Journal of Colloid and Interface Science 377 (2012) 184–190

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Journal of Colloid and Interface Science

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Magnetic a-Fe2O3/MCM-41 nanocomposites: Preparation, characterization,

and catalytic activity for methylene blue degradation
Irina Ursachi a, Alexandru Stancu a, Aurelia Vasile b,⇑
a
Department of Physics ‘‘Alexandru Ioan Cuza’’ University of Iasi, 11 Carol I Bvd., 700506 Iasi, Romania
b
Department of Chemistry, ‘‘Alexandru Ioan Cuza’’ University of Iasi, 11 Carol I Bvd., 700506 Iasi, Romania

a r t i c l e i n f o a b s t r a c t

Article history: Catalysts based on nanosized magnetic iron oxide stabilized inside the pore system of ordered mesopor-
Received 10 February 2012 ous silica MCM-41 have been prepared. The obtained materials were characterized by powder X-ray dif-
Accepted 23 March 2012 fraction analysis (XRD), scanning electron microscopy (SEM), vibrating sample magnetometer (VSM), and
Available online 4 April 2012
N2 adsorption–desorption isotherm. XRD analysis showed that the obtained materials consist from the
pure hematite crystalline phase (a-Fe2O3) dispersed within ordered mesoporous silica MCM-41. Mag-
Keywords: netic measurements show that the obtained nanocomposites exhibit at room temperature weak ferro-
Hematite
magnetic behavior with slender hysteresis. The catalytic activity of the magnetic a-Fe2O3/MCM-41
MCM-41
Magnetic nanoparticles
nanocomposites was evaluated by the degradation of methylene blue (MB) aqueous solution. For this
Magnetic properties purpose, an ultrasound-assisted Fenton-like process was used. The effect of solution pH on degradation
Ultrasonic irradiation of MB was investigated. The results indicated that US–H2O2–a-Fe2O3/MCM-41 nanocomposite system is
Degradation effective for the degradation of MB, suggesting its great potential in removal of dyes from wastewater. It
Methylene blue was found that the degradation rate of MB increases with decrease in the pH value of the solution.
Hydrogen peroxide Ó 2012 Elsevier Inc. All rights reserved.

1. Introduction reduction in the duration of synthesis, only a few examples of sono-

Magnetic iron oxide nanoparticles have attracted increasing
attention due to their wide range of potential applications in catal-
ysis, magnetic recording, microwave absorption, biological sensors,
in vitro/in vivo applications, and environmental depollution [1–5].
Among iron oxides, hematite (a-Fe2O3) is a promising material
for different catalytic applications [6,7]. Generally, magnetic iron
oxide nanoparticles have a low specific surface area that causes
poor catalytic performances. Moreover, obtaining and maintaining
these particles in nanosized form is difficult due to the natural ten-
dency of aggregation. One way used to overcome these drawbacks
is to disperse iron oxide nanoparticles within a porous matrix hav-
ing a high specific surface area. Due to their uniform pores with
size in the range 1.5–20 nm [1,8], high specific surface area and
tunable surface functional groups [1] in conjunction with high
hydrothermal and chemical stability, ordered mesoporous silica
materials such as MCM-41 and SBA-15 can be used as a nanoreac-
tor for the synthesis and stabilization of magnetic iron oxide nano-
particles [9].
Various methods have been reported in the literature for the syn-
thesis of ordered mesoporous silica focused on reducing synthesis
time without affecting the quality of the material [10–12]. Although
ultrasonic irradiation has the major advantage of a very pronounced
⇑ Corresponding author. Fax: +40 232 201313.
E-mail address: aurelia@uaic.ro (A. Vasile).
chemical synthesis of mesoporous silica materials [13–15] have yet
been reported. The sonochemical technique for the synthesis of or-
dered mesoporous silica can reduce the preparation time from 48
to 72 h to several hours. Moreover, ordered mesoporous silica
MCM-41 obtained by sonochemical technique is thermally more
stable compared with the corresponding material obtained by the
conventional method. This stability is attributed to the thicker pore
walls of MCM-41 obtained by sonochemical synthesis [13].
In recent years, increasing interest has been paid to the use of
ultrasound in the degradation of hazardous organic pollutants
[16–18]. The phenomenon of acoustic cavitation provides unique lo-
cal conditions of extremely high temperature and pressure, which
induce the formation of hydroxyl radicals (HO) and hydrogen atoms
[17]. The non-volatile, hydrophilic hazardous pollutants can be de-
graded by HO at the bubble surface or in the solution bulk. However,
ultrasonic processes are limited by low degradation rate due to the
high stability of non-volatile dyes [19]. Thus, the coupling of ultra-
sonic irradiation with other oxidation processes (photocatalysis,
ozonization or Fenton-type processes) should enhance the degrada-
tion rate of organic pollutants. The coupling of ultrasound with
photocatalysts or ultrasound with Fenton-like processes has at-
tracted attention of many researchers in recent years. In these cases,
promising results were obtained in the degradation of hazardous or-
ganic pollutants such as phenol [20] and methylene blue [17].
In the present paper, we report the preparation of a catalyst
based on magnetic iron oxide nanoparticles dispersed inside pores

