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Ultrasonics Sonochemistry 15 (2008) 257–264

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Sonochemical synthesis of amorphous nanoscopic iron(III) oxide

from Fe(acac)3
a,*
Jiri Pinkas , Vendula Reichlova a, Radek Zboril b, Zdenek Moravec a,
Petr Bezdicka c, Jirina Matejkova d
a
Department of Inorganic Chemistry, Masaryk University, Kotlarska 2, CZ-61137 Brno, Czech Republic
b
Department of Physical Chemistry, Palacky University, Svobody 26, CZ-77146 Olomouc, Czech Republic
c
Institute of Inorganic Chemistry ASCR, CZ-25068 Rez, Czech Republic
d
Institute of Scientific Instruments ASCR, Kralovopolska 147, CZ-61264 Brno, Czech Republic

Received 14 October 2006; accepted 23 March 2007

Available online 3 April 2007

Abstract

Amorphous nanoscopic iron(III) oxide with interesting magnetic properties was prepared by sonolysis of Fe(acac)3 under Ar in
tetraglyme with a small amount of added water. The organics content and the surface area of the Fe2O3 nanoparticles can be controlled
with an amount of water in the reaction mixture and it increases from 48 m2 g 1 for dry solvent up to 260 m2 g 1 when wet Ar is
employed. For further monitoring of the particle size and morphology and for the study of the surface, magnetic and thermal properties,
the sample with 2 vol.% of H2O was chosen. SEM showed nanoscopic composite particles of a uniform size distribution and nearly
spherical shapes with an estimated diameter of 20 nm. Such composites are built from amorphous iron(III) oxide nanoparticles
(3 nm) embedded in an acetate matrix as proved by TEM and IR spectroscopy. Temperature-dependent Mössbauer spectra demonstrate
a very narrow magnetic transition with an unusually low transition temperature around 25 K reflecting the system of magnetically non-
interacting ultrasmall particles with a narrow size distribution. The in-field (5 T) Mössbauer spectrum recorded at 5 K shows a minimum
change compared to the zero-field spectrum indicating an absence of the long-range magnetic ordering. The composite particles are ther-
mally stable up to 150 C, which is confirmed by DSC, TG, and by the constant surface area. At higher temperatures, acetate groups are
removed from the particle surface, which is documented by the increased surface area and disappearance of their IR bands.
 2007 Elsevier B.V. All rights reserved.

Keywords: Iron; Amorphous oxides; Ultrasound; Sonochemistry; Solvents; Nanoparticles

1. Introduction able method for the preparation of amorphous phases, new

The ultrasound-activated reactions were in recent times
employed in many areas of chemistry, one of them being
the field of inorganic materials synthesis [1,2]. The sono-
chemical process relies on the cavitation effects produced
by collapsing bubbles in liquids. Factors such as rapid
cooling rates, atomic level mixing and the nonequilibrium
nature of the reactions render sonochemistry the most suit-
*
Corresponding author. Tel.: +420 54946493; fax: +420 549492443.
E-mail address: jpinkas@chemi.muni.cz (J. Pinkas).
mixed-element compounds, and nanoscopic structures. The
study of ultrasound-activated routes to nanomaterials is a
rapidly growing research area [3,4]. Judicious choice of pre-
cursors, solvents, additives and other variations in the reac-
tion parameters and conditions allow control of the
chemical nature of the product, its composition, external
form and morphology, and crystallinity.
Nanoparticles of various polymorphic forms of iron oxi-
des [5] found their applications in such diverse areas as
magnetic liquids, photocatalysis, catalytic destruction of
chlorinated organics, diagnostic imaging, and drug deliv-
ery. A multitude of preparative methods for iron oxide

