Journal of Magnetism and Magnetic Materials 342 (2013) 38–46

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Journal of Magnetism and Magnetic Materials

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Synthesis, characterization and magnetic behavior of Mg–Fe–Al mixed

oxides based on layered double hydroxide
Angélica C. Heredia a,n, Marcos I. Oliva b,c, Ulises Agú a,c, Carlos I. Zandalazini c,d, Sergio
G. Marchetti e, Eduardo R. Herrero a, Mónica E. Crivello a
a
Universidad Tecnológica Nacional, Facultad Regional Córdoba-CITeQ, Maestro López esq. Cruz Roja Argentina, Ciudad Universitaria, 5016 Córdoba,
Argentina
b
IFEG, Universidad Nacional de Córdoba, Córdoba, Argentina
c
CONICET, Argentina
d
INFIQC, FCQ Universidad Nacional de Córdoba, Córdoba, Argentina
e
CINDECA, UNLP, Buenos Aires, Argentina

art ic l e i nf o a b s t r a c t

Article history: In the present work, Mg–Al–Fe layered double hydroxides were prepared by coprecipitation reaction
Received 22 November 2012 with hydrothermal treatment. The characterization of precursors and their corresponding calcinated
Received in revised form products (mixed oxides) were carried out by X ray diffraction, X-ray photoelectron spectroscopy (XPS),
12 April 2013
termogravimetric analysis and differential scanning calorimetry, diffuse reflectance UV–vis spectroscopy,
Available online 25 April 2013
specific surface area, Mössbauaer and magnetic properties. The Fe3+ species were observed in
Keywords: tetrahedrally and octahedrally coordination in brucite layered. The XPS analysis shows that the Fe3+
Layered doubled hydroxides ions can be found in two coordination environments (tetrahedral and octahedral) as mixed oxides, and as
Coprecipitation spinel-structure. Oxides show a decrease in the specific surface areas when the iron loading is increased.
Mixed oxides
The magnetic and Mössbauaer response show that MgAlFe mixed oxides are different behaviours such as
Magnetic properties
different population ratios of ferromagnetic, weak-ferromagnetic, paramagnetic and superparamagnetic
phases. The better crystallization of spinel structure with increased temperature, is correlated with the
improved magnetic properties.
& 2013 Published by Elsevier B.V.

1. Introduction large variety of anions that can be incorporated between the

Mixed oxides with iron obtained by thermal decomposition of
layered double hydroxides (LDH) have been attracting interest
because of their exclusive properties and potential applications in
numerous technological fields. In particular, they are mainly
important in medicine, as adsorbents, anion exchangers, and most
importantly as basic catalysts. Besides, if iron is used, the final
compounds show interesting magnetic properties [1–5]. LDH are
represented by the general formula [M2+ (1−x) Mx
3+
(OH)2] (An−x/n)

mH2O], where the divalent ion may be Mg , Co2+, Zn2+, Ni2+,
2+
Mn2+, and the trivalent ion may be Al3+, Fe3+, Cr3+. Their structure
consists of brucite-type layers, where the substitution of M2+ with
M3+ cations results into a net positive charge, compensated by
interlayer anions (A). There is also water crystallization into the
interlayer region [6,7]. The interlayer distance depends on both,
the nature of anions and the state of hydration. Because of the
n novel drugs–anionic clay structures, strongly dependent on synth-
Corresponding author. Tel.: +543514690585.
E-mail addresses: angelicacheredia@gmail.com,
aheredia@scdt.frc.utn.edu.ar (A.C. Heredia).
brucite-like layers, the high anionic exchange capacity of these
materials, and the large specific surface area values, LDH can be
successfully used as matrices for tailoring specific organic–clay
hybrid structures with new potential applications in pharmaceu-
ticals or as new biocompatible materials [8–10]. It is possible to
synthesize LDH containing more of two cations in the layers.
To use LDH precursors produces an excellent dispersion of metals
compounds on a matrix of magnesium and aluminum. Thermal
decomposition of LDH containing iron start at 300 1C and leads to
mixed oxides. The final decomposition product is a mixture of
spinel and oxides depending of M2+/M3+ ratio and synthesis
method. This allows obtaining a wide range of magnetic proper-
ties, according to the variable cation distribution in the crystalline
structure because magnetic properties are strongly dependent of
spin structure. Thus, magnesium-ferrite aluminate is the first
system where canting of Fe3+ spins on A-site has been observed
when Fe3+ spins on B-site has a collinear spin structure [11].
Recent studies have indicated interesting magnetic properties for
esis conditions, internal structure and the drug nature stability
[12,13]. Qi et al. [14] reported the synthesis of Co0.9Mn0.1Fe2O4