0021-9797/$ - see front matter Ó 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcis.2012.03.066
 I. Ursachi et al. / Journal of Colloid and Interface Science 377 (2012) 184–190
of amino functionalized mesoporous silica MCM-41 and its appli-
cation to the degradation of methylene blue (MB) by means of a
coupled heterogeneous Fenton-like process with ultrasonic irradi-
ation. Amino functionalized MCM-41 used as catalyst support was
obtained by ultrasound-assisted synthesis using cetyltrimethylam-
monium bromide (CTAB) as structure-directing agent, followed by
post-synthesis functionalization with 3-aminopropyltriethoxysi-
lane (APTES). The magnetic iron oxide precursor (iron nitrate)
was loaded into the amino functionalized mesoporous support by
the wet impregnation technique. The choice of MB is motivated
by its positive charge in solution, which excludes volatility and
gas-phase pyrolysis. Moreover, the blue color allows easy spectro-
photometric monitoring of the system during MB degradation
experiments. The effect of solution pH on the degradation of MB
was investigated as well.
2. Materials and methods
2.1. Materials
Tetraethyl orthosilicate (TEOS, 98%) and sodium hydroxide
(NaOH) were purchased from Merck; cetryltrimethylammonium
bromide (CTAB, 99%) and methylene blue (MB, C16H18N3Cl3H2O)
were purchased from Sigma. Iron nitrate nonahidrate (Fe(-
NO3)39H2O, 98%), 3-aminopropyltriethoxysilane (APTES, 99%),
and aqueous ammonia (30% NH3) were purchased from Aldrich;
ethanol (EtOH, 99%) and hydrogen peroxide (30%, w/w) were pur-
chased from S.C. Chemical Company S.A. (Romania). All chemicals
were used as received without further purification. Deionized
water used throughout the experiments was prepared with an
ELGA purelab water system.
2.2. Mesoporous silica MCM-41 preparation
Pure ordered mesoporous silica MCM-41 was prepared by ultra-
sound-assisted synthesis and conventional method [21,22]. Both
synthetic methods, which have been detailed in [15], were per-
formed using an initial reaction mixture with the following molar
composition: 1TEOS:0.3CTAB:58EtOH:11NH3:144H2O. The prod-
uct obtained via ultrasonic irradiation was denoted U, while the
product obtained by conventional method was denoted M.
Modification of pure mesoporous silica samples with amino
functional groups was carried out by post-synthesis procedure as
follows: 0.5 g MCM-41 prepared as above was dispersed in the eth-
anol-diluted APTES under vigorous stirring at room temperature
for 4 h. The mixture was then carefully heated to evaporate the sol-
vent. The resulting products were denoted pU and pM.
2.3. Preparation of nanosized magnetic iron oxide/MCM-
41nanocomposites
In order to disperse iron oxide inside pores of amino functional-
ized mesoporous silica MCM-41 matrix, the samples pU and pM,
respectively, were impregnated with an aqueous solution containing
Table 1
Description of the synthesized samples.
Sample Synthesis methods
U Sonochemical
pU Sonochemical
M Conventional
pM Conventional
pUF Wet impregnation
pMF Wet impregnation
a
Molar ratio used at functionalization.
b
Molar ratio used at impregnation.
185
an appropriate amount of Fe(NO3)39H2O to achieve the designed
concentration (see Table 1). Impregnation was carried out at room
temperature (20 ± 2 °C) for 4 h under vigorous stirring. Wet
impregnation technique was followed by solvent evaporation.
The dried powders were heated at 550 °C (heating rate of 2 °C/
min) and then calcined at 550 °C for 6 h; the obtained samples
were denoted pUF and pMF, respectively.
2.4. Characterization
The powder X-ray diffraction (XRD) patterns were recorded on a
Shimadzu diffractometer operating at intensity of 40 kV and 30 mA
0
and using Ni-filtered Cu Ka (k = 1.542 ÅA) radiation. The diffracto-
grams were recorded in the 2h range of 1.5–8° and 20–80° with
a 2h step size of 0.02° and a step time of 12 s. Scanning electron
microscopy (SEM) investigations were performed using a Vega Tes-
can electron microscope. Nitrogen adsorption–desorption iso-
