mL) of EG and distilled water under vigorous magnetic stirring. Until completely dissolved, KOH
(2.46 g) was added while stirring, forming a suspension due to the precipitation of iron hydroxide.
After continuously stirring for 1h, the suspension as feedstock was sealed in a homemade
Teflon-lined stainless-steel autoclave (50 mL) and maintained at 200 oC for 6 h for hydrothermal
crystallization. Following nature cooling to ambient temperature, the resulting solid samples were
washed with distilled water and ethanol for several times, respectively, and finally dried in oven at
60 oC for 24 h for characterization. In order to realize the synthesis of the magnetite Fe3O4
nanoparticles and the hematite α-Fe2O3 crystals from oblique hexagonal microdisks to drum-like
particles, and spindles, the volume ratio of EG and distilled water in the feedstock suspension is
designed as 40:0, 35:5, 30:10, 26:14, 20:20 and 0:40 in turn.
X-ray powder diffraction (XRD) patterns were obtained by a Rigaku D/max-RA X-ray
diffractometer with high-intensity Cu Ka (λ=1.5418 Å) radiation with a step size of 0.02º.
Scanning electron microscopy (SEM) measurements were performed using a Hitachi S-4800
microscope (Japan). Transmission electron microscopy (TEM) and high-resolution TEM images
were taken with a FEI Tecnai G2 F30 TEM. Magnetic hysteresis loops of the products were
measured by a physical property measurement system of PPMs-9T, Quantum Design. In order to
investigate the catalytic activity, 10 mg of the synthesized hematite α-Fe2O3 crystals with different
morphology and 1000 mg ammonium perchlorate (AP) were mixed well for measuring the
differential temperature analysis (DTA) curve. The DTA was carried out on a NETZSCH TG 209
thermal analyzer from room-temperature to 800 °C at a heating rate of 10 °C/min in air.
3. Results and discussion
Fig.1 shows the XRD patterns of the hydrothermally synthesized samples in the presence of EG
at different volume ratio of EG and water. When the volume ratio of EG and water is higher than
35:5, all diffraction peaks of the obtained samples can be indexed to cubic lattice of Fe3O4
(JCPDS No. 26-1136), indicating that the synthesized samples are composed of pure crystalline
magnetite Fe3O4 crystals. However, when the volume ratio of EG and water decreases lower than
30:10, all the diffraction peaks of the obtained samples can be indexed to rhombohedral lattice of
α-Fe2O3 (JCPDS No. 33-0664), implying the synthesized powders are composed of pure hematite
α-Fe2O3 crystals. Nonetheless, only the intensity of the diffraction peaks of the α-Fe2O3 samples
hydrothermally synthesized without any EG agree well with the reported in the standard card of
JCPDS No.33-0664. As for the α-Fe2O3 samples hydrothermally synthesized in the presence of
EG, the diffraction peak of (11-20) become much higher compared to the reported in the standard
card, indicating more amount of (11-20) planes contribute to the X-ray diffraction.
Fig.2 shows the SEM images of the hydrothermally synthesized iron oxide samples in the
presence of EG at different volume ratio of EG and water. From the SEM image shown in Fig.2a
and b, one can find that the as-prepared magnetite Fe3O4 samples entirely consist of nanoparticles
with a narrow distribution. Moreover, with the addition of water the as-prepared magnetite Fe3O4
nanoparticles slightly enlarge. The SEM image shown in Fig.2c-e reveals that the synthesized
hematite α-Fe2O3 samples in the presence of EG consist of uniform regular crystals. Moreover,
with the EG/water volume ratio decreasing from 30:10 to 26:14 and 20:20, the uniform hematite
α-Fe2O3 regular crystals change from microdisks to drum-like particles, and spindles. Observed in
detail, the α-Fe2O3 microdisks obtained at the EG/water volume ratio of 30:10 are oblique
hexagonal and the size in diameter is ca. 250 nm, in thickness ca. 100 nm, respectively. With
regard to the drum-like particles, the size in length between the two flat surfaces is ca. 300 nm and
in diameter is about 250 nm. Otherwise, a few drum-like particles erected on the flat surfaces
express hexagonal shape (indicated by arrow in Fig.2d) similar the oblique hexagonal microdisks
obtained at the EG/water volume ratio of 30:10. Thus, it can be inferred that the decrease of EG in
the hydrothermal system induces the α-Fe2O3 hexagonal microdisks grow larger along the axis
and result in the drum-like particles. Meanwhile, the α-Fe2O3 spindles are ca. 400 nm in length
along the axis direction and ca. 250 nm in the maximum diameter. However, as without any EG is
added into the hydrothermal system, the synthesized α-Fe2O3 samples express irregular shape and
of broad size distribution. Therefore, it is believed that EG plays an important role in the
formation of the uniform α-Fe2O3 oblique hexagonal microdisks, drum-like particles and spindles.