1350-4177/$ - see front matter  2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.ultsonch.2007.03.009
258 J. Pinkas et al. / Ultrasonics Sonochemistry 15 (2008) 257–264
nanoparticles were developed, such as MW irradiation [6],
forced hydrolysis and precipitation [7], laser pyrolysis [8],
microemulsion [9], sol–gel, electrochemical [10], solid-state
thermal decomposition [11], oxidation of metallic iron
nanoparticles [12,13], solvothermal decomposition [14],
combustion method [15], and others.
Thermally induced processes provide crystalline nano-
particles in many cases. In contrast, ultrasound-driven
reactions yield amorphous materials that are produced in
collapsing cavitation bubbles as enormous cooling rates
(1010 K s 1) prevent their crystallization during quenching.
Sonochemical synthetic routes leading to iron oxides rely
most frequently on Fe(CO)5 [16,17] as a precursor, how-
ever, FeCl3 [18], Fe(NO3)3 [19], Fe(OAc)2 [20], and
Fe(OEt)3 [21] were also employed. Nanoscopic amorphous
Fe2O3 occupies a special position among various forms of
iron oxides because of several factors [11]. A large surface
area predestines it to be a good candidate for gas sorption,
sensor, and electrode materials. Its disturbed surface struc-
ture with a large number of unsaturated bonds endows it
with a high catalytic activity and superparamagnetic
behavior of Fe2O3 nanoparticles in colloidal solutions led
to their use as magnetic fluids. Moreover, amorphous
Fe2O3 nanopowder was found to be a suitable precursor
for solid-state systems of Fe2O3 or a-Fe magnetic nanopar-
ticles [22]. The ultrasound-activated route led to the synthe-
sis of amorphous Fe2O3 nanopowders of variable particle
size [16,17] and parameters influencing the yield in the
sonoreaction of Fe(CO)5 were examined in detail [23]. Fur-
thermore, nanocomposites of amorphous Fe2O3 with SiO2
[24] and TiO2 [25], mesoporous forms [21], amorphous
Fe2O3 coating layers on alumina [26] and surface-function-
alized amorphous Fe2O3 particles can be prepared by soni-
cations of Fe(CO)5 solutions [27].
Fe(acac)3 is an easily available, organics-soluble, solid
precursor that is, in contrast to Fe(CO)5, nontoxic and thus
safe to handle on a large scale. Thermal decomposition of
this precursor to Fe2O3 in air at normal pressure starts at
170 C and is completed below 400 C [28]. It was used in
the preparation of iron oxide nanoparticles by solution
thermolysis in various organic solvents [14,29], sol–gel
methods [30], and precursor thermolysis in an MCM41
matrix [31]. Sonochemical decomposition of Fe(acac)3
was studied only sparsely. For example, sonolysis in hex-
adecane was found to follow a first order kinetic law with
respect to Fe(acac)3 concentration and from the estimated
sublimation temperature of 220 C, authors concluded that
the reaction takes place inside the cavitation bubbles [32].
The solid oxide product was X-ray amorphous, contained
an admixture of ligand degradation products, and featured
characteristic acetate bands in the IR spectra. By heating to
700 C, it was converted to a-Fe2O3 with 20–40 nm particle
size.
Tetraglyme is an ether type of solvent that has physical
and chemical properties suitable for sonochemical experi-
ments. It dissolves well diketonate precursors and is also
known to coordinate through its oxygen atoms to metal
centers and solvate large cations. Therefore, it should sta-
bilize colloidal particles similarly to PEG in the MW irra-
diation assisted synthesis of Fe2O3 from FeCl3 and urea
[6]. Use of tetraglyme in sonochemical systems has not
been reported so far.
Considering the favorable properties of Fe(acac)3 as a
precursor and tetraglyme as a solvent, we set out to inves-
tigate this system. Herein we report on the sonochemical
synthesis of amorphous Fe2O3 nanoparticles with an
organic matrix and uniform size distribution which exhibit
unusual magnetism. Decomposition under power ultra-
sound activation of nontoxic precursor Fe(acac)3 in high-
boiling coordinating solvent tetraglyme provided nano-
powders with large surface areas of up to 260 m2 g 1.
The effect of water added to the reaction mixture was
examined with the aim to facilitate the ligand removal as
Hacac. The addition of water decreased organic content
in the powders and increased surface area of the products.
2. Experimental
2.1. Chemicals
Fe(acac)3 was prepared from acetylacetone and
FeCl3 Æ 6H2O. Tetraethyleneglycol dimethylether (tetrag-
lyme) from Aldrich was vacuum distilled (93–105 C/
3 Pa) and stored under dry N2.
2.2. Sonochemical experiments
Sonication was carried out on a Sonics and Materials
VXC system with 500 W input power and working fre-
quency of 20 kHz. In a typical experiment, iron(III) acetyl-
acetonate precursor (0.50 g, 1.4 mmol) was dissolved in
tetraglyme (50 cm3) to a clear red solution (0.028 M) which
was then purged with argon for 10 min before irradiation
and also during the reaction (flow rate 60 cm3 min 1).
The high-intensity Ti horn with a diameter of 13 mm and
tip surface area of 3.5 cm2 was inserted into a standard
conical 250 cm3 sonochemical vessel (Ace Glass) which
was filled with 50 cm3 of the reaction mixture to ensure a
constant immersion depth of 4 cm. The power transmitted
into the solution was determined calorimetrically as
13 W cm 2 at 75% amplitude. The gas-tight connection
of the horn to the vessel was ensured by a Teflon adapter
attached at the nodal point and excess gas was released
through an oil bubbler. The irradiation was set to an inter-
val of 2 s with a delay of 2 s. Before starting any experi-
ment, the content of the reaction vessel was precooled
with a Julabo F 25-MP thermostat to 0 C. Sonication
was run for 4, 8, 12, 16, 18, and 38 h. The solution temper-
ature rose to about 40 C during irradiation. After the reac-
tion, the resulting colloidal solution was left to stand for a
week and then filtered to remove a small amount of fine Ti
powder sputtered from the horn. The product was precip-
itated by the addition of hexane (20 cm3) and the solid