therms were recorded on a Quantachrome Nova 2200 Instrument
& Pore Size Surface Area Analyzer at 77 K on samples degassed at
473 K for 2 h under high vacuum. The Brunauer–Emmett–Teller
(BET) specific surface area was calculated from the linear part of
the BET plot. Pore size distribution was calculated using Barrett–
Joyner–Halenda (BJH) method. Magnetic measurements were per-
formed on a vibrating sample magnetometer (VSM) Princeton
Instruments Micromag™ 3600 at room temperature under an ap-
plied field of 10,000 Oe. Contributions of holder and silica matrix
were subtracted from the recorded magnetic data.
2.5. Degradation of methylene blue aqueous solution
An ultrasonic processor SONICS VIBRA Cell™ Model CV 33 with
a 1.13 cm diameter titanium horn operating at 20 kHz was used for
ultrasonic MB degradation experiments. Sonication was applied in
pulsed mode (4 s on/1 s off). During experiments, the temperature
was maintained at 20 ± 2 °C. A specific quantity of magnetic iron
oxide/MCM-41 nanocomposite (0.1 g) was dispersed into 100 mL
of 0.03 mM methylene blue aqueous solution, and the pH value
was fixed to pH 3 using NaOH. The degradation of MB was initiated
by addition of 0.4 mL H2O2 (30% w/w) and immediately turning on
the ultrasonic irradiation. At given time intervals, 5 mL solution
was withdrawn from the reaction medium and immediately cen-
trifuged at 4000 rpm for 15 min to remove the suspended catalyst
particles. The absorbance of the liquid sample was measured at
665 nm (which corresponds to the maximum absorbance of the
MB) with a Shimadzu UV-2401PC Spectrophotometer to determine
the MB concentration. For comparison, the MB degradation exper-
iment was also done without ultrasounds or hydrogen peroxide.
3. Results and discussion
The synthetic methods, description of samples, functionaliza-
tion level, and Fe loading level are presented in Table 1.
Sample description APTES:Sia Fe:Sib
Pure MCM-41 – –
Amino-functionalized MCM-41 0.1:0.9 –
Pure MCM-41 – –
Amino-functionalized MCM-41 0.1:0.9 –
Iron oxides nanoparticles/pU 0.1:0.9 0.02
Iron oxides nanoparticles/pM 0.1:0.9 0.02
186 I. Ursachi et al. / Journal of Colloid and Interface Science 377 (2012) 184–190
3.1. Structural and textural analysis
It is well known that the X-ray diffraction pattern of ordered
mesoporous silica MCM-41 presents a small number of reflections
always located at small angles of diffraction. Typically, only three
diffraction peaks are well resolved and correspond to (1 0 0),
(1 1 0), and (2 0 0) reflections. The fourth diffraction peak is usually
of very low intensity and corresponds to (2 1 0) reflection.
The small-angle XRD results of the pure and amino functional-
ized mesoporous silica samples are shown in Fig. 1.
The pure mesoporous silica sample prepared by conventional
synthesis (Fig. 1a, M sample) exhibits three diffraction peaks corre-
sponding to (1 0 0), (1 1 0), and (2 0 0) reflections assigned to the
hexagonal unit cell. The XRD pattern can be indexed to a highly or-
dered hexagonal lattice typical of MCM-41 (space group p6mm).
The pure mesoporous silica sample obtained by ultrasound-as-
sisted synthesis (Fig. 1b, U sample) exhibits a well resolved diffrac-
tion peak corresponding to (1 0 0) reflection, while diffraction
peaks corresponding to (1 1 0) and (2 0 0) reflections have very
low intensity and could not be resolved. Pinavaia et al. [23] have
demonstrated that such XRD patterns are obtained for samples
with crystallographic structure analogous to MCM-41 material,
which means that the synthesized samples may be considered
material of MCM-41 type.
The XRD patterns of MCM-41 samples functionalized by post-
synthesis treatment show a single diffraction peak corresponding
to (1 0 0) reflection (Fig. 1c, pM sample; Fig. 1d, pU sample). For
both samples, a significant decrease in the intensity of (1 0 0) dif-
fraction peak and the reduction to detection limit of (1 1 0) and
(2 0 0) reflections present in the parent sample was noticed. This