The synthesized α-Fe2O3 microdisks, drum-like particles and spindles were further
characterized by TEM and HRTEM, respectively. Fig.3a and b present the TEM and HRTEM
images of the microdisks synthesized at the EG/water volume ratio of 30:10. The TEM image
reveals the α-Fe2O3 microdisks are of the oblique hexagonal side same as the SEM observations
(Fig.2c). The SAED pattern as inset shown in Fig.3a is taken from the hematite α-Fe2O3 microdisk
pointed out by white arrow and can be indexed as the incident electron beam along the direction of
[0001]. Moreover, the 0.252 nm interval of the lattice fringes observed in the HRTEM image
agrees well with the spacing of (11-20) planes. The results of the SAED and HRTEM together
argue that the top and bottom surfaces of the single-crystalline α-Fe2O3 microdisks are (0001) and
(000-1) planes, respectively. Whereas the hematite α-Fe2O3 microdisks are of oblique hexagonal
side, it can be further inferred that the side of the hematite α-Fe2O3 microdisks are closed of
{11-20} planes, well reflecting the intrinsic symmetry of the hematite lattice structure.
The TEM image of the α-Fe2O3 drum-like particles obtained at the EG/water volume ratio of
26:14 was shown in Fig.3c. A lot of α-Fe2O3 drum-like particles self-assemble to necklaces by
contacting one another with the flat. The regular SAED pattern (inset in Fig.3c) taken from one
α-Fe2O3 necklace can be indexed as [11-20], perpendicular to [0001]. On the other hand, the SEM
image shown in Fig. 2d has demonstrated that the α-Fe2O3 drum-like particles are of hexagonal
side at the cross section of the maximum diameter. It is suggested that the flat of the α-Fe2O3
drum-like particles is perpendicular to [0001] direction, similar with the α-Fe2O3 microdisks
obtained at the EG/water volume ratio of 30:10. Fig.3d, e and f show the TEM and HRTEM image
of the α-Fe2O3 spindles synthesized at the EG/water volume ratio of 20:20. A regular SAED
pattern indexed as [11-20] (right-down inset in Fig.3d) is taken from one nominal α-Fe2O3 spindle,
which lies on the axis. Moreover, two sets of lattice fringes with 0.369 and 0.270 nm intervals,
which agree well with the spacing of (01-12) and (10-14) planes, respectively, are observed in the
HRTEM image shown in the Fig.3e. It is indicated that the axis of the α-Fe2O3 spindle is parallel
to the direction of [0001]. Especially, among the spindles there is one oblique hexagonal particle
pointed out by a white arrow. The SAED pattern caught from the oblique hexagonal particle
(light-up inset in Fig.3d) can be indexed as the incident electron beam along the direction of
[0001]. Moreover, two sets of lattice fringes with a same interval of 0.252 nm and an angle of 60º,
which agree well with the spacing of {11-20} and the angle among the planes involved in the
group of {11-20}, are observed in the corresponding HRTEM image shown in Fig. 3f. It is argued
that the oblique hexagonal particles observed in the TEM image shown in Fig. 3d is the α-Fe2O3
spindle happens to erect along the [0001] axis by inserted in the copper grid. In summary above,
the α-Fe2O3 drum-like particles and the spindles take on a same axis direction along [0001] and
oblique hexagonal side enclosed of {11-20} planes at the cross section of the maximum diameter
with the α-Fe2O3 microdisks along [0001].