was separated from the solvents by centrifugation for
 J. Pinkas et al. / Ultrasonics Sonochemistry 15 (2008) 257–264
20 min on a Heraeus Labofuge 400 at 3000 rpm. The pow-
ders were washed to remove organic-soluble residues by
three cycles of resuspending them in isopropanol or light
petroleum (15 cm3) and subsequent centrifugations. They
were left to dry in an open air.
2.3. Characterization techniques
Thermal analyses (TG/DTG/DTA) were carried out on
a MOM Derivatograph-C instrument under static air of
flowing Ar (7 dm3 min 1) with 5 C min 1 ramp from
room temperature to 1000 C. Samples (20–50 mg) were
contained in corundum crucibles. The a-Al2O3 powder
was used as a reference material. DSC measurements
(DSC XP-10, THASS GmbH) were performed under static
air within the range of 25–400 C with the heating rate of
2.5 C min 1. A Stoe-Cie transmission diffractometer
STADI P operating with a Ge monochromatized Co
(k = 0.1788965 nm) radiation (40 kV, 30 mA) and
equipped with a PSD detector was used for the XRD data
acquisition at room temperature. ICP spectrometer Jobin
Yvon 170 Ultrace (lateral observation, generator
40 MHz, output 1.0 kW, plasma gas flow 12 l min 1,
monochromator 1 m) was used for the determination of
the Fe metal content in the synthesized samples. The mea-
surements were performed at the 238.204 nm line. Scanning
electron microscopy (SEM) micrographs were taken on a
Jeol 6700 field emission microscope. Dried Fe2O3 powder
samples were resuspended in isopropanol and a drop of
colloidal solution was placed on a cleaned silicon (1 0 0)
slide. After solvent evaporation, the sample was briefly
sputtered with Au/Pd alloy to avoid charging. Transmis-
sion electron microscopy (TEM) was carried out on JEOL
JEM2010 and 3010 microscopes operated at 200 and
300 kV, respectively. Instruments were equipped with a
LaB6 cathode, an EDX (energy dispersive X-ray) detector,
and characterized by a point-to-point resolution of 1.7 Å.
Images were recorded by a CCD camera with resolution
of 1024 · 1024 pixels using the Digital Micrograph soft-
ware package. Powder samples were dispersed in ethanol
and the suspension was treated in ultrasound for 10 min.
A drop of very dilute suspension was placed on a car-
bon-coated grid and allowed to dry by evaporation at
ambient temperature. Surface areas and pore volumes were
determined by N2 adsorption at 77.4 K by volumetric tech-
nique on a Quantachrome Autosorb-1MP instrument.
Prior to the measurements, the samples were degassed at
25 C for at least 24 h until the outgas rate was less than
0.4 Pa min 1. The adsorption–desorption isotherm was
measured for each sample at least three times. The specific
surface area was determined by the multipoint BET
method with at least five data points with relative pressures
between 0.05 and 0.23. Analysis was performed with the
instrument software package. Transmission 57Fe Möss-
bauer spectra of 512 channels were collected using a Möss-
bauer spectrometer in a constant acceleration mode with a
57
Co(Rh) source. Measurements were carried out at vari-
259
ous temperatures between 300 and 5 K using a cryomag-
netic system of Oxford Instruments. In-field spectra were
recorded at 5 K in an external magnetic field of 5 T applied
parallel with the gamma ray propagation. Isomer shift
parameters are related to metallic a-Fe as a reference mate-
rial. IR spectra (4000–400 cm 1) were recorded on a Bru-
ker EQUINOX 55/S/NIR or IFS 28 instrument. Samples
of solids were prepared as KBr pellets while neat liquids
were spread between KBr disks. Microanalyses were per-
formed on a ThermoFinnigan Co. CHN Analyzer Flash
EA 1112.
3. Results and discussion
3.1. Synthesis
Tetraglyme was selected as an inert solvent for the sono-
chemical experiments because its physical and chemical
parameters are favorable for the ultrasound processing:
its high normal boiling point (276 C) imparts a low vapor
pressure that is necessary for effective cavitation. This boil-
ing point is higher than the one of a frequently used sono-
chemical solvent decalin (cis-decalin 195.8 C). Tetraglyme
density (1005.68 kg m 3 [33]) and ultrasound speed
(1381 m s 1 [34]) also allow to attain a sufficient acoustic
pressure amplitude.
We studied the influence of water added to the reaction
solution with the aim of facilitating the protonation and
removal of the diketonate ligand from the iron center as
Hacac and the formation of an oxide. Beneficial effects of
added H2O were observed in the CVD fabrication of cop-
per oxide films from Cu(hfacac)2, where 18O labelling study
evidenced the retention of water oxygen in the solid oxide
product and decomposition of the hfacac ligands to ace-
tone and acetate [35]. Sonolytical reactions were carried
out for comparison in dried tetraglyme under dry Ar gas,
with water added to the reaction mixture (2% or 6%) or
under Ar gas wetted by passing through a water bubbler
at room temperature. The amount of water had an impact
on the surface area and residual organics content in the
prepared samples as it will be discussed below (Table 1).
Sonolysis was typically carried out for 8 h. The variation
of the reaction time between 4 and 38 h had little effect
on the yield.
The ultrasound treatment of the Fe(acac)3 solution pro-
duced ruby red colloidal solutions that were stable for
weeks. We observed a small amount of rutile (JCPDS card
21-1276) and pseudobrookite (JCPDS card 41-1432) in the
calcined oxide product as a result of sputtering of metallic
Ti particles from the ultrasound horn. The synthetic proce-
dure was therefore modified and settling of Ti powder and
filtration through a fine frit was performed to completely
eliminate these admixtures. The addition of hexane to the
colloidal solution induced the precipitation of a red-brown
solid on standing overnight. Centrifugation, washing with
3–4 portions of hexane and drying in air yielded 100–
190 mg of the product. Expected yield of pure Fe2O3 from
260 J. Pinkas et al. / Ultrasonics Sonochemistry 15 (2008) 257–264

