Available online at www.sciencedirect.

com

Catalysis Communications 8 (2007) 2037–2042

www.elsevier.com/locate/catcom

Manganese ferrite nanoparticles synthesized through a

nanocasting route as a highly active Fenton catalyst
Teresa Valdés-Solı́s *, Patricia Valle-Vigón, Sonia Álvarez, Gregorio Marbán,
Antonio B. Fuertes
Instituto Nacional del Carbón (CSIC), Francisco Pintado Fe, 26, 33011 Oviedo, Spain

Received 4 March 2007; received in revised form 27 March 2007; accepted 28 March 2007
Available online 10 April 2007

Abstract

Spinel ferrite MnFe2O4 nanoparticles were synthesized by means of a nanocasting technique using a low-cost mesoporous silica gel as
a hard template. The magnetic nanoparticles, of <10 nm diameter and with a surface area of around 100 m2/g, were tested as a heter-
ogeneous Fenton catalyst for the decomposition of hydrogen peroxide under neutral and basic conditions. This catalyst shows a much
higher activity than previous heterogeneous catalysts reported in the literature, which is mainly ascribed to its small particle size. Fur-
thermore, the magnetic catalyst can be easily separated from the reaction medium by means of an external magnetic field. The effects of
residual silica and the purity of the catalyst (hematite formation) on catalytic activity have been studied and correlated. The results
obtained show this catalyst to be a suitable candidate for the removal of pollutants in wastewaters by means of the Fenton heterogeneous
reaction.
Ó 2007 Elsevier B.V. All rights reserved.

Keywords: Hydrogen peroxide decomposition; Template method; Manganese ferrite spinel; Nanoparticle; Heterogeneous Fenton reaction

1. Introduction gradability products because homolytic scission yields two

Heterogeneous catalysts made up of nanoparticles are,
for many applications, an attractive alternative to classical
supported catalysts [1,2]. They exhibit a high catalytic
activity derived from their large external surface area and
their easy accessibility to active centres (low diffusional
resistance). A field of growing interest for the application
of nanocatalysts is that of liquid phase catalysis.
Catalytic wet oxidation is a well known method for
removing organic pollutants from wastewaters [3,4]. At
ambient temperature, ozone and hydrogen peroxide are
preferred as oxidants because they only produce innocuous
O2 and H2O. H2O2 is preferred when treating solutions
with total carbon content in a medium range. Moreover
H2O2 is safer than ozone and more suitable for low biode-
*
Corresponding author. Tel.: +34 985 119 090; fax: +34 985 297 662.
E-mail address: tvaldes@incar.csic.es (T. Valdés-Solı́s).
hydroxyl radicals from H2O2 [5]. The catalytic generation
of hydroxyl radicals by iron ions (Fenton mechanism) is
well known and can be basically described by the following
reactions [3]:
Fe2þ þ H2 O2 ! Fe3þ þ OH þ HO ð1Þ
3þ 2þ þ 
Fe þ H2 O2 ! Fe þ H þ HOO ð2Þ
However, the homogeneous Fenton process requires stoi-
chiometric amounts of Fe2+ and large quantities of acid,
usually H2SO4, to produce the optimum pH (pH 3). After
the process, the effluent must be neutralized with a base to
be safely discharged. This gives rise to significant amounts
of sludge, which represents a serious drawback to the process
due to disposal problems. In order to overcome this obstacle,
several heterogeneous Fenton catalysts have recently been
developed, including iron-exchanged Nafion membranes,
iron modified clays and iron-exchanged zeolites, as recently
reviewed by Pignatello et al. [3]. Additionally, a number of