It is well known that KOH is a strong alkali. While it dissolves in water, KOH ionize to OH-
and K+ ions. During the feedstock preparation, therefore, with the KOH addition into the Fe(NO3)3
transparent solution, the Fe3+ ions combine with OH- ions to Fe(OH)3 hydroxide precipitates. In
the subsequent hydrothermal treatment processing, according to the formation mechanism of
oxides derived from hydroxides under the hydrothermal conditions[30], the Fe(OH)3 hydroxides
precipitates dehydrate and condense to Fe2O3 species under the effect of OH- ions. As the formed
Fe2O3 species accumulate to a moderate concentration, a number of hematite α-Fe2O3 nuclei
larger than the critical size form. These nuclei then grow to α-Fe2O3 crystals by incorporating the
additional Fe2O3 species. Because the hydrothermal conditions only with water as reaction
medium are far from equilibrium, moreover, the obtained hematite α-Fe2O3 crystals are of
irregular morphology and broad size distribution (Fig.2f).
However, when the reaction medium solvent is almost composed of EG but for a trace of water,
due to the reducibility of EG under the alkali conditions some Fe3+ ions are reduced to Fe2+ ions
[31,32]. In consequence, in the present experiment at the EG/water volume ratio of 40:0 and 35:5
the formed iron oxide species are composed of Fe3O4 and crystallize to magnetite Fe3O4
nanoparticles (Fig.1a-b and Fig.2a-b). Otherwise, it is known that the presence of trace water
involved in the feedstock is essential for the metal oxide crystals derived from the metal
hydroxides under the solvothermal conditions [25,28,33]. Whereas the volume fraction of the
involved water in the feedstock is very small, the formed Fe3O4 species located in the water
accumulate to of high concentration. According to the crystal nucleation and growth theory [34],
on the other hand, it is well known that high concentrations facilitate the decrease of the critical
nucleus size. Thus, it is relational to think that a larger number of magnetite Fe3O4 nuclei larger
than the critical nucleus size fast form for growing to crystals. These nuclei larger than the critical
nucleus size then grow to magnetite Fe3O4 crystals by incorporating the additional Fe3O4 species
still present in the reaction medium. Due to the formation of the large number of nuclei and the
finite iron oxide precursors for the crystal growth, the magnetite Fe3O4 nanoparticles are obtained.
Otherwise, compared to the pure EG, more amount of water is involved in the mixture solvent of
EG and water with an EG/water volume ratio of 35:5. Therefore, it is inferred that the critical
nucleus size in the hydrothermal system with the mixture solvent of EG/water ratio of 35:5 is
larger than that with pure EG as reaction medium. In consequence, the size of the obtained Fe3O4
nanoparticles at the EG/water volume ratio of 35:5 is slightly larger than that obtained with pure
EG as reaction medium solvent (Fig. 2a and b).
With the addition of the water into the hydrothermal system, the volume ratio of EG/water
decreases and the reducibility of EG becomes weak. When the EG/water volume ratio decrease
lower than 30:10, the reducibility of EG is too weak to reduce Fe3+ ions to Fe2+ ions. Therefore,
after hydrothermal treatment the hematite α-Fe2O3 crystals form instead of the magnetite Fe3O4
nanoparticles. Nonetheless, EG is an organic solvent with two hydroxyls in the molecular
structure and easily adsorbs on the solid surface by hydrogen bonding. Many experiments have
demonstrated that the adsorption of organic modifiers strongly affects the crystallization and
growth [24-29]. In the present experiment, the adsorption of EG makes the hematite α-Fe2O3
crystals evolved from oblique hexagonal microdisks, drum-like particles and spindles with the
EG/water volume ratio changing from 30:10 to 26:14 and 20:20.