Table 1
Dependence of the surface area, pore volume, and Fe and organics
contents on the amount of water in the reaction solution
Water SAa Hb Pore Fe C H TG mass
content (m2 g 1) volume (%) (%) (%) loss (%) at
(vol.%) (cm3 g 1) 500 C
Dry 48 H3 0.304 22.0 30.5 4.52 63.1
2 105 H3 0.611 35.6 22.6 3.48 46.0
6 147 H3 0.455 43.6 15.3 2.75 35.2
2 + wet 260 H2 0.291 42.0 15.5 2.73 37.3
Arc
a
SA = surface area.
b
H = hysteresis type.
c
Ar gas wetted by passing through a water bubbler.

0.50 g of staring iron complex is 113 mg. A higher product

weight resulted from residual organic groups that are
retained in the final solid. The higher retention of organics
was particularly prominent in the reaction carried out
under dry conditions. Actual isolated yields recalculated
from elemental analyses to pure Fe2O3 were between 60%
and 75%. For elemental compositions see Table 1. The
solid product could be redispersed in isopropanol by shak-
ing overnight.
3.2. Characterization
SEM was used to establish the morphology of materials
isolated from the colloidal reaction solution. SEM images
of as-prepared iron(III) oxide were taken on samples pre-
pared by resuspending the isolated powders in isopropanol
and these colloidal solutions were deposited on Si wafers.
They were observed both as native and Au sputtered. There
was no noticeable difference in the particle size or shape of
Au-coated and uncoated Fe2O3. The identical appearance
of the particles was also observed in the samples prepared
from the tetraglyme colloidal solutions obtained directly
after sonolysis by the solvent evaporation at 260 C under
vacuum. A micrograph of a powder obtained from the
reaction with 2 vol.% of water is shown in Fig. 1. It
revealed uniform spherical nanoparticles with a diameter
of about 20 nm. Increasing the amount of water in the reac-
tion mixture to 6 vol.% led to a smaller particle size (about
5–10 nm). However, the smaller particles are more highly
agglomerated. On the other hand, the use of rigorously
dried tetraglyme solvent and desiccated Ar gas resulted in
larger particles (about 70 nm) that were fused to large
irregular chunks. This shows that the product particle size
can be controlled by adding water to the reaction. Addi-
tional complementary information was obtained form the
surface area measurements. The BET method applied to
the nitrogen isotherms provided the surface area of pow-
ders. The specific surface area data of as-prepared samples
of Fe2O3 were obtained by N2 adsorption–desorption mea-
surements at 77.4 K. Prior to analyses, samples were
degassed at 25 C for 24 h. This low temperature was
employed to avoid any thermally induced changes in the
Fig. 1. SEM of sonochemically prepared Fe2O3 powder.
particle surface. Typically, C constants were in the range
35–80 attesting to the validity of BET approximation.
The total pore volumes (cm3 g 1) were estimated from
the amounts adsorbed at a relative pressure of about 0.97
(Table 1). The N2 isotherm of the as-prepared nanoparti-
cles is of IIb type with the hysteresis loop of H3 type.
The surface area of iron(III) oxides displayed relation to
the amount of water in the reaction mixture and increased
with its larger quantity (Table 1). For dry reaction condi-
tions, a value of 48 m2 g 1 was obtained. Addition of
2 vol.% of H2O to the starting solution led to 105–
110 m2 g 1, 6 vol.% to 147 m2 g 1 and wetting of the Ar
stream in a bubbler filled with water maximized the surface
area to 260 m2 g 1. The difference between adding of excess
water directly to the reaction mixture and delivering of
moistened Ar gas was reflected in the larger surface area
for the later, but the organic group content reflected in ele-
mental analysis data and weight loss at 500 C were
approximately the same for both reaction setups.
We tried to establish the chemical and phase composi-
tion of the prepared particles by the X-ray diffraction
experiment. However, the sonochemically prepared iron
oxide powders appeared amorphous in XRD. The crystal-
lization behavior was examined in a separate study by the
authors. The variable temperature XRD under isothermal-
dynamic heating program and also under linear heating
ramp provided above 300 C different modifications of iron