indicates a distortion of the long-range ordering of the mesoporous
structure during functionalization process.
The small-angle XRD results of the pure and amino functional-
ized mesoporous silica showed that the obtained samples by both
methods exhibit ordered hexagonal lattice that is typical for MCM-
41.
The wide-angle XRD and small-angle XRD results of the iron
oxide/MCM-41 nanocomposites (pMF and pUF samples) are shown
in Fig. 2. Presence of diffraction peaks corresponding to (1 0 4),
(1 1 0), (1 1 3), (2 0 2), (0 2 4), (1 1 6), (0 1 8), and (2 1 4) reflections
in wide-angle patterns clearly indicate the formation of hematite
phase (a-Fe2O3) (space group R3c (167), JCPDS No. 72-0469). The
broad peak at around 2h = 22° is assigned to amorphous silica.
The small-angle XRD patterns of impregnated samples (Fig. 2, in-
set) show that the diffraction peaks were shifted toward higher
Fig. 1. Small-angle XRD patterns of pure mesoporous silica and amino function-
alized MCM-41 samples.
values of diffraction angle and (1 0 0) peak intensity decreased. This
result is due to functionalization agent removal by calcination.
Also, the decrease in peak intensity could be attributed to a de-
crease in the electron density contrast between the silica wall
and mesopore due to location of iron oxide particles inside mesop-
ores of silica matrix [24].
Textural properties of prepared samples were determined from
nitrogen adsorption–desorption isotherms. The main structural
and textural characteristics of the prepared samples are presented
in Table 2. Nitrogen adsorption isotherms and corresponding pore
size distribution of M and U samples are shown in Fig. 3. Both iso-
therms are of type IV with a H1-type hysteresis loop [25] which is
characteristic of mesoporous materials. A sharp inflection in the
relative pressure (p/p0) between 0.2 and 0.3 corresponds to capil-
lary condensation inside uniform mesopores. The sharpness of this
step demonstrates the narrow pore size distribution (see Fig. 3B).
For pure MCM-41 prepared by ultrasound-assisted synthesis (sam-
ple U), the position of adsorption–desorption curve is slightly
shifted to lower values of p/p0 indicating decrease in the mesopore
size (see Table 2). The obtained data show that ultrasound-assisted
synthesis favors the formation of mesoporous structures with low-
er values of interplanar spacing, pore diameter, and volume, com-
pared with samples obtained by conventional synthesis.
The N2 sorption results reveal that modification with amino
functional groups leads to a decrease in the porosity of samples
compared with that of the corresponding pure silica samples
(see Table 2). The decrease in textural characteristics is a conse-
quence of the grafting of organic functional groups onto pores
walls of the MCM-41 materials. Nevertheless, although the bind-
ing of amino functional groups induce a certain decrease in silica
porosity, a significant volume of pores still remains unobstructed,
as can be deduced from the textural properties listed in Table 2.
The high specific surface area and average pore diameter of the
iron oxide/MCM-41 nanocomposites indicate that the mesopor-
ous structure is still maintained after loading of iron oxide spe-
cies. Furthermore, the textural characteristics of obtained
nanocomposites suggest that organic phase removal (functionali-
zation agent) by calcination gives rise to an increase in the poros-
ity of the nanocomposite compared with the corresponding
amino functionalized MCM-41 samples. A decrease in the total
pore volume and specific surface area is registered for iron
oxide/MCM-41 samples compared with the pure mesoporous sil-
ica. This result could be attributed to the deposition of iron oxide
nanoparticles into the mesopores of the silica matrix [24].
Fig. 2. Wide-angle XRD and small-angle XRD (inset) patterns of magnetic iron
oxide/MCM-41 nanocomposites: (a) pMF sample and (b) pUF sample.
 I. Ursachi et al. / Journal of Colloid and Interface Science 377 (2012) 184–190 187