At the time of the EG/water volume ratio of 30:10, because the shape of the synthesized
hematite α-Fe2O3 oblique hexagonal microdisks well reflects the intrinsic symmetry of the
rhombohedral lattice, it is reasonable to suggest that the crystallization occurs at equilibrium [37].
Whereas the morphology of the hematite α-Fe2O3 crystals evolves from the oblique hexagonal
microdisks to drum-like particles and spindles with EG/water volume ratio changing from 30:10
to 26:14 and 20:20, it can be inferred that the further addition of water in the hydrothermal system
makes the equilibrium disturbed. In our previous researching work, it has demonstrated that the
water involved in the solvothermal system plays an important role in the formation of the SrTiO3
nanosheets [25]. Because the volume fraction of water is very low in the solvothermal system, the
local concentration of the formed SrTiO3 species in the water is very high. As a result, the SrTiO3
species with high local concentration crystallize to nanocrystallites and subsequently
self-assemble to SrTiO3 nanosheets. In the present experiment, with the EG/water volume ratio
decreasing to 26:14 and 20:20 the water volume fraction in the hydrothermal system enlarges.
Whereas the reactive precursors for the hydrothermal synthesis of the α-Fe2O3 crystals are settled,
it is reasonable to think that at same time the formed Fe2O3 species during the hydrothermal
treatment process are very close in reaction solvent medium with different EG/water volume ratio.
Thus, the local concentration of the formed Fe2O3 species in the water accordingly declines with
the EG/water volume ratio decreasing to 26:14 and 20:20. This disturbance in the local
concentration of the Fe2O3 species further makes the crystallization of the hematite α-Fe2O3
departed from equilibrium.
It is well known that the deposition of the Fe2O3 species on the crystal surfaces is a reversible
process during the crystallization under the hydrothermal conditions. Whilst the hematite α-Fe2O3
crystals grow larger by adsorbing the Fe2O3 species on the surfaces, some Fe2O3 species dissolve
into the aqueous solution. Because of high specific surface area, it is relational to think that the
concentration of the Fe2O3 species around the edges of the oblique hexagonal α-Fe2O3 microdisks
is higher than that around the flat top and bottom surfaces. An Ostwald ripening process occurs, in
which the Fe2O3 species dissolve from the edges and deposit onto the flat top and bottom surfaces
of the oblique hexagonal α-Fe2O3 microdisks. In consequence, the flat top and bottom surfaces of
the microdisks shrink and the length along the axis enlarges. At the time of EG/water volume ratio
of 26:14, because the condition for the crystallization departs from the equilibrium slightly, the
hematite α-Fe2O3 crystals ripen to drum-like particles (Fig.2d and Fig.3c). Whereas the condition
for the crystallization far departs from the equilibrium at the time of EG/water volume ratio of
20:20, the hematite α-Fe2O3 spindles are obtained by undergoing a much strong Ostwald ripening
process (Fig.2e and Fig.3d-f). Therefore, the hematite α-Fe2O3 drum-like particles and spindles
are of a same direction axis of [0001] with the hematite α-Fe2O3 microdisks. The schematic
illustration on the shape evolution process of the hematite α-Fe2O3 crystals from oblique
hexagonal microdisks to drum-like particles and spindles with the changing of the EG/water
volume ratio is simply described in Fig.4.