0304-8853/$ - see front matter & 2013 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.jmmm.2013.04.057
 A.C. Heredia et al. / Journal of Magnetism and Magnetic Materials 342 (2013) 38–46
using the LDH precursors, which displayed magnetostrictive
properties that were similar to the traditional ceramic method.
Zhang et al. [15] investigated the effects of the high magnetic field
on products obtained by calcinations of Co–Fe LDH precursors
under the applied field (10 T) at different temperatures.
In the last years, some oxides mixed have been successfully
prepared using LDH as precursors [16,17], but they were synthe-
sized varying the temperature, cations ratio or pH value.
In this work, we report that mixed oxides can be prepared from
Mg2+/Fe3+/Al3+–LDH precursors. They were synthesized by copre-
cipitation at 60 1C under ambient atmosphere, the pH value was
9 and hydrothermal method was used. The content of iron was
changing in order to assess this effect on the structural properties
of the LDH and magnetic behaviors of the calcinations materials.
Due to the properties of these materials, they can be used as
catalysts in reactions of ethylbenzene dehydrogenation [18],
photocatalysis [19], catalysis for remediating the contaminated
waters with organic compounds in solution [20,21].
2. Experimental
2.1. Sample preparation
The Mg, Al, Fe LDH precursors were prepared by coprecipita-
tion at low supersaturation method at constant pH (9 70.5), with
M2+/M3+ ¼3 M ratio constant [22] while the molar ratios Al3+/Fe3+
was changed in order to assess this effect on the structural and
magnetic properties of the LDH and their calcinations products.
Two solutions, A and B, were prepared. In order to obtain A
solution, Mg(NO3)2
6H2O, Al(NO3)3
9H2O and Fe(NO3)3
9H2O were
dissolved together in distilled water. The amounts of nitrates were
selected to obtain the total cation concentration of 0.7 M. The B
solution contains 0.085 M of Na2CO3 (according to the relation
of [CO32−]¼0.5 [M3+]); both solutions were added simultaneously
to 30 mL of distilled water at drip rate of 50 mL/h, the solution was
continuously magnetically stirred, while the pH was maintained
constant by adding NaOH 2 M. The coprecipitation was carried out at
60 1C. The gel was transferred into Teflon-lined stainless-steel
autoclave and kept in an oven at 200 1C for 18 h, then was separated
by centrifugation at 2800 rpm, and washed with distilled water until
a sodium content lower than 0.13 wt%. Finally, the solid was dried
overnight at 90 1C in air. All samples were calcined in atmosphere of
air at 550 1C for 9 h. The HT100 sample was calcined at three different
temperatures to analyze the different structures formed. The LDH
precursors will be called HT100, HT75, HT50, HT25 and HT0, according
to the iron loading (keeping in mind only cations M3+), and the
calcined solids will be named CHT100, CHT75, CHT50, CHT25 and CHT0.
Compositions of the samples are presented in Table 1.
2.2. Sample characterization
The XRD powder patterns were collected on a Rigaku diffract-
ometer, using monochromatized Cu Kα radiation (λ ¼1.54 Ǻ) at a
Table 1
Chemical composition of the studied LDH.
LDH sample M3+ M2þ
%Fe3þ ¼ Fe3þ
M3þ Al
3þ
þFe3þ
Theoretical ICP Theoretical
HT0 Al 3 2.82 0 0
HT 25 Al–Fe 3 3.03 25
HT 50 Al–Fe 3 3.22 50
HT 75 Al–Fe 3 3.09 75
HT 100 Fe 3 2.42 100
39
scan speed of 1/41 min in 2θ and interfaced to a DACO-MP data
acquisition microprocessor provided with Diffract/AT software.
The diffraction pattern was identified by comparing with those
included in the JCPDS (Joint Committee of Powder Diffraction
Standards) data base.
Inductively coupled plasma (ICP) optical emission spectroscopy
was used for the determination of the metal content in the oxides.
The measurements were performed with a Varian Spectra AA.
Diffuse reflectance UV–vis (DRUV-vis) spectroscopic measure-
ments of the LDH precursors were recorded using an Optronics OL
750-427 spectrometer in the wavelength range 200–600 nm.
Termogravimetric analysis (TGA) and differential scanning
calorimetry (DSC) were carried out in a TA instrument SDT Q600
(0–1500 1C) instrumentation apparatus in a flowing air atmo-
sphere. Approximately 30 mg of sample were loaded and heated
at a rate of 10 1C/min up to 550 1C.
X-ray photoelectron spectroscopy (XPS) analyses were carried
out using an ESCA (VG microtech) spectrometer with a non-
monochromatic Mg Kα radiation (υ¼ 1253.6 eV) as the excitation
source. High-resolution spectra were recorded in the constant pass
energy mode at 20 eV, using a 720 mm diameter analysis area.
Under these conditions, the Au 4f7/2 line was recorded with 1.16 eV
FWHM (full width at half maximum) at a binding energy (BE) of
84.0 eV. The spectrometer energy scale was calibrated using Cu
2p3/2, Ag 3d5/2 and Au 4f7/2 photoelectron lines at 932.7, 368.3 and
84.0 eV, respectively. Charge referencing was done against adven-
titious carbon (C 1s, 284.8 eV). The pressure in the analysis
chamber was maintained lower than 10–9 Torr. PHI ACCESS
ESCA-V6.0 F software package was used for acquisition and data
analysis. A Shirley-type background was subtracted from the
signals.
Specific surface area was determined by the BET method, which
was recorded on a Micromeritics ASAP 2000 instrument. The
precursors were degassed at 200 1C and the calcined materials at
390 1C, both for 60 min.
The magnetic measurements were performed in a commercial
vibrating sample magnetometer (Lakeshore 7300) at room tem-
perature varying the applied field between 0 and 15000 Oe. The
powder samples were compacted applying 5 Tn to make a disc
shaped sample of 5 mm diameter and 2 mm height to measure
magnetization as function of applied field (M vs H). Hysteresis
loops were well fitted using the function:
 h i  
BH
MðHÞ ¼ M s  ð1−αÞ  1−eð−H=Hs Þ þ α  L
T
where LððB  HÞ=TÞ is the Langevin's function [23], T is the system
temperature, α is the paramagnetic and/or superparamagnetic
fraction, (1−α) is the ferromagnetic fraction, Hs is the ferromag-
netic saturation magnetic field, Ms is the total magnetization of
saturation. The B factor is an adjustable parameter, B ¼μ/k where μ
is the dipolar magnetic moment per paramagnetic molecule [11]
and k is the Boltzmann's constant. The parameters α, Ms y Hs are
also obtained from the fitting.
The SEM images were obtained using JEOL JSM-6380 LV
(accelerating voltage: 20 kV) and a Zeiss Supra 40.
The Mössbauer spectra were obtained in transmission geome-
try with a 512-channel constant acceleration spectrometer.
A source of 57Co in Rh matrix of nominally 50 mCi was used.
 100
Velocity calibration was performed against a 12-μm-thick α-Fe foil.
All isomer shifts (δ) mentioned in this paper are referred to this
ICP
standard at 298 K. The Mössbauer spectra were evaluated using a
commercial program with constraints named Recoil [24].
23.51 Lorentzian lines with equal widths were considered for each
45.02 spectrum component. The spectra were folded to minimize geo-
70.69
metric effects. In order to consider the existence of different iron
100
environments, hyperfine magnetic field distributions were used.
40 A.C. Heredia et al. / Journal of Magnetism and Magnetic Materials 342 (2013) 38–46