Table 2
The main structural and textural characteristics of the prepared samples.

Sample d100a (nm) a0b (nm) Wtc (nm) Dpd (nm) Vpe (cm3/g) SBETf (m2/g)
U 3.38 3.9 1.74 2.16 1.086 1699
M 3.48 4.01 1.77 2.24 1.129 1601
pU 3.41 3.93 2.93 1.00 0.449 232
pM 3.38 3.9 2.92 0.98 0.131 106
pUF 3.39 3.91 1.92 1.99 0.788 1456
pMF 3.49 4.03 2.17 1.86 0.555 1042
a
d-Spacing of (1 0 0) reflection.
b p
Unit cell constant, a0 = (2d100)/ 3.
c
The pore wall thickness estimated from the difference (a0  Dp).
d
Average pore diameter, estimated using the desorption branch of the isotherm and the Barrett–Joyner–Halenda (BJH) method.
e
Total pore volume, taken from the volume of N2 adsorbed at p/p0 = 0.95.
f
BET surface area, calculated from the linear part of the BET plot. See experimental section for designations of samples.

Fig. 3. (A) Nitrogen adsorption–desorption isotherms and (B) pore size distribution of pure mesoporous silica samples.

3.2. Scanning electron microscopy analysis
Representative SEM micrographs of amino functionalized
MCM-41 and magnetic a-Fe2O3/MCM-41 nanocomposites are
shown in Fig. 4. SEM images revealed that all samples clearly pres-
ent spherical morphology that is preserved after functionalization
(Fig. 4a and b) and after impregnation and calcination (Fig. 4c and
d). Particle surface morphology is smooth and does not detect the
odd structures on the surface of all samples.
3.3. Magnetic properties
To investigate the magnetic properties of the synthesized sam-
ples, measurements were carried out in an applied magnetic field
at room temperature. The field dependence of isothermal magneti-
zation for a-Fe2O3/MCM-41 nanocomposite measured at room
temperature is shown in Fig. 5. The magnetization curves recorded
on synthesized samples show weak ferromagnetic behavior. The
measured coercive force (Hc ) and saturation magnetization (M s )
values were less than 39 Oe and 0.35 emu g1, respectively. The
calculated saturation magnetization values (listed in Table 3) are
smaller than that of commercial hematite (0.6 emu/g) [26]. A de-
crease in M s was observed in nanoparticles, and it was attributed
to the surface contribution: spin canting, stoichiometry deviation,
surface disorder and cation distribution [27]. In our case, this phe-
nomenon can be caused by the presence of the mesoporous matrix.
The hysteresis loop of the samples indicates similar types of
magnetic behavior. On the basis of the criteria given by Dunlop
et al. [28], the value of Mr/MS should be larger than 0.5 for sin-
gle-domain (SD) particles, between 0.1 and 0.5 for pseudosingle-
domain (PSD) particles and lower than 0.1 for multidomain (MD)
particles. As seen from Table 3, the iron oxide nanoparticles dis-
persed in MCM-41 show an MD-type behavior (Mr/MS < 0.1).
3.4. Degradation of MB on a-Fe2O3/MCM-41 nanocomposites
Our experiments showed that the MB degradation is insignifi-
cant when only US–H2O2 system was used (see Fig. 6B). Futher-
more, MB degradation experiments in the absence of ultrasounds
using only H2O2–a-Fe2O3/MCM-41 nanocomposite systems
showed that MB adsorption occurs on the surface of catalyst that
changes its color to green (see Fig. 6C). The ultrasonic degradation
of MB was investigated in the US–H2O2–a-Fe2O3/MCM-41 nano-
composite systems at pH 2–5.
The temporal changes in the spectral features of the solutions
were studied by monitoring the absorbance of UV–vis spectra at
665 nm. As shown in Fig. 7A, MB was degraded slowly under ultra-
sonic irradiation when US–H2O2 system was used. The very small
decrease in the absorbance at 665 nm indicates that the ultrasonic
irradiation produce only a weak increase in MB degradation due to
generation of additional HO free radicals by H2O2 decomposition.
In the catalytic systems US–H2O2–pMF and US–H2O2–pUF, it can
be observed a clear decrease in the absorbance at 665 nm
(Fig. 7B and C) and no new peaks were observed after sonocatalytic
degradation. As shown in Fig. 7B and C, ultrasonic irradiation for
30 min caused a significant discoloring of the solution (decrease
in the absorbance at 665 nm) and after 60 min the blue color al-
most disappeared.
The temporal changes in the spectral features of the catalytic
systems US–H2O2–pMF and US–H2O2–pUF are similar. However,
some slight differences can be observed between the two systems
studied. In the case of US–H2O2–pMF catalytic system, after
188 I. Ursachi et al. / Journal of Colloid and Interface Science 377 (2012) 184–190