Magnetization measurements were performed to investigate the phase- and shape-dependence
of the magnetite Fe3O4 nanoparticles and the uniform hematite α-Fe2O3 oblique hexagonal
microdisks, drum-like particles and spindles. Fig.5a shows the magnetic hysteresis loop at room
temperature of the as-prepared magnetite Fe3O4 nanoparticles with pure EG as the reaction
medium solvent. It is revealed that the as-prepared magnetite Fe3O4 nanoparticles exhibit typical
ferromagnetic behavior. The saturation magnetization (Ms), remnant magnetization (Mr) and
coercive force are 77.3 emu/g, 14.6 emu/g, and 85.8 Oe, respectively, similar to the previous
reported [38]. Fig.5b presents the magnetic hysteresis loops of the synthesized α-Fe2O3 oblique
hexagonal microdisks, drum-like particles and spindles. As a control, the magnetic hysteresis of
the α-Fe2O3 irregular particles hydrothermally synthesized assisted without any EG is also
pictured in Fig.5b. The noticeable magnetic hysteresis loops shown in Fig.5b clearly display that
the four α-Fe2O3 samples are in a weak ferromagnetic state at room temperature. All the magnetic
hysteresis loops for the four α-Fe2O3 samples do not reach their saturation point up to the
maximum applied magnetic field, which is similar to the reported in the literatures [39,40].
The detailed values of remnant magnetization (Mr) and coercive force (Hc) of the
as-synthesized α-Fe2O3 oblique hexagonal microdiscks, drum-like particles, spindles and the
control sample of α-Fe2O3 irregular particles obtained from Fig. 5b are summarized in Table 1.
With the evolution of the morphology from uniform the oblique hexagonal microdisks to
drum-like particles and spindles, the Hc and Mr express regular decrease and increase,
respectively. The maximum Hc is achieved from the α-Fe2O3 oblique hexagonal microdisks, about
of 942.5 Oe. With the morphology evolution to drum-like particles and spindles, the Hc decrease
to 647.5 and 417.0 Oe in turn. However, the minimum Mr of the α-Fe2O3 oblique hexagonal
microdisks is 0.0178 emu/g. With the morphology evolution to drum-like particles and spindles,
the Mr increases to 0.0244 and 0.0268 emu/g in turn. Otherwise, it should be noticed that the Hc
of the α-Fe2O3 spindles is even small to that of the hydrothermally synthesized α-Fe2O3 irregular
particles, while the α-Fe2O3 drum-like particles exhibit adjacent Mr to the hydrothermally
synthesized α-Fe2O3 irregular particles.
It is well known that hexagonal hematite α-Fe2O3 is an important magnetic material. Below the
temperature of TN (955 K), α-Fe2O3 is antiferromagnetic [41]. Nonetheless, due to the occurrence
of the spin-canted ferromagnetism and defect ferromagnetism, α-Fe2O3 shows weak ferromagnetic
properties at room temperature [42]. Many previous reports have demonstrated that there are three
main factors affecting the magnetism of the synthesized ferromagnetic particles. The first is the
adsorption of the modifier on the surfaces of the ferromagnetic particles. Due to the contribution
on the pinning of the surface domain walls and the blocking of the spin-flip conversion, the
adsorption of modifiers on the surfaces of the magnetic particles enhances the coercive force
[10,43,44]. The second is the ferromagnetic particle size. According to the reported by Wang and
his co-workers [45], there is a critical particle size, Rm, for the coercive force enhancement with
the particle decreasing. As the particle size is larger than Rm, with the particle decreasing the
coercive force enhances, while less than Rm, with the particle further decreasing the coercive
force decreases. With regard to the α-Fe2O3 magnetic materials, moreover, it has been confirmed
that the Rm is about 183 nm [10]. In addition to the above mentioned factors, the magnetism is
also sensitive to the morphology, especially, the exposed facets of the ferromagnetic particles
[46,47]. As for hematite α-Fe2O3, the easiest magnetization direction is [11-21,47]. By applied a
magnetic field parallel to the direction of [11-21], the antiferromagnetic α-Fe2O3 can be induced to
weak ferromagnetic.