1566-7367/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2007.03.030
2038 T. Valdés-Solı́s et al. / Catalysis Communications 8 (2007) 2037–2042
iron oxides such as c-FeOOH [6], Fe2O3/Fe2Si4O10(OH)2 [7],
or transition metal ferrites MxFe3xO4 (M = Cu, Mn, Co
and Ni) [8–11] have been investigated. However, the hetero-
geneous Fenton reaction is frequently too slow to be used for
the treatment of wastewater. Therefore, most of the hetero-
geneous Fenton catalysts developed until now have relied on
UV irradiation to accelerate the reaction. This implies the
need for specific equipment at an additional cost and
requires that the whole catalyst be accessible to light. As
indicated by Hyeon et al. [12] the development of novel cat-
alysts with a greater surface area could facilitate the Fenton
reaction, thus avoiding the need for UV irradiation to accel-
erate the process. The nanocasting technique has recently
been proved to be an attractive alternative for synthesizing
nanosized inorganic materials [13,14]. This synthetic strat-
egy applied to the preparation of nanoparticles involves
the use of porous solids (mainly silica or carbon) as sacrificial
templates [15–18]. The pores of the template act as nanoreac-
tors where synthesis reactions take place in the desired prod-
ucts. Under these conditions, the growth of the solids formed
is restricted, resulting in nanosized materials with a high sur-
face area once the template framework is removed. In partic-
ular, the use of mesoporous silica gel as template for the
synthesis of metal oxide nanoparticles is of great interest
for its availability, low cost and inertness. Recently we
reported the preparation of various nanosized ferrites with
a size <10 nm using a commercial silica gel as template [19].
The main purpose of the present work is to analyse the
catalytic decomposition of H2O2 in liquid phase using man-
ganese ferrite (MnFe2O4) nanoparticles prepared by the
nanocasting technique.
2. Experimental
2.1. Preparation of materials
Nanosized MnFe2O4 was prepared following the proce-
dure developed in our laboratory [14,16] and already
applied in the synthesis of magnetic nanoferrites [19].
Briefly, stoichiometric amounts of hydrated metal nitrates
(Mn/Fe atomic ratio of 0.5) were dissolved in ethanol. A
silica gel purchased from Aldrich (Ref. 28,8500) was
employed as hard template. This material was impregnated
with the nitrate solution until incipient wetness. The
impregnated sample was dried at 100 °C and the impregna-
tion–drying cycle was repeated until a theoretical molar Si/
(Mn + Fe) = 4 molar relationship was attained. Subse-
quently, this material was treated under a N2 atmosphere
at 800 °C (5 °C/min) for 4 h. Spinel ferrite nanoparticles
were obtained after dissolution of the silica framework in
a 2 M NaOH solution (two steps of 20 h).
2.2. Characterization of materials
Nitrogen adsorption isotherms were obtained at
196 °C on a Micromeritics ASAP 2010 volumetric
adsorption system. The BET surface area was evaluated
from the isotherm analysis in the relative pressure range
of 0.04–0.20. The silica contents of the samples were
studied by means of a scanning electron microscope
(DSM 942, Zeiss) and an attached energy dispersive
X-ray detector (EDX). Transmission electron microscopy
(TEM) images were obtained in a JEOL-2000 FXII.
X-ray diffraction (XRD) patterns were recorded over a
wide-angle range (2h = 20–70°) on a Siemens D5000
instrument operating at 40 kV and 20 mA and using
Cu Ka radiation (k = 0.15406 nm). Crystal size values
were estimated from the XRD patterns by using Scher-
rer’s equation.
2.3. Catalytic activity measurements
Hydrogen peroxide decomposition experiments were
performed in a flask subjected to orbital stirring. The cata-
lyst (20 mg) was added to 25 mL of 0.2 M H2O2. The
decomposition of H2O2 was analysed at two different pH
values: (a) at a pH 13 (KOH 2 M) to minimise the self-
decomposition of the hydrogen peroxide [9] and (b) at a
pH 6. The decomposition reaction was followed by mea-
suring the formation of gaseous oxygen in a volumetric
system.
3. Results and discussion
3.1. Structural characteristics of the catalyst
The procedure employed to obtain the nanosized
MnFe2O4 catalyst involves three simple steps: (1) filling
the porosity of a silica gel with the inorganic precursor,
(2) conversion of the infiltrated compound to inorganic
nanoparticles through thermal treatments (nanocomposite)
and (3) dissolution of the silica framework with an etching
agent (NaOH).
Evidence of the formation of the manganese ferrite spi-
nel is obtained by X-ray diffraction analysis. The XRD pat-
tern shown in Fig. 1a reveals that the diffraction peaks are
located in the position expected for MnFe2O4 (JCPDS 10-
319), although several peaks corresponding to a-Fe2O3
were also detected (JCPDS 33-664). The size of the
MnFe2O4 crystallites as deduced by applying the Scherrer
equation to the main diffraction peaks are in the 7–9 nm
range. In Fig. 1a the XRD pattern for the MnFe2O4/
SiO2 composite (prior to the dissolution of silica with
NaOH) is also presented. The particle size calculated for
the MnFe2O4 nanoparticles embedded in the silica matrix
is similar to that deduced for the non-confined nanoparti-
cles (7–9 nm).
Representative TEM images obtained for the ferrite
nanoparticles and silica–ferrite nanocomposites are shown
in Fig. 2a and b respectively. The MnFe2O4 sample consists
of nanoparticles of approximately 10 nm, which aggregate
to form large clusters (see Fig. 2a). The size of these nano-
particles as deduced by TEM inspection is in agreement
with that calculated by XRD analysis. The TEM image
 T. Valdés-Solı́s et al. / Catalysis Communications 8 (2007) 2037–2042 2039