oxide, namely hematite and maghemite with a controllable
particle size. Amorphous state of the as-prepared oxide
below 300 C cannot be proved unambiguously from the
featureless XRD pattern alone. Therefore, the results of
the TEM and Mössbauer spectroscopy experiments have
to be also considered. As it was discussed above, the as-pre-
pared iron oxide powders contain organic residues whose
amount can be controlled by added water (see the results
of CHN elemental analyses in Table 1). We examined the
sonochemically prepared samples of iron(III) oxide by
 J. Pinkas et al. / Ultrasonics Sonochemistry 15 (2008) 257–264
thermal analysis methods in the 25–1000 C range under
air and Ar to establish the amount of removable organic
groups, dynamics of decomposition and transformation
temperatures and crystallization mechanism. Except a
slightly different shape of exothermic peaks, no remarkable
changes in the heat effects, mass loss and transformation
temperatures were observed in argon atmosphere com-
pared to air. A typical thermogram (simultaneous TG/
DTA) and a DSC curve recorded in air with heating rates
of 5 and 2.5 C min 1 are depicted in Figs. 2 and 3,
respectively.
Generally, decomposition of organics takes place in
three partially overlapping steps and the separation of
the mass loss events is better at faster ramping. The end
temperatures of the complete organic group removal shift
progressively to higher values at faster heating rates. The
value of the total mass loss at 500 C depends on the
amount of water added to the reaction mixture. Powders
prepared in dry tetraglyme under dried Ar featured the
largest weight drop of about 63%, samples synthesized in
the presence of 2 vol.% of water released about 46% of
weight, while products of the reaction with 6 vol.% of
added water showed only 35% mass decrease on heating.
This demonstrates the beneficial influence of water on
ligand release and the lower content of organic matrix.
The nature of the organic species entrained in the particles
Fig. 2. TG and DTA traces of amorphous Fe2O3, heating rate 5 C min 1,
in air.
Fig. 3. DSC curve of amorphous Fe2O3 sample. Heating rate of
2.5 C min 1.
261
is also of interest; therefore, we studied the product after
sonication by FT-IR spectroscopy in KBr pellets to gain
information about the characteristic organic groups. A rep-
resentative IR spectrum is shown in Fig. 4. The striking
feature is the absence of the bands characteristic for the
residual acac groups. Strong vibrations ms(C@O)ring and
mas(CACAC)ring, that were observed in the product of
interaction of Fe(acac)3 with Fe2O3 at 1590 and
1530 cm 1, respectively [36], are clearly missing. The
methine stretch at 3090 cm 1 is also absent. The spectrum
is dominated by the bands at 1566 and 1432 cm 1 that
belong to the mas(COO) and ms(COO) vibrations of chelat-
ing acetate, respectively. The carboxylate deformation
bands are observed at 660 and 615 cm 1. It is reasonable
to suppose that under high-power ultrasonic conditions,
the conversion of acac to acetate takes place. Thermal
decomposition of Fe(acac)3 under N2 was studied by ther-
moanalytic and IR spectroscopic methods [28] which
revealed the presence of acetates as intermediate species
in the course of the reaction. Similarly, the conversion of
surface bound acac groups to acetates was observed by
IR on heating the films of alumina (200 C) [37] and zirco-
nia (110 C) [38]. The binding mode of acetates on the par-
ticle surface can be deduced from the Deacon–Phillips rules
[39]. The difference between the asymmetric and symmetric
COO stretch is 134 cm 1 which is comparable to 164 cm 1
for ionic acetate and points to the bridging binding mode.
Amorphous Fe2O3 samples were treated with water in
attempts to remove residual acetate. IR spectra after wash-
ing still displayed acetate bands attesting to stability of ace-
tate binding. Calcination at 5 C min 1 to 300 C decreased
the acetate band intensities and heating to 500 C resulted
in their near disappearance (see Fig. 4).
The results of all methods used to characterize the sono-
chemically prepared iron oxide powders show that particles
are composed of organic material and metal oxide. The
1.0
0.9