3. Results and discussion
3.1. X-ray diffraction
By X-ray diffraction, the hydrotalcite phase was detected in all
precursor samples. Most of the peak positions were matched with
the ICDD (International Centre for Diffraction Data) PCPDFWIN
data.
Powder X-ray diffraction patterns of precursors with different
(Al3+/Fe3+) molar ratio are shown in Fig. 1. The hydrotalcite phase
(PCPDFWIN 70-2151) was observed in all samples. Two peaks
located at 2θ of 11.61 and 23.41 are associated to diffraction by
(0 0 3) and (0 0 6) planes characteristics of hydrotalcite phase. The
secondary phase MgCO3 (magnesium carbonate PCPDFWIN 83-
1761) was observed only in HT75.
After calcinations at 550 1C, the (0 0 3) and (0 0 6) reflections
disappeared (Fig. 2). The MgO phase (periclase PCPDFWIN
78-0430) was detected in all samples. The XRD patterns showed
that Fe+3 species were crystallized in two structures: MgFe2O4
(Magnesium Iron oxide PCPDFWIN 71-1232) and α-Fe2O3 (Hema-
tite PCPDFWIN 79-1741). The transformation of the phases pro-
duced after calcinations are also demonstrated by the analysis of
the correspondent XRD patterns. Fig. 3 displays the XRD patterns
of HT100 sample heated in air at different temperatures. From this
XRD patterns, three peaks are observed at 35.41, 431, 62.21 for
samples calcined corresponding to characteristic diffractions of
MgFe2O4, MgO and Fe2O3. As the calcination temperature further
increases, the intensities of these peaks are increased together
with the peaks at 301 and 571 of MgFe2O4 spinel structure,
indicating that this phase is enhanced at high temperature [25].