a (311) b
500
2.5 12 nm
(440)

dV/dlog(D), c m /g
MnFe2O4

Adsorbed volume, cm3 STP/g

2.0

3
(511) SiO2
(220) (400) nanoparticles 400
1.5
Intensity, a.u.

1.0

300 0.5
(440) MnFe2O4/SiO2
(104) 0.0
(220) nanocomposite
1 10 100
(511) 200 Pore size (D), nm

JCPDS: 33-664 ( -Fe2O3) 100

MnFe2O4/SiO2
JCPDS: 10-319 (MnFe 2O4)

MnFe2O4 nanoparticles
0
10 30 50 70 90 0 0.2 0.4 0.6 0.8 1

Relative pressure P/P0

Fig. 1. (a) XRD patterns of the synthesized materials. The spectra for MnFe2O4 and a-Fe2O3 from the database are included. (b) Nitrogen sorption
isotherms of silica template, silica–ferrite nanocomposite and MnFe2O4 nanoparticles.

Fig. 2. (a) TEM image of the MnFe2O4 nanoparticles. (b) TEM image of the MnFe2O4/SiO2 nanocomposite (the dark spots correspond to areas
containing MnFe2O4 nanoparticles).

obtained for the MnFe2O4/SiO2 composite (Fig. 2b) shows
that the MnFe2O4 (dark points in Fig. 2b) are randomly
dispersed along the silica matrix, which exhibits a large
and open porosity.
Fig. 1b shows the nitrogen sorption isotherm and the
pore size distribution (Fig. 1b, inset) obtained for the
MnFe2O4 nanoparticles, MnFe2O4/SiO2 nanocomposites
and silica template. The silica used as template has a
BET surface area of 340 m2/g, a pore volume of
0.89 cm3/g and a porosity resulting from mesopores of
approximately 12 nm (Fig. 1b, inset). The composite
MnFe2O4/SiO2 still retains a large porosity with a BET sur-
face area of 222 m2/g and a pore volume of 0.52 cm3/g,
which consists of mesopores with a size similar to that of
the template. This result demonstrates that the size of pores
in the composite is unaffected by the deposited nanoparti-
cles and, consequently, it has a porosity that is widely
accessible to reactants. This is coherent with the results
deduced from TEM inspection (Fig. 2b). The BET surface
area and the pore volume calculated for the MnFe2O4
nanoparticles are 93 m2/g and 0.39 cm3/g, respectively.
The nitrogen sorption isotherm of this material (Fig. 1b)
does not exhibit a capillary condensation step and shows
a large nitrogen uptake at high relative pressures
(p/p0 > 0.8). These findings suggest that the material does
not contain framework-confined pores but is made up of
individual nanoparticles, which is in accordance with the
results deduced by TEM inspection (Fig. 2a). From this
result we can estimate the effective size of the nanoparticles
on the basis of the values of the BET surface area, which
can be identified with the external surface area of the nano-
particles. The value obtained in this way for the particle
size is 13 nm, which is slightly larger than that deduced
from TEM inspection and XRD analysis.
2040 T. Valdés-Solı́s et al. / Catalysis Communications 8 (2007) 2037–2042