0.8
0.7
Absorbance
0.6
0.5
0.4
0.3
0.2
0.1
0.0
4000 3000 2000 1000
Wavenumber(cm-1)
Fig. 4. IR spectrum of the as-synthesized Fe2O3 powder in a KBr pellet
(red) and after calcination to 500 C (blue). (For interpretation of the
references to color in this figure legend, the reader is referred to the web
version of this article.)
262 J. Pinkas et al. / Ultrasonics Sonochemistry 15 (2008) 257–264
transmission electron microscopy provided several pieces
of information on crystallinity and constitution of these
composite particles. The amorphous nature of the sono-
chemical iron oxide product was revealed in TEM micro-
graphs shown in Fig. 5. The apparent size and shape also
agree well with the data obtained from SEM. However,
the particles appear to contain smaller oxide islands (1–
2 nm) dispersed in organic matrix Fig. 6. We tried to eluci-
date the true nature of the primary oxide particles as other
Fig. 5. TEM of amorphous Fe2O3.
Fig. 6. TEM of amorphous Fe2O3 showing 2–3 nm oxide particles
embedded in a matrix.
techniques hinted at the composite character. Therefore,
we heated the samples dynamically up to 250 C to par-
tially remove the acetate groups (see TGA and DSC results
above) and to expose the iron oxide primary particles. At
250 C the crystallization exothermic effect is not yet
apparent in DSC curve and also XRD pattern reflects a
high content of amorphous phase. TEM micrographs of
the heated sample showed clearly small oxide particles
(around 3 nm) embedded in a matrix. A conspicuous
change from featureless amorphous particles to crystallites
was observed in samples heated to 300 C with 5 C min 1
heating rate; the size was around 5 nm, in accordance with
XRD data. Furthermore, the analysis of electron diffrac-
tion pattern revealed the presence of maghemite.
It is worth to mention the gradual crystallization of
amorphous nanoparticles under the electron beam during
the TEM experiments. It was demonstrated by recording
the electron diffraction pattern during the exposure. At
the beginning of experiments, the sample is completely
amorphous. After several minutes, Bragg diffractions
appeared, that were characteristic for c-Fe2O3 (or Fe3O4)
produced by the crystallization (reduction of iron) under
the electron beam.
Magnetic characterization of the materials was obtained
from Mössbauer spectroscopy. Room temperature (RT)
Mössbauer spectra of sonochemically prepared iron oxides
display the broadened doublet (C = 0.53–0.56 mm s 1)
with the isomer shift of 0.33–0.34 mm s 1 and quadrupole
splitting of 0.81–0.85 mm s 1 (see Table 2). Such doublet
with a not-fully Lorentzian shape and similar isomer shift
values, corresponding to the high-spin Fe3+ ions in octahe-
dral environment, was previously observed in amorphous
Fe2O3 samples prepared by various other routes [11,40–
44]. As a unique phenomenon, only quadrupole interaction
is observed even at very low temperatures up to 28 K as
clearly seen from the thermal evolution of Mössbauer spec-
tra (see Fig. 7). The sextet component appears firstly at
20 K and the hyperfine magnetic field increases with the
temperature lowering down to 5 K. Let us emphasize that
such low magnetic transition temperature has not been
described for any of amorphous or nanocrystalline iro-
n(III) oxides yet [5,11,45]. For comparison, amorphous
Fe2O3 nanopowder prepared by the solid-state reaction
and containing ultrasmall particles with similar size (1–
3 nm) exhibited Mössbauer transition temperature of
about 60 K [11]. It seems that the unrecorded low magnetic
transition yielded by sonochemically prepared amorphous
particles is related not only to the restricted particle dimen-
sions but also to the suppressed interparticle magnetic
interactions due the acetate matrix.
In order to understand the magnetic regime and local
ordering in the iron environment, Mössbauer spectrum
was recorded at 5 K in an external magnetic field of 5 T
and compared with that collected in a zero-field at the same
temperature. The zero-field spectrum can be fitted by two
sextets differing slightly in isomer shift and mainly in
hyperfine magnetic fields (see Table 2). Their origin is prob-
 J. Pinkas et al. / Ultrasonics Sonochemistry 15 (2008) 257–264 263