3.2. DRUV–vis spectroscopy

The DRUV–vis spectra of the LDH precursors are shown in

(003)

(006)

Fig. 4. All precursor exhibited band at ∼210 and ∼275 nm. They
HT0 could be assigned to Fe3+ in tetrahedrally and octahedrally [26,27]
(009)

(015)

(018)

(110)
(113)

coordination in brucite layered. The band between∼350 and

550 nm is assigned to octahedral Fe3+ present in small clusters,
isolated species and large particles [27]. The temperature during of
HT25
the coprecipitation (60 1C) and the aging by hydrothermal method
in the autoclave, can promote the clusters production and particles
Intensity (a.u)

of great size outside the laminar structure [7].

HT50 Fig. 5 show the diffuse reflectance UV–vis spectra of mixed oxides.
The two characteristic bands at ∼210 nm and ∼275 nm present in LDH
lose their definition and intensity, when the laminar structure
disappears in the calcined samples. In all samples the band at
HT75
∼290 nm was observed, indicating the presence of Fe3+ species. The
peak around 350 nm is assigned to isolated Fe3+ in either periclase Mg
(Fe, Al)O or MgFe2O4 spinel in mixed oxide [27]. Between450
HT100
and 550 nm is observed a band, which can probably be assigned to
the aggregated Fe3+ oxide clusters.
10 20 30 40 50 60 70
3.3. Measurement of specific surface areas
2θ
Fig. 1. X-ray diffraction patterns of the LDH precursors with different iron The specific surface areas of precursor and calcined samples
percentage. (▲) Magnesium Carbonate MgCO3. were determined by BET method. The values obtained are

CHT0 850 °C

CHT25
Intensity (a.u)

Intensity (a.u)

700 °C
CHT50

CHT75
550 °C

CHT100

10 20 30 40 50 60 70 80 30 40 50 60 70 80
2θ 2θ
Fig. 2. X-ray diffraction patterns of calcined samples. (●) spinel MgFe2O4, Fig. 3. X-ray diffraction patterns of HT100 at different temperatures. (□) periclase
(□) periclase MgO, and (+) hematite Fe2O3. MgO, (●) spinel MgFe2O4, (+) α-Fe2O3.
 A.C. Heredia et al. / Journal of Magnetism and Magnetic Materials 342 (2013) 38–46 41

Fe3+ content is increased. This result is attributed to the decrease of

Octahedral
aluminum content, since the Al2O3 amorphous phase produces an
increase of the specific surface area. In agreement with this
Fe3+
Tetrahedral concept, Table 2 shows that the largest area was obtained in the
CHT0, while in the sample without iron the area was only 48 m2/g.

3.4. Thermal analyses (TGA and DSC)

Absorbance (a.u)

