Environmental Science and Pollution Research

https://doi.org/10.1007/s11356-018-1586-1

NEW CHALLENGES IN THE APPLICATION OF ADVANCED OXIDATION PROCESSES

TiO2-based (Fe3O4, SiO2, reduced graphene oxide) magnetically

recoverable photocatalysts for imazalil degradation in a synthetic
wastewater
Dunia E. Santiago 1,2 & Luisa M. Pastrana-Martínez 3 & Elisenda Pulido-Melián 1 & Javier Araña 1 & Joaquim L. Faria 4 &
Adrián M. T. Silva 4 & Óscar González-Díaz 1 & José M. Doña-Rodríguez 1

Received: 1 November 2017 / Accepted: 16 February 2018

# Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
Magnetite (Fe3O4), a core-shell material (SiO2@Fe3O4), and reduced graphene oxide-Fe3O4 (referred as rGO-MN)
were used as supports of a specific highly active TiO2 photocatalyst. Thermal treatments at 200 or 450 °C, different
atmospheres (air or N2), and TiO2:support weight ratios (1.0, 1.5, or 2.0) were investigated. X-ray diffractograms
revealed that magnetite is not oxidized to hematite when the core-shell SiO2@Fe3O4 material—or a N2 atmosphere
(instead of air) in the thermal treatment—was employed to prepare the TiO2-based catalysts (the magnetic properties
being preserved). The materials treated with N2 were first tested for degradation of imazalil (a well-known fungicide)
in deionized water. The best compromise between the photocatalytic activity, magnetic separation, and Fe leached
(1.61 mg L−1, i.e., below the threshold for water reuse in irrigation) was found for the magnetic catalyst prepared with
SiO2@Fe3O4, an intermediate TiO2:support ratio (1.5), and treated at 200 °C under N2 atmosphere (i.e., SiO2@Fe3O4-
EST-1.5-200-N2). This material was then tested for the treatment of imazalil in a synthetic wastewater, SW (with a
chemical composition simulating an effluent resulting from fruit postharvest activity). This SW has a pH of 4.2 and
the experiments were carried out at this natural pH0 and at neutral conditions (keeping pH at 7 along the reaction).
The magnetic catalyst was more active than bare TiO2 for the treatment of imazalil in SW at natural pH. Since Fe
leaching was observed (3.53 mg L −1 ), added H 2 O 2 enhanced both imazalil degradation and mineralization.
Conveniently, these catalysts can be readily recovered by using a conventional magnetic field, as demonstrated over
three consecutive recycling runs.

Keywords Imazalil . Photocatalysis . TiO2 . Magnetic . Fe3O4 . SiO2

Responsible editor: Suresh Pillai

Electronic supplementary material The online version of this article
(https://doi.org/10.1007/s11356-018-1586-1) contains supplementary
material, which is available to authorized users.

* Dunia E. Santiago 2
Dpto. de Ingeniería de Procesos, Universidad de Las Palmas De Gran
dsantiago@proyinves.ulpgc.es Canaria, Campus Universitario de Tafira, 35017 Las Palmas, Spain
* José M. Doña-Rodríguez 3
Carbon Materials Research Group, Department of Inorganic
jose.dona@ulpgc.es Chemistry, Faculty of Sciences, University of Granada, Campus
Fuentenueva s/n, 18071 Granada, Spain
1
Grupo FEAM, Unidad Asociada al CSIC (a través del ICCMM de 4
Laboratory of Separation and Reaction Engineering—Laboratory of
Sevilla), i-UNAT - Universidad de Las Palmas de Gran Canaria, Catalysis and Materials (LSRE-LCM), Faculdade de Engenharia,
Edificio del Parque Científico Tecnológico de la ULPGC, 35017 Las Universidade do Porto, Rua Dr. Roberto Frias,
Palmas, Spain 4200-465 Porto, Portugal