Fig. 4. SEM images of prepared samples: (a) pM; (b) pU; (c) pMF, and (d) pUF.

Fig. 6. Photographs of MB aqueous solution before (A) and after degradation

experiment using: (B) US–H2O2 system, and (C) H2O2–a-Fe2O3/MCM-41 nanocom-
Fig. 5. Room-temperature magnetization curves of a-Fe2O3/MCM-41 posite system.
nanocomposites.

with US–H2O2–pUF catalytic system. The significant decrease in

Table 3 the absorbance at about 200 nm indicates that the consumption
Magnetic properties of iron oxide/MCM-41 samples.
of H2O2 in the US–H2O2–pMF system is higher than for US–
Sample HC (Oe) Mr (emu/g) MS (emu/g) Mr/MS H2O2–pUF. Also, it can be seen from Fig. 7 that the two major
pMF 19 0.05 0.94 0.05 absorbance peaks of MB became weaker in intensity as the ultra-
pUF 39 0.009 0.35 0.02 sonic irradiation treatment time increased. After 60 min, these
two peaks almost disappeared, indicating that the benzene ring
and heteropolyaromatic linkage of MB were almost destroyed [30].
30 min, one can observe a significant decrease in the absorbance at Experimental results on the degradation of MB were presented
wavelength of about 200 nm (attributed of H2O2 [29]) compared also in the form of a plot of the percentage of degradation of MB
 I. Ursachi et al. / Journal of Colloid and Interface Science 377 (2012) 184–190
Fig. 7. Changes of UV–vis spectra during the degradation of MB in different systems: (A) US–H2O2, (B) US–H2O2–pMF, and (C) US–H2O2–pUF; inset photographs of solution at
the end of the experiment.
Fig. 8. Removal efficiency of MB by using different systems: US–H2O2, US–H2O2–
pMF and US–H2O2–pUF. The initial concentration of MB was 0.03 mM; pH 3; the US
was applied in pulsed mode (4 s on/1 s off); the reaction temperature was 20 ± 2 °C.
versus irradiation time (Fig. 8). In the simple system US–H2O2, the
degradation rate of MB can be considered insignificant. The de-
crease in MB concentration was only 17% of the initial concentra-
tion after 270 min ultrasonic irradiation. The slow degradation of
MB in the US–H2O2 system indicates a very limited ultrasonic deg-
radation rate of MB. In the catalytic systems US–H2O2–pMF and
US–H2O2–pUF, the degradation rate of MB is increased signifi-
cantly. As shown in Fig. 8, the pMF and pUF samples exhibit a high
catalytic activity and removed about 94% and 96%, respectively, of
189
the initial quantity of MB within 60 min. If it is not necessary to re-
move the MB total content from wastewater, then 60 min time
may be considered sufficient. After 270 min, the decrease in MB
concentration was about 99% of the initial concentration value
for both systems. The almost complete degradation of the MB by
the US–H2O2–pMF and US–H2O2–pUF systems suggested that a-
Fe2O3/MCM-41 nanocomposites behaved as a Fenton-like hetero-
geneous catalyst with high catalytic activity.
A Fenton-type catalyst (Fe2+ + H2O2) makes possible the degra-
dation of non-volatile hydrophilic organic dyes molecules via
highly reactive free radicals HO attack. The degradation efficiency
is dependent on the formation rate of these radicals. Our results
suggest that hematite nanoparticles dispersed in mesoporous silica
MCM-41 pores produce an increase in the decomposition rate of
H2O2 with formation of hydroxyl radicals. Furthermore, the exis-
tence of heterogeneous catalyst in the system facilitates the pro-
cess of cavitation. Also, the fast degradation of MB suggests a