HT100

HT75 Thermal properties of the samples have been assessed by TGA

and DSC. These studies were carried out in air. To understand the
decomposition procedure of the Mg–Al–Fe LDH the TGA–DSC profiles
HT50
were analyzed in detail. Two weight loss stages can be observed on
the TGA curve, corresponding to the two endothermic peaks on DSC
HT25
profile, demonstrating that the decomposition proceeded in two
steps. In the TGA curves (Fig. 6), all samples show a weight loss below
∼100 1C, due to the water physically adsorbed, which corresponds to
a shoulder in the DSC profiles (Fig. 7), after this step starts the
200 250 300 350 400 450 500 550 600
decomposition proceeds. In the region between 100 and ∼300 1C the
TGA profiles show a weight loss which corresponds to the loss of
Wavelength (nm)
interlayer water, with a first maximum endothermic peak in the DSC
Fig. 4. UV–vis diffuse reflectance spectra of precursors with different iron profiles centered between 119 and 217 1C (Table 3). The dehydrox-
percentages. ylation of the brucite-like sheets and the loss of carbonates take place
between 300 and 410 1C. This weight loss is accompanied by a
maximum endothermic peak in the DSC profile centered between
345 and 396 1C approximately (Fig. 7). TGA curves showed a decrease
in the total weight loss when the iron content is increased due the
lower expulsion of CO2 and H2O from the LDH. This is consistent with
a decrease of LDH phase production observed by DRX and the
decrease of the specific surface area. Besides, the shift to lower
Absorbance (a.u)

CHT100
temperature of dehydroxylation of the brucite-like sheets with an
increase in the Fe content was observed, indicating a weakening of
CHT75 the brucite-like structure.
Final thermal decomposition products have shown to be metal
CHT50 oxides as well as mixed oxides and spinel-like species.

CHT25 3.5. XPS analysis

The XPS analysis has been done in order to obtain information

about the surface composition of the Mg–Al–Fe mixed oxides
derived from LDH precursors. Fig. 8 shows the Fe 2p spectra for
200 250 300 350 400 450 500 550 600 the oxides. All spectra show the main Fe 2p3/2 peak at BE of around
Wavelength (nm) 710.15 70.27 eV, accompanied by a satellite line visible at BE of

Fig. 5. UV–vis diffuse reflectance spectra of the oxides with different iron
percentages.
100

Table 2
Specific surface area of the samples. 90

% Fe (M+3) Specific surface area (m2/g)

Precursor Oxide 80
Weight (%)

0 48 179
25 20 150
50 19 119 70
75 18 96
100 17 48 HT100
HT75
60 HT50
summarized in Table 2. The specific surface area is inversely HT25
related with the iron content. HT0
Upon calcination at 550 1C for 9 h the surface areas of the
oxides are higher than their corresponding precursors. This 50
35 100 165 230 295 360 425 490 555 620 685
increase can be attributed to the formation of micro and meso-
Temperature (°C)
pores due to expulsion of CO2 and H2O from the LDH [28]. The
samples calcined showed a decrease in the areas when the iron Fig. 6. Precursor TGA curves with different iron percentages.
42 A.C. Heredia et al. / Journal of Magnetism and Magnetic Materials 342 (2013) 38–46

Table 3
Results of the TGA–DSC for different samples. Fe2p3/2
Sample temperature range Observed weight loss DSC maximum (1C) Fe3+ Satellite
(1C) (%) 7 0.01 1C
Fe2p1/2
Peak II Fe3+
HT0
Until 100 1.92 45.22
CHT100
100–300 15.6 261.9
300–550 25.19 395.03
Total weight loss 42.71
HT25

Intensity (a.u)
Until 100 1.57 64.41
100–300 13.84 206.62
CHT75
300–550 25.14 378.73
Total weight loss 40.55
HT50
Until 100 1.19 64.33
100–300 8.99 151.97
300–550 26.62 373.43 CHT50
Total weight loss 36.8
HT75
Until 100 1.87 102.59
100–300 5.56 179.34
300–550 22.94 363.37
Total weight loss 30.37
CHT25
HT100
Until 100 1.53 119.36
100–300 4.08 120
300–550 15.86 345
Total weight loss 21.47 700 705 710 715 720 725 730
BE (eV)
Fig. 8. XPS of the Fe 2p regions in the oxides.

-1
O1s OI
-3
OII
CHT100
Heat Flow (W/g)

-5

-7
Intensity (a.u)

CHT75
HT100 -9
HT75
HT50
HT25 -11
HT0
CHT50
-13
35 100 165 230 295 360 425 490 555 620 685
Temperature (°C)
Fig. 7. Precursor DSC curves with different iron percentages.