Introduction
Advanced oxidation processes (AOPs) are conceptually based
on the degradation of organic pollutants by the formation of
hydroxyl radicals. Among them, the classical Fenton process
implements hydrogen peroxide (H2O2) and Fe2+/Fe3+ as cat-
alyst. Alternatively, materials based on metal oxides, such as
magnetite (Fe3O4), maghemite (γ-Fe2O3), and hematite (α-
Fe2O3), have been used (in this case known as heterogeneous
Fenton-like process) (Panda et al. 2011; Sun and Lemley
2011; Xia et al. 2011; Xu and Wang 2012; Rusevova et al.
2012; Ferroudj et al. 2013; Pastrana-Martínez et al. 2014).
These materials have been also investigated in photo-
assisted routes (e.g., photo-Fenton process) due to their low
bandgap energies (≈ 2.1–2.3 eV) (Cunningham et al. 1988;
Bandara et al. 2001, 2007; Du et al. 2008; Mahmoud et al.
2012; Wei et al. 2014; Pastrana-Martínez et al. 2014).
Nevertheless, the respective photogenerated charge carriers
have short diffusion lengths, favoring charge recombination
and hindering the formation of surface radical species
(Bandara et al. 1999; Kay et al. 2006). Moreover, when none
or very low amounts of Fe2+/Fe3+ are leached to the liquid
phase, the mineralization of the organic pollutants have been
found negligible (Zeng et al. 2011; Ferroudj et al. 2013). Thus,
in general, these Fe-containing materials have low quantum
efficiencies and catalytic activity when compared to TiO2-
based photocatalysts, but they can be useful as magnetic sup-
ports (Recillas et al. 2011; Zhang et al. 2013; Palanisamy et al.
2013; Lucas et al. 2013). The magnetic property allows the
effective separation of the suspended catalyst particles from
the treated water/wastewater, avoiding more complicated sep-
aration steps.
Among the catalysts already tested, TiO2/SiO2@Fe3O4
(or Fe3O4/SiO2/TiO2) photocatalysts have been reported
for degradation of Rhodamine B (Liu et al. 2011; Yuan
et al. 2012; Ma et al. 2015), methylene blue (Absalan and
Nikazar 2016), Reactive Black 5 (Lucas et al. 2013),
benzoic acid, tartrazine, and Sunset Yellow (Habila et al.
2016). α-Fe2O3 has been also combined with graphene
derivatives, such as reduced graphene oxide (rGO), for
phenol degradation (Pradhan et al. 2013) and water oxi-
dation (Meng et al. 2013), the enhancement in the photo-
catalytic activity being ascribed to the suppressed charge
recombination since the photogenerated electrons migrate
from α-Fe 2 O 3 to rGO. Composites combining TiO 2 ,
Fe3O4 and rGO have been also prepared and mostly tested
for the photocatalytic degradation of organic dyes, such as
methylene blue (Li et al. 2015) and Rhodamine B (Cheng
et al. 2016), under both UV and visible light irradiation.
However, most of the studies do not provide mineraliza-
tion results and have been performed with distilled water
rather than investigating the matrix effect, which has a
Environ Sci Pollut Res
significant influence on the performance of these treat-
ment options. This is particularly the case for heteroge-
neous photocatalysis where the interaction of inorganic
matter present in natural water has shown to be a limiting
factor in the overall photocatalytic process (Santiago et al.
2014).
In the present study, three magnetic materials, namely
magnetite (Fe3O4) as well as the respective core-shell mag-
netic silica (SiO2@Fe3O4) and rGO- Fe3O4 (rGO-MN),
were used as supports to prepare multi-component cata-
lysts using a specific TiO2 material (EST-1023t) that was
developed and optimized in our previous publications
(Santiago et al. 2013, 2014). We have demonstrated that
this bare TiO2 material has very high photocatalytic activ-
ity for degradation of several organic pollutants, including
imazalil (surpassing the benchmark photocatalyst for this
application, Evonik Degussa TiO2 P25). The target in the
present report is to combine, for the first time, this TiO2
material with magnetite (Fe 3 O 4 ) in order to obtain a
photocatalyst with magnetic properties, also exploring the
respective core-shell magnetic silica (SiO2@Fe3O4) in the
way to increase the catalyst stability. The graphene deriv-
ative (rGO) was also selected to prepare the catalysts be-
cause it can enhance the photoefficiency of different semi-
conductors (such as TiO2) under UV and visible light con-
ditions (Pastrana-Martínez et al. 2012; Morales-Torres
et al. 2012), in the present work prepared with magnetic
properties.
The photocatalytic performance of the prepared
photocatalysts was investigated for both degradation and
mineralization of imazalil (a widely used fungicide) in two
different aqueous matrices: deionized water (DW) for cat-
alyst screening experiments and a synthetic wastewater
(SW) resembling the typical chemical characteristics of a
wastewater that is obtained from postharvest handling in
agriculture. Some specific experiments were also per-
formed by adding H 2 O 2 (i.e., mimicking the photo-
Fenton process).
Experimental
Chemicals and synthetic wastewater
Iron(III) chloride hexahydrate (FeCl3·6H2O, > 99.0%), iron
(II) chloride tetrahydrate (FeCl2·4H2O, > 99.0%), hydrogen