In the present three α-Fe2O3 samples with uniform particles, the smallest size in length along
the axis direction of [0001] is achieved for the α-Fe2O3 oblique hexagonal microdisks, and the
biggest one for the α-Fe2O3 spindles, the middle for the α-Fe2O3 drum-like particles, respectively,
whilst the maximum diameter of the α-Fe2O3 drum-like particles and spindles samples is similar
to that of the α-Fe2O3 oblique hexagonal microdisks. On the other hand, because the uniform
α-Fe2O3 oblique hexagonal microdisks, drum-like particles and spindles are obtained by a facile
hydrothermal method, in which the EG involved in the hydrothermal reaction medium solvent
decrease in turn, it is relational to suggest that the strongest adsorption of EG occurs on the
surfaces of the α-Fe2O3 oblique hexagonal microdisks, and the weakest on the α-Fe2O3 spindles,
the middle on the α-Fe2O3 drum-likes particles. Therefore, the α-Fe2O3 oblique hexagonal
microdisks exhibit the biggest coercive force, and the α-Fe2O3 spindles the smallest one, the
α-Fe2O3 drum-like the middle one (Fig.5b and Table 1). On the third hand, the shape and the
exposed facets of the α-Fe2O3 particles still propose the dominant contribution on the coercive
force. Due to the dominant exposition of the (0001) facets, which have a larger angle with easiest
magnetization direction of [11-21], the α-Fe2O3 oblique hexagonal microdisks are of larger
coercive force. With the basis of the crystal structure of the hematite α-Fe2O3, it is known that
based on the hexagonal (0001) plane, α-Fe2O3 tetrakaidecahedrons and dodecahedrons bound by
high-index (11-21) facets can be extracted. Moreover, the α-Fe2O3 tetrakaicahedrons and
dodecahedrons have been realized in the reported experimental researching works [14,10,40].
Although the broad features of tetracaicahedron and dodecahedron are clearly observed, whereas
the axis direction of the present α-Fe2O3 drum-like particles and spindles is along [0001], it can be
argued that with the shrinkage of the (0001) basal planes, the side gradually becomes parallel to
(11-21) planes. In consequence, the coercive force decreases with the morphology of the hematite
α-Fe2O3 crystals from oblique hexagonal microdisks to drum-like particles, and spindles [47].
Especially, the coercive force of the α-Fe2O3 spindles is smaller than that of the hydrothermally
synthesized α-Fe2O3 irregular particles (Fig.5b and Table 1).
Whereas an orbiting electron in an atom will have a magnetic dipolar moment, it is reasonable
to hypothesize that the α-Fe2O3 spindles with sharp tips may show strong dipolar interactions
between electrons [38]. In view of the suppression on the thermal fluctuations and the alignment
of the spins with the applied field, the saturation and remnant magnetizations increase. Therefore,
due to the presence of the tip, the α-Fe2O3 spindles are of the most remnant magnetization.
Similarly, the flat top and bottom planes make the α-Fe2O3 oblique hexagonal microdisks of the
smallest remnant magnetization (Fig.5b and Table 1).
4. Conclusions
In summary , magnetite Fe3O4 nanoparticles and uniform hematite α-Fe2O3 oblique hexagonal
microdisks, drum-like particles and spindles have been successfully synthesized via a facile
hydrothermal reaction route by adjusting the EG/water volume ratio of the used reaction medium
mixture solvent. The hematite α-Fe2O3 oblique hexagonal microdisks well reflect the lattice
intrinsic symmetry, with the basal (0001) plane and the side enclosed of {11-20} planes. The
hematite α-Fe2O3 drum-like particles and spindles take on a same axis direction along [0001] and
oblique hexagonal side enclosed of {11-20} planes at the cross section of the maximum diameter
with the α-Fe2O3 microdisks. EG plays important roles in the formation of the magnetite Fe3O4
nanoparticles and the shape evolution of the uniform hematite α-Fe2O3 crystals from oblique
hexagonal microdisks to drum-like particles and spindles. Because of the strong reductive ability
of pure EG, some Fe3+ ions reduce to Fe2+ ions and magnetite Fe3O4 nanoparticles are obtained at
the high volume ratio of EG/water. As the EG/water volume ratio is lower than 30:10, the obtained
iron oxide samples are only of the hematite α-Fe2O3 crystals because the reductive ability of EG is
too low to reduce Fe3+ ions to Fe2+ ions. As an organic modifier， EG strongly affects the
morphology of the hematite α-Fe2O3 crystals by adsorbing on the surfaces. Due to the adsorption
of EG, with the EG volume fraction decreasing the hematite α-Fe2O3 crystals crystallize to oblique
hexagonal microdisks, drum-like particles and spindles in turn. Furthermore, the magnetic
properties show strong shape-dependent nature. With the shape of the hematite α-Fe2O3 crystals
changing from oblique hexagonal microdisks to drum-like particles and spindles, the coercive
force change from 942.5 Oe to 647.5, 417.0 Oe, whereas the remnant magnetization increase from
0.0178 to 0.0244, 0.0268 emu/g.