Table 2
Hyperfine parameters and relative spectral areas of Mössbauer spectra of as-prepared amorphous and thermally treated Fe2O3 samples measured at
various temperatures and applied fields
Sample Bexta Tb Spectrum dc ±0.01 DEQ(eQ)d ±0.01 Bhyp(Beff)e ±0.5 RAf ±2 Assignment
(T) (K) (mm s 1) (mm s 1) (T) (%)
As-prepared am-Fe2O3g 0 300 Doublet 0.34 0.81 – 100 Octahedral Fe(III)
As-prepared am-Fe2O3 0 5 Sextet 0.46 0.02 43.4 68 Surface Fe(III)
Sextet 0.47 0.01 47.3 32 Bulk Fe(III)
As-prepared am-Fe2O3 5 5 Sextet 0.46 0.02 42.1 67 Surface Fe(III)
Sextet 0.48 0.01 46.7 33 Bulk Fe(III)
am-Fe2O3 heated up to 0 300 Doublet 0.34 0.84 – 92 am-Fe2O3 + SPh
250 C c-Fe2O3
Doublet 1.02 2.34 – 8 Fe(II)
am-Fe2O3 heated up to 0 300 Doublet 0.34 0.86 – 96 am-Fe2O3 + SP
300 C c-Fe2O3
Doublet 1.05 2.30 – 4 Fe(II)
am-Fe2O3 heated up to 6 20 Sextet 0.44 0.01 43.4 21 am-Fe2O3*
300 C Sextet 0.36 0.02 53.2 31 c-Fe2O3 – tetrahedral
Sextet 0.47 0 47.2 48 c-Fe2O3 – octrahedral
am-Fe2O3 heated up to 0 300 Sextet 0.34 0 41.8 39 Ferrimagnetic c-Fe2O3
360 C Doublet 0.34 0.90 – 58 am-Fe2O3 + SP c-Fe2O3
Doublet 1.04 2.32 – 3 Fe(II)
a
Bext = external magnetic field.
b
T = temperature of measurement.
c
d = isomer shift related to metallic iron.
d
DEQ(eQ) = quadrupole shift (splitting).
e
Bhyp(Beff) = hyperfine (effective) magnetic field; Beff = Bhyp+Bext.
f
RA = relative spectrum area.
g
am = amorphous.
h
SP = superparamagnetic fraction.
*
Amorphous phase fitted by one broadened sextet including contributions of both surface and bulk Fe(III) atoms.