CHT25

around 718.87 70.40 eV, only indicating the presence of Fe3+

cations [29–31]. Whereas the contribution at 723.9 eV is assigned 526 528 530 532 534 536
to Fe 2p1/2. [32]. BE (eV)
The signal at 710.1570.27 eV can be decomposed in two
Fig. 9. XPS of the O1s regions in the oxides.
contributions; which indicate that the Fe3+ species exist in more
than one chemical state. Most probably, the two chemical states
may be related to different coordination environments of the Fe3+:
tetrahedral (A sites) at higher binding energy and octahedral OII, representing two different kinds of surface oxygen species.
(B sites) at lower binding energy [31,33]. The peak at 714.027 There is general agreement between the literature and the present
0.28 eV (peak II) could be related to the coordination environment results such that the OI with the lower oxygen bound to metal
of the Fe3+ cations in spinels phase (tetrahedral sites) [29]. cations of the structure, while OII with the higher BE al ca. 531.1 eV
Fig. 9 shows the O1s spectra for the surface oxides. The signal belongs most likely to surface oxygen, including mainly oxygen
to 529.5 70.2 eV can be deconvoluted in two contributions, OI and species of hydroxyl group [34].
 A.C. Heredia et al. / Journal of Magnetism and Magnetic Materials 342 (2013) 38–46 43

3.6. Magnetism 15

CHT100
The room temperature hysteresis loops (only the first quadrant
is shown in order to get a better comprehension) for all samples 10
are displayed in Fig. 10. The magnetization curves of these mixed
oxides are well fitted by equation (1), supposing a paramagnetic
and/or superparamagnetic contribution and a ferromagnetic one. 5
From these fittings the saturation magnetizations Ms, saturation

M [emu/g]
fields Hs, and the B parameter, were calculated and they are shown
0
in Table 4. 550°C
The saturation magnetization of sample with 100% Fe content,
is lower than reported values (10.6–24.1 emu/g) for MgFe2O4 -5 700°C
produced by calcination of the intercalated LDH at 750–1100 1C
for 2 h [35]. This result would indicate that the precursor is not
fully transformed in MgFe2O4 after calcination at 550 1C for 9 h. -10
It is in total agreement with both XRD analysis and calorimetric
850°C
studies. As expected, the substitution of Fe+3 cations by Al+3 affect
these magnetic parameters. There are different behaviors with the -15
incorporation of aluminum, given that MgFe2O4 is almost an -15 -10 -5 0 5 10 15
inverse spinel, and MgAl2O4 is a normal spinel, then when we H [KOe]
replace Fe by Al, to obtain compounds of the type MgAlxFe2−x O4, Fig. 11. Hysteresis curves and their corresponding fittings for CHT100 at different
the Fe3+ ions, that occupy A sites, could be replaced by Al3+ ions or calcinations temperatures.
by the migration of Mg2+ ions from site B to site A [11]. This phase
was not detected by XRD in the samples; this could be due to their
small size. In any case, if a magnetic ion is substituted in any of the
sub-lattices of the spinel by a diamagnetic one, the magnetic
interactions between networks of the spinel will be changed.
These phenomena can be explained by ramdon canting model
[36,37] and for a chemically disordered system such as MgAlxFe2−x
O4, Modi et al. [38] explained that the canting is no uniform shown
a locally dependent upon non-magnetic neighboring ions

CHT25
Fit Ec (1) CHT75
3.5

3.0
CHT100
2.5
M [emu/g]

2.0
Transmission (a.u)

CHT50

1.5 CHT50

1.0
CHT25
CHT75
0.5

0.0
0 2500 5000 7500 10000 12500 15000
H [Oe]
Fig. 10. First quadrant of the room temperature hysteresis loops whit fitting curve
using equation (1).

CHT100
Table 4
Saturation magnetization, saturation field, B parameter and paramagnetic percen-
tage fraction (α) resulting from fitting Eq. (1) to the curves in Fig. 10.

% Fe Ms [emu/g] Hs [Oe] B¼μ/k %α

100 2.93 7900 7.7 26.6

75 3.88 7100 5.6 43.4
-12 -10 -8 -6 -4 -2 0 2 4 6 8 10 12
50 1.33 7700 4.1 57.9 Velocity (mm/s)
25 1.13 6800 4.1 65
Fig. 12. Mössbauer spectra of the mixes oxides samples.
44 A.C. Heredia et al. / Journal of Magnetism and Magnetic Materials 342 (2013) 38–46