3.2. Catalytic activity three factors: (i) the differences in particle size of the nano-
particles (7–9 nm), (ii) the negative effect of the remaining
The decomposition of H2O2 by the MnFe2O4 nanopar- silica, not completely dissolved by NaOH, and (iii) the pres-
ticles was examined at two pH values, 6 and 13. The results ence of small amounts of hematite (a-Fe2O3) in the nanom-
obtained under these conditions show that catalytic activity aterials [11]. The effect of the residual silica content on the
is similar at both pHs. Moreover, we also observed that catalytic activity of MnFe2O4 nanoparticles is illustrated
under the reaction conditions used here, the leaching of in Fig. 3b. In this figure, a catalyst containing 5.4 wt% of sil-
iron species into the solution does not take place, which ica was subjected to successive NaOH treatments in order to
rules out the occurrence of homogeneous Fenton processes. reduce the silica content of the material to 1.6 wt%, while
The ability of MnFe2O4 nanoparticles to decompose keeping the particle size and the hematite content constant.
hydrogen peroxide is exemplified in Fig. 3 which depicts The reduction in silica content gives rise to a significant de-
the temporal conversion of H2O2. Total decomposition is crease in tX=0.5 from 3.58 min to 1.59 min and consequently
achieved in around 5 min, regardless of the initial H2O2 the rate constant (k) increases from 807 to 1291 g1 s1. The
concentration (0.2 M or 3 M). For purposes of comparison proportion of a-Fe2O3 in the nanocatalyst was related to
the data reported by other authors, who used ferrites made XRD peak area ratios for a-Fe2O3(1 0 4) and
up of large particles (SBET = 14–16 m2/g [11], 28 lm MnFe2O4(2 2 0). By correlating the experimental data of k
[8,9]) are plotted in Fig. 3a. As illustrated, the nanosized obtained for different catalysts with these parameters we de-
ferrites prepared in our study exhibit a much higher cata- duced the following expression for the rate constant:
lytic activity than the literature catalysts, which clearly k calc ¼ k 0 ð1  a  rFe2 O3  b  d p  c  SiO2 Þ ð4Þ
require longer times for the decomposition of H2O2 to be
completed. where rFe2 O3 ¼ Areað1 0 4Þ=Areað2 2 0Þ, dp the particle size
The reaction rate of H2O2 decomposition was analysed (nm) and SiO2 the silica content (wt%). In Fig. 4 the values
by assuming first order kinetics and defining tX=0.5 as the of kcalc calculated from Eq. (4) are compared with the
time needed to achieve a conversion of 50%. The kinetic experimental values of k. An excellent agreement between
constant k was estimated by performing the integration the two values is observed. The influence of each parameter
in the X = 0–0.5 range (Eq. (3)). (subtracting terms in Eq. (4)) on the calculated kinetic con-
Z 0:5 stant differs. Thus, dp is the factor that has the strongest
dX dX influence on the value of kcalc (66% of the terms in brackets
¼ kW cat ð1  X Þ !
dt 0 ð1  X Þ in Eq. (4)), while the average effect of the presence of hema-
Z tX ¼0:5 tite is 22% and that of silica content is 12%.
0:693
¼ kW cat dt ! k ¼ ð3Þ Although it has been stated that the total removal of
0 W cat  tX ¼0:5
SiO2 has a positive effect on the kinetics of the decomposi-
We examined the H2O2 decomposition by using nanosized tion process, the use of MnFe2O4/SiO2 composites remains
MnFe2O4 catalysts of slightly different compositions (in a subject of interest. The use of nanocomposites instead of
residual silica content and hematite content) and particle nanoparticles affords two advantages: (i) the synthetic
sizes as a result of the slight variations in drying and silica method is simpler because the silica removal step is avoided
etching times. The values obtained for the rate constant k and (ii) the use of an MnFe2O4/SiO2 composite could
for these samples are in the range of 130–1600 g1 s1 range. reduce the aggregation between nanoparticles that usually
These variations in the rate constant are associated with takes place in magnetic nanomaterials. Recently, Hyeon

a MnFe2O4 (0.2 M H2O2) b SiO2 content: 1.6 wt%

1.0 1.0
Fractional conversion (X)
Fractional conversion (X)