also used for the in-field spectrum, where the effective mag-
netic fields are reduced partially compared to the values of
Bhyp in zero-field spectrum as an expected response to the
applied field. As a key conclusion, the second and the fifth
spectral lines are neither suppressed nor intensified as
should be expected in the external magnetic field applied
parallel with the gamma ray propagation if the ferrimag-
netic (maghemite) or antiferromagnetic (hematite) compo-
nents are present in the sample, respectively [5,45]. This is
another indirect marker of amorphicity of sonochemically
prepared iron(III) oxide. No or negligible change of inten-
sities of the second and the fifth spectral lines evidence for
an absence of the long range magnetic ordering as in spero-
magnetic systems. Such speromagnetic behavior has been
previously observed in Mössbauer spectra of ultrasmall
amorphous nanoparticles of various ferrites such as
CdFe2O4, ZnFe2O4 and NiFe2O4 [46,47].

Fig. 7. Zero-field Mössbauer spectra of amorphous Fe2O3 recorded

between 300 and 5 K and in-field spectrum measured at 5 K in external
field of 5 T applied parallel with gamma ray.
ably in non-equivalent surrounding of the surface Fe3+
ions being in the bonding interaction with the acetate
groups compared to the bulk iron. The similar fit can be
4. Conclusions
A novel ultrasound-driven synthesis of the amorphous
Fe2O3 nanoparticles starting from nontoxic Fe(acac)3 as
a precursor and tetraglyme as a new sonochemical solvent
was developed. As-prepared iron(III) oxide nanoparticles
are embedded in biocompatible acetate matrix resulting
in magnetic composites with large surface area applicable
264 J. Pinkas et al. / Ultrasonics Sonochemistry 15 (2008) 257–264
mainly in biomagnetic separation processes. The amount of
water in the reaction mixture represents a key variable
allowing control the organics content as well as the size
and surface area of the composite particles. The maximum
surface area of 260 m2 g 1 can be reached if moistened Ar
gas is delivered to the reaction mixture. The presence of
organic matrix significantly affects the magnetism and ther-
mal behavior of amorphous Fe2O3 nanophase. Such sur-
face modified ultrasmall (1–2 nm) nanoparticles exhibit
an unrecorded low magnetic transition temperature of
about 25 K, below which they behave as speromagnetic
highly magnetically disordered systems with a high contri-
bution of the surface anisotropy.
Acknowledgements
This work was supported by the Grant Agency of the
Czech Republic (203/04/0296) and the Ministry of Educa-
tion, Youth and Sports (MSM0021622410, 1M6198959201
and MSM6198959218). Authors thank Prof. Z. Travnicek
for CHN elemental analyses, Dr. K. Novotny for ICP mea-
surements, and Dr. M. Klementova for TEM micrographs.
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