distribution. Also the magnetic behavior of this compound
depends on procedures and synthesis conditions [11]. However,
a correlation between the magnetic properties and aluminum
content was not observed. These results would indicate that the
samples are complex, with different population ratios of ferrimag-
netic (MgFe2O4), weak-ferromagnetic (α-Fe2O3), paramagnetic and
superparamagnetic phases depending on the aluminum content.
Fig. 11 shows the curves of hysteresis and their corresponding
fittings for CHT100 for different calcination temperatures. The
magnetization of saturation increases with the calcination tem-
perature, corresponding to the observed increase of the ferrimag-
netic phase and the crystallinity appreciated in X-ray diagrams.
3.7. Mössbauer
Fig. 12 shows the Mössbauer spectra of mixed oxides at room
temperature and their hyperfine parameters are listed in Table 5.
The spectra were fitted with one doublet and three sextets,
except the CHT100 spectrum in which only two sextets were used.
The sextet of higher hyperfine magnetic field (H≅51.5 T) present in
all samples corresponds to α-Fe2O3 with all hyperfine parameters
consistent with this species, with a hyperfine field value slightly
decreased in comparison with the “bulk” value [39]. This decrease
in H can be attributed to crystal size effects due to the process of
collective magnetic excitations [40], and/or to isomorphic replace-
ment of Fe3+ ions by Al3+[39].
The second sextet of the sample CHT100 corresponds to the sum
of the two sites, tetrahedral (A sites) and octahedral (B sites)
occupied by Fe3+ions in MgFe2O4 spinel [41]. The presence of a
large distribution of neighbors would produce a broadening of the
signals. Therefore, is not possible to distinguish between both
sites.
The other two sextuplets present in the samples with iron
content between 25 and 75% have hyperfine parameters assigned
to Fe3+ ions located in tetrahedral sites (sites A) and octahedral
(B sites) of MgFe2O4 [42].
The presence of A and B sites occupied by Fe3+ ions in the
spinel structure is consistent with that observed by XPS surface
analysis.
Another aspect is that the magnetic hyperfine field values of
the two sites are significantly diminished compared to a pure
spinel MgFe2O4 (between 14 and 15% for A site and between 11
and 9% for B site). The isomorphic Fe3+ substitution by diamag-
netic Al3+ ions would explain this result. This would produce
different environments for Fe3+ ions depending on the nature and
number of nearest neighbors which is reflected in a broadening of
the hyperfine magnetic field distributions of both sites. However, it
can not completely ruled out the existence of collective magnetic
excitations.
Finally, the doublet present in all samples could be attributed to
several species:
– isolated paramagnetic Fe3+ions dissolved in MgO matrix.
– superparamagnetic α-Fe2O3 (as very small crystals)
– susperparamagnétic MgFe2O4 with crystallite sizes below
12 nm [43]
– MgFexAl2−xO4 with x o1, since, the presence of a high concen-
tration of diamagnetic cations (Al3+) in the oxide, causes the
formation of small magnetic “clusters” inside the particles (for
this reason the MgFexAl2−xO4 phase was not detected by XRD),
which show superparamagnetism. If the diamagnetic ions
concentration is very high, these “clusters” can be completely
isolated, and the spectrum shows a doublet even at low
temperatures [44].
3.8. Scanning electron micrograph (SEM)
Fig. 13(a)–(d) shows the micrographs of MgAlFe LDH with
different iron content. The images were taken with secondary
electrons; all images show the presence of lamellar phase. When
the iron content is increased, smaller and exfoliated sheets are
produced. The layered double hydroxide structure is distinguished
in all samples except in the HT100.
Fig. 14(a) shows the image of the CHT75 sample. It was formed
by secondary electrons indicating a rough surface, and the
presence of small clusters generated by the calcination. When this
micrograph is compared with the corresponding LDH (Fig. 13(c)) it
is possible to see that has a greater porosity and dispersion of the
particles as well as the breakdown of the laminar structure. This
observation is consistent with the increased specific surface area,
when precursors are calcined.
The image of the CHT100 sample (Fig. 14(b)) was formed with
secondary electron and backscattered. Note the presence of a

Table 5
Oxides Mössbauer parameters at 298 K.