0.8 0.8 SiO2 content: 5.4 wt%

MnFe2O4 (3M H2O2)
0.6 0.6
Cux Fe 3-x O4 (Onuchukwu, 1990) [8]
0.4 0.4

0.2 0.2
Mn0.53Fe2.47O4 (Costa et al., 2006) [11]
0.0 0.0
0 5 10 15 20 25 0 5 10 15 20 25
Time (min) Time (min)

Fig. 3. (a) Conversion of H2O2 with time in the presence of nanosized MnFe2O4. Conditions reported as 0.2 M corresponds with the experimental
conditions used by Onuchukwu [8] ([H2O2] = 0.2 M, 20 mg, 25 mL, [KOH] = 2 M), experiments reported as 3 M were performed under the experimental
conditions reported by Costa et al. [11] ([H2O2] = 3 M, 30 mg and 7 mL). (b) Effect of SiO2 content on H2O2 decomposition ([H2O2] = 0.2 M, 20 mg,
25 mL, [KOH] = 2 M).

Fig. 4. Comparison between the experimental (k) and calculated (kcalc) kinetic constants for the decomposition of H2O2 ([H2O2] = 0.2 M, 20 mg, 25 mL,
[KOH] = 2 M). The values of kcalc were obtained by means of Eq. (4) (k0 = 5340 g1 s1, a = 0.243 g1 s1, b = 0.062 g1 s1 nm1, c = 0.021 g1 s1).
A: MnFe2O4 (this work)
1.0 B: MnFe2O4/SiO2 (this work)
Fractional conversion (X)
0.8
0.6
0.4
Catalyst Conversion time (min)
0.2 A 0.98
B 0.99
C 0.88
0.0
0 500 1000
Time (min)
Fig. 5. Variation of the H2O2 decomposition with time for the MnFe2O4
nanoparticles, MnFe2O4/SiO2 and FeAlSi composite reported by Hyeon
et al. [12] (active phase 0.2 g l1, [H2O2] = 5 mM). Time values to achieve
the highest conversion degrees are included in the table. Inset: illustration
of the magnetic separation of nanoparticles from the liquid media.
et al. [12] reported the preparation of two heterogeneous
Fenton catalysts consisting of iron oxide–silica (FeSi) and
iron oxide–alumina–silica (FeAlSi) nanocomposites and
analysed their activity for H2O2 decomposition (0.005 M).
They observed a notable increase in the reaction rate when
iron oxide nanoparticles were synthesized over the alumina
covered silica (FeAlSi) and assumed that this result was
related to the small particle size of the catalyst and a high
dispersion of hematite in FeAlSi. The catalytic activity of
the MnFe2O4 nanoparticles and MnFe2O4/SiO2 nanocom-
posites prepared in this work was compared with the data
reported by Hyeon [12] for the FeAlSi catalyst (Fig. 5). It
can be seen that, even if the activity of the MnFe2O4/
SiO2 nanocomposite (72 SiO2 wt%) is considerably lower
than the activity of MnFe2O4 nanoparticles, the MnFe2O4/
SiO2 sample exhibits a very high activity compared to that
of the FeAlSi composite prepared by Hyeon et al. [12].
MnFe2O4 nanoparticles and MnFe2O4/SiO2 can easily be
recovered from the reaction media by applying an external
magnetic field. It was experimentally observed that the mate-
rials synthesized are rapidly attracted (<1 min) by a conven-
tional magnet placed close to the reaction vessel (inset of
Fig. 5), demonstrating the efficacy of magnetic separation.