Acknowledgements
This work is supported by the National Natural Science Foundation of China under grant Nos.
61274004 and 51232006, and the Zhejiang Natural Science Foundation, China, under grant No.
LY12B07007, and Key Science and Technology Innovation Team of Zhejiang Province, China,
under grant No. 2010R50013.
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Fig. 1 XRD patterns of the samples hydrothermally synthesized at different EG/water volume ratio
of (a) 40:0, (b) 35:5, (c) 30:10, (d) 26:14, (e) 20:20, (f) 0:40.

Fig. 2 SEM images of the hydrothermally synthesized iron oxide samples at different EG/water
volume ratio of (a) 40:0, (b) 35:5, (c) 30:10, (d) 26:14, (e) 20:20, (f) 0:40.

Fig. 3 (a) TEM and (b) HRTEM images of the hematite α-Fe2O3 oblique hexagonal microdisks,
inset in (a) is the SAED pattern take from the one microdisk pointed out by white arrow(c) TEM
image of the hematite α-Fe2O3 drum-like particles, inset is the SAED pattern taken from one
α-Fe2O3 necklace(d) TEM image of the hematite α-Fe2O3 spindles, the right-down inset SAED
pattern and (e) HRTEM image are caught from one normal spindles lying on the axis, and the
light-up inset SAED pattern and the (f) HRTEM image are taken from the erected spindles along
the axis direction.

Fig. 4 Schematic illustration picture on the shape evolution mechanism of the hematite α-Fe2O3
crystals from oblique hexagonal microdisks to drum-like particles and spindles.

Fig.5. (a) Magnetic hysteresis loop of the magnetite Fe3O4 nanoparticles synthesized with pure EG
as reaction medium solvent.(b) Magnetic hysteresis loops at room temperature of α-Fe2O3 uniform
microdisks, drum-like particles, spindles and irregular particles.
Table 1. Values of remnant magnetization (Mr) and coercive force (Hc) of the as-synthesized uniform α-Fe2O3
oblique hexagonal microdisks, drum-like particles, spindles and irregular particles
Samples Mr / (emu/g) Hc / (Oe)
Hexagonal microdisks 0.0178 942.5
Drum-like particles 0.0244 647.5
Spindles 0.0268 417.0
Irregular particles 0.0209 448.6
 Graphical Abstract

Phase- and shape-controlled synthesis of the magnetite Fe3O4 nanoparticles and the hematite
α-Fe2O3 uniform oblique hexagonal microdisks to drum-like particles and spindles has been
realized by simply adjusting the volume ratio of ethylene glycol (EG) and water of the
hydrothermal reaction medium solvent and the magnetic properties of the hematite α-Fe2O3
crystals express regular change with the shape evolution from uniform oblique hexagonal
microdisks to drum-like particles, spindles and irregular particles.
1. Different morphology of hematite α-Fe2O3was synthesized by a hydrothermal route.
2. The volume ratio of EGand distilled water is designed as 40:0-0:40.
3. The EG affects the morphology of the hematite α-Fe2O3 crystals
4. A possible formation mechanism of hematite α-Fe2O3has been proposed.
5. The magnetism perfoemance has a significant change .