Species Parameters HT25 HT50 HT75 HT100

α-Fe2O3 H (T) 51.487 0.08 51.46 70.06 51.5 70.3 51.3 7 0.1
δ (mm/s) 0.37 70.01 0.38 70.01 0.39 70.05 0.38 70.02
2ε (mm/s) −0.21 70.02 −0.217 0.02 −0.20 7 0.09 −0.20 7 0.03
% 297 6 24 72 57 1 317 2
Fe3+ ions in sites (A+B) of MgFe2O4 H (T) — — — 42.8 70.7
δ (mm/s) — — — 0.32 70.06
2ε (mm/s) — — — 0.17 0.1
% — — — 157 2
Fe3+ ions in A sites of MgFe2O4 H (T) 397 1 39.8 70.8 39.5 70.4 —
δ (mm/s) 0.27n 0.27n 0.27n —
2ε (mm/s) −0.017 0.06 0.017 0.04 0n —
% 257 11 217 4 14 72 —
Fe3+ ions in B sites of MgFe2O4 H (T) 447 1 45.2 70.2 45.3 70.2 —
δ (mm/s) 0.35n 0.35n 0.35n —
2ε (mm/s) 0.047 0.06 0.02 70.02 0n —
% 247 11 297 3 257 2 —
Fe3+ paramagnetic and/or superparamagnetic Species Δ 0.85 7 0.03 0.777 0.01 0.707 0.01 0.687 0.01
δ 0.32 7 0.02 0.337 0.01 0.357 0.01 0.31 70.01
% 227 4 267 2 567 2 54 7 2

H: hyperfine magnetic field in Tesla; δ: isomer shift (all the isomer shifts are referred to α-Fe at 298 K); 2ε: quadrupole shift; Δ: quadrupole splitting.
n
Parameters held fixed in fitting.
 A.C. Heredia et al. / Journal of Magnetism and Magnetic Materials 342 (2013) 38–46 45

2 µm 2 µm

5 µm 2 µm

Fig. 13. Micrographs of MgAlFe LDH with different iron content. (a) HT0, (b) HT50, (c) HT75, (d) HT100.

1 µm 1 µm

Fig. 14. Micrographs of mixed oxides. (a) CHT75, (b) CHT100.

smooth surface roughness and small clusters. This can be attrib-
uted to sintering of the oxides, in absence of the amorphous
phase (Al2O3). This phase and the MgO are the cause of the iron
oxides dispersion [45]. Comparing the precursor area (17 m2/g)
with its oxide (48 m2/g) is not observed a significant increase after
calcination.
4. Conclusions
A series layered double hydroxides (LDH) as potential mixed
oxides precursors containing Mg2+, Al3+ and Fe3+ cations in the
brucite-like layers were obtained. The precursors have been
prepared by coprecipitation method at 60 1C with hydrothermal
treatment and a M2+/M3+ ¼3 constant molar ratio.
Powder X-ray diffraction shows the presence of the hydrotal-
cite phase. It was observed that the change the aluminum by iron,
the layer structure not was modified. On the other hand, when the
samples were calcined at 550 1C, MgO, MgFe2O4 and α-Fe2O3 were
detected by DRX; but by Mössbauer and magnetism the MgFexAl2−xO4
phase could be assigned.
The formation of MgFe2O4 spinel structure is enhanced at high
temperature. By UV–vis-DRS were observed Fe3+ in tetrahedrally
and octahedrally coordination in brucite layered. In the calcined
samples was observed the presence of isolated Fe3+ in either
periclase Mg(Fe, Al)O or MgFe2O4 spinel in mixed oxide and Fe3+
oxide clusters.
A lower expulsion of CO2 and H2O of the interlayer when the
iron content is increased could be observed by a decrease in the
total weight loss from the LDH and in the specific surface areas in
the oxides.
The XPS analysis shows that the Fe3+ ions can be found in two
coordination environments (tetrahedral and octahedral) as mixed
oxides, and as spinel-structure.
46 A.C. Heredia et al. / Journal of Magnetism and Magnetic Materials 342 (2013) 38–46
The combined magnetic and Mössbauer results analysis of the
complete series show that the samples are complex, with different
population ratios of ferrimagnetic (MgFe2O4), weak-ferromagnetic
(α-Fe2O3), paramagnetic and superparamagnetic phases depending
on the aluminum content. Magnetic properties were significantly
improved when the calcination temperature was increased as a
consequence of a better crystallization of spinel structure.
Due to the magnetic phase (spinel) in the materials calcined at
temperatures above 550 1C, they could be used as catalysts in
reactions of photocatalysis and dehydrogenation of ethylbenzene.
Acknowledgements
This work was supported by the UTN-FRC of Argentina.
We thank UTN for doctoral fellowship for Angélica C. Heredia.
We thank geol. Julio D. Fernández (UTN-FRC, Córdoba, Argentina)
for help in recording specific surface area data and to Dra.
Valentinuzi of LAMARX for SEM photografies.
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