T. Valdés-Solı́s et al. / Catalysis Communications 8 (2007) 2037–2042 2041
2000
1500
k (g -1 s -1)
1000
500
0
0 500 1000 1500 2000
kcalc (g-1 s-1)
4. Conclusions
C: FeAlSi (Hyeon, 2006) [12]
In summary, we have demonstrated that the MnFe2O4
nanoparticles obtained through a nanocasting route, using
a silica gel as a sacrificial hard template, serve as a very
active heterogeneous Fenton catalyst for the decomposi-
tion of H2O2. This catalyst exhibits a high performance
Magnet
for a wide range of pH values (6 and 13) and H2O2 concen-
33
360
trations (0.005–3 M). The activity measured for these
2858
nanoparticles is clearly superior to that observed for the
1500 2000 2500 3000 nanoparticles embedded in a porous silica matrix. The
results obtained show that the catalytic activity of
MnFe2O4 nanoparticles is reduced by residual silica and
also by the presence of hematite impurities. A comparison
of the catalytic activity of the materials reported in the
present work (MnFe2O4 nanoparticles and MnFe2O4/
SiO2 nanocomposite) with that of other heterogeneous
Fenton catalysts reported in the literature shows that our
catalysts exhibit a superior performance.
Acknowledgements
T.V.-S. thanks the CSIC-ESF for the I3P postdoctoral
contract. The financial support provided by MCyT
(MAT2005-00262) and FICYT (IB05-001) is gratefully
acknowledged.
References
[1] R. Schlögl, S.B. Abd Hamid, Angew. Chem., Int. Ed. 43 (2004) 1628.
[2] A.T. Bell, Science 299 (2003) 1688.
[3] J.J. Pignatello, E. Oliveros, A. MacKay, Crit. Rev. Env. Sci. Technol.
36 (2006) 1.
[4] P.R. Gogate, A.B. Pandit, Adv. Environ. Res. 8 (2004) 501.
[5] G. Centi, S. Perathoner, T. Torre, M.G. Verduna, Catal. Today 55
(2000) 61.
[6] S.S. Chou, C.P. Huang, Chemosphere 38 (1999) 2719.
[7] J.Y. Feng, X.J. Hu, P.L. Yue, H.Y. Zhu, G.Q. Lu, Water Res. 37
(2003) 3776.
[8] A.I. Onuchukwu, Mater. Chem. Phys. 25 (1990) 331.
[9] A.I. Onuchukwu, Mater. Chem. Phys. 37 (1994) 129.
[10] R.C.C. Costa, M.F. Fontes Lelis, L.C.A. Oliveira, J.D. Fabris, J.D.
Ardisson, R.R.V.A. Rios, et al., Catal. Commun. 4 (2003) 525.
2042 T. Valdés-Solı́s et al. / Catalysis Communications 8 (2007) 2037–2042

[11] R.C.C. Costa, M.F.F. Lelis, L.C.A. Oliveira, J.D. Fabris, J.D.
Ardisson, R.R.V.A. Rios, et al., J. Hazard Mater. 129 (2006) 171.
[12] H. Lim, J. Lee, S. Jin, J. Kim, J. Yoon, T. Hyeon, Chem. Commun.
(2006) 463.
[13] T. Valdés-Solı́s, A.B. Fuertes, Mater. Res. Bull. 41 (2006) 2187.
[14] T. Valdés-Solı́s, G. Marbán, A.B. Fuertes, Chem. Mater. 17 (2005) 1919.
[15] F. Schüth, Angew. Chem., Int. Ed. 42 (2003) 3604.
[16] A.B. Fuertes, J. Phys. Chem. Sol. 66 (2005) 741.
[17] B.Z. Tian, X.Y. Liu, H.F. Yang, S.H. Xie, C.Z. Yu, B. Tu, et al.,
Adv. Mater. 15 (2003) 1370.
[18] M. Schwickardi, T. Johann, W. Schmidt, F. Schüth, Chem. Mater. 14
(2002) 3913.
[19] T. Valdés-Solı́s, P. Tartaj, G. Marbán, et al., Nanotechnology 18
(2007) 145603.