strong synergistic effect between the ultrasonic irradiation and
catalytic activity of a-Fe2O3/MCM-41 nanocomposites. Magnetic
a-Fe2O3/MCM-41 nanocomposite used as heterogeneous catalyst
has the advantage of an easy recovery from reaction mixture by
magnetic separation or centrifugation.
3.5. Influence of pH
The sonocatalytic degradation of MB was investigated at differ-
ent values of pH. Fig. 9 shows that the catalytic systems US–H2O2–
pMF and US–H2O2–pUF give rise to different removal efficiency. At
this initial pH value, the catalytic system US–H2O2–pUF exhibits a
lower catalytic activity within 180 min sonication compared with
190 I. Ursachi et al. / Journal of Colloid and Interface Science 377 (2012) 184–190
Fig. 9. Effect of pH value on the removal efficiency of methylene blue: US–H2O2–pMF system (A) and US–H2O2–pUF system (B).
US–H2O2–pMF. However, within 300 min sonication, the degrada-
tion percentage of MB achieved 94% in both cases. When the initial
pH value is adjusted at 3 and 2, respectively, the limiting efficiency
is clearly enhanced and slowly increases with the decreasing pH.
As at pH 2 and 3 the performance of the two studied systems is
rather similar, the MB degradation can be performed at pH 3 for
60–90 min when approximately 95–97% of the initial amount of
MB is removed.
It is known that in homogenous systems pH of 3–4 is the opti-
mal value for Fenton reactions and decreased catalyst efficiency
with increase in the pH value is closely related to the stability of
Fe (at high pH values (pH > 5)) occurs precipitation of ferrous com-
pounds) [18].
Based on the obtained results, it seems that in the heteroge-
neous Fenton ultrasound-assisted MB degradation technique the
used pH values lead to good efficiency of the system. However, de-
tailed studies are needed to determine the optimal pH value where
stability and activity of the catalyst are the highest.
4. Conclusion
Magnetic a-Fe2O3/MCM-41 nanocomposites were stabilized
within the pore system of the MCM-41 mesoporous silica synthe-
sized by conventional and ultrasounds-assisted methods, and this
catalyst was tested toward the MB degradation by coupling ultra-
sounds with Fenton-like process at room temperature.
It was found that the obtained a-Fe2O3/MCM-41 nanocompos-
ites exhibit high activity in the degradation of MB by coupling
ultrasound with Fenton-like processes. Ultrasonic irradiation of
a-Fe2O3 stabilized inside channel of the MCM-41 may promote
very reactive hydroxyl radicals formation that initiate a series of
chemical reactions that promote the degradation of MB. Magnetic
a-Fe2O3/MCM-41 nanocomposites obtained by ultrasound-as-
sisted synthesis showed catalytic activity similar to that of the
nanocomposites synthesized by conventional method but the first
are synthesized in a very short time, which could be favorable in
practical applications. Magnetic a-Fe2O3/MCM-41 nanocomposite
catalysts have the advantage of an easy catalyst recovery of the
material by magnetic separation or centrifugation.
The results have indicated that MB could be degraded at room
temperature faster by coupling ultrasonic irradiation with a Fen-
ton-like process using a heterogeneous catalyst based on a-
Fe2O3/MCM-41 nanocomposites.
Acknowledgments
This work was financially supported by Romanian CNCS-UEFI-
SCDI project IDEI-EXOTIC No. 185/25.10.2011.
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