peroxide (H2O2, 30 wt.%), iron(II) sulfate heptahydrate
(FeSO 4·7H 2O, > 99.5%), ammonia solution (25 wt.%),
cetrimonium bromide (CTAB, > 99.0%), tetraethyl
ortosilicate (TEOS, > 99%), and ethanol (96.%) were supplied
by Panreac. Hydrazine hydrate (NH2NH2·H2O, 50–60 wt.%)
Environ Sci Pollut Res
was purchased from Sigma-Aldrich. These reagents were used
in the synthesis of the magnetic materials.
Sodium chloride (NaCl), aluminum sulphate
(Al2(SO4)3·18H2O), and calcium hydroxide (Ca(OH)2),
purchased from Panreac (PRS purity), were used to pre-
pare the synthetic wastewater (SW) with 100 mg L−1 of
chloride, 300 mg L−1 of sulphate, and 20 mg L−1 of calci-
um, respectively. This SW (as well as DW) was spiked
with 50 mg L−1 of imazalil (commercial Fruitgard-IS-
7.5). Imazalil concentration and SW composition were
chosen according to mean concentrations found in waste-
water samples collected from banana postharvest facilities
in Gran Canaria, as previously reported (Santiago et al.
2014). The pH of the aqueous solutions was adjusted using
diluted sulfuric acid (H 2 SO 4 ) and sodium hydroxide
(NaOH) solutions.
Synthesis of the nanostructured materials
Synthesis of magnetic supports
Fe3O4 was synthesized by a method adapted from elsewhere
(Massart 1981). Briefly, 40 mL of 1 M FeCl3 solution and
10 mL of 2 M FeCl2 solution (prepared in 2 M HCl) were
added to 500 mL of 0.7 M NH3 solution. The resulting pre-
cipitate was magnetically extracted, washed with ethanol sev-
eral times, dried at 60 °C over 12 h under vacuum, grinded,
and sieved (100 μm).
Core-shell SiO2@Fe3O4 nanoparticles were obtained by
the modified Stöber method, a SiO2 coating being formed
around the Fe3O4 nanoparticles (Liu et al. 2014). In this
case, 0.4 g of Fe3O4 was dispersed in a solution containing
40 mL of water, 320 mL of ethanol, 18 mL of NH3 (25%
p/v), and 7 mM of CTAB. The mixture was sonicated
(Ultrasons-HD Selecta, 40 kHz) for 10 min, then 25 mL
of a 0.01% v/v TEOS:ethanol solution was slowly added
and the mixture kept under sonication for 30 min. The
product (SiO2-coated Fe3O4 nanoparticles) was then cen-
trifuged, washed three times with DW, and then dried at
60 °C over 12 h under vacuum. The material was calcined
at 450 °C in air during 3 h (4 °C min−1) in order to elim-
inate the CTAB traces. The powder was grinded and sieved
(100 μm).
Graphene oxide (GO) was prepared by oxidation of syn-
thetic graphite through an adapted modified Hummers
method (Hummers and Offeman 1958; Rivera-Utrilla
et al. 2001) which involves strongly oxidizing species such
as KMnO4 in acidic medium (H2SO4) and exfoliation un-
der sonication. The magnetic rGO material (rGO-MN) was
obtained in a single step, following a procedure described
elsewhere (Su et al. 2011). Briefly, 50 mL of a GO suspen-
sion was mixed with FeCl3·6H2O (1 mmol) and ascorbic
acid (3 mmol), and sonicated in an ultrasound bath
(UP400S, 24 kHz) for 15 min. Then, 10 mL of hydrazine
was added to the dispersion and the mixture was placed in
an autoclave heated at 180 °C for 8 h. The product was
filtered (0.45 μm) and washed three times using DW and
ethanol. The material was then left to dry in air and
grinded.
The three materials referred above (Fe3O4, SiO2@Fe3O4,
and rGO-MN) were then used to prepare the magnetic TiO2-
based catalysts.
Synthesis of TiO2 and magnetic TiO2-based catalysts
The TiO2 sample (EST-1023t) was synthesized by a sol-gel
method involving titanium butoxide and ethanol, as described
in our previous reports (Santiago et al. 2013, 2014). Briefly, a
solution containing 17 mL of titanium butoxide and 40 mL of
ethanol was added dropwise (over 2 h) into 15 mL of a 0.6 M
H2SO4 solution (in ethanol). The mixture was then stirred for
30 min and aged for 48 h. The resulting material was dried at
100 °C for 24 h and sieved (63 μm mesh) before treatment at
750 °C (0.5 °C min−1) for 3.5 h.
To prepare the magnetic TiO2-based catalysts, different
TiO2:support weight ratios (1.0, 1.5, or 2.0) were used consid-
ering a total of 2 g L−1 of catalyst. In each case, the materials
(i.e., TiO2 and respective supports) were suspended in 1:1 (v/
v) ethanol:water under strong stirring at room temperature
during 30 min, and then sonicated (UP400S, 24 kHz) for
1 h. The resulting powder was filtered (0.45 μm), washed
several times with DW, and dried under vacuum at 60 °C over
12 h. The dried product was grinded and sieved (100 μm) and
then subjected to thermal treatment at either 200 or 450 °C
during 2 h (10 °C min−1) under air or inert (N2) atmosphere.
The catalysts are labeled as x-EST-z-T-w, where x refers to
the magnetic support (Fe3O4, SiO2@Fe3O4 or rGO-MN), EST
to the TiO2 catalyst (EST-1023t), z to the TiO2:magnetic sup-
port ratio (1.0, 1.5, or 2.0), T to the treatment temperature (200
or 450 °C), and w to the employed atmosphere (air or N2).
Experimental conditions
Adsorption experiments
Adsorption-desorption equilibrium experiments were per-
formed with 200 mg of catalyst in 200 mL of a 50 mg L−1
imazalil solution. This solution was stirred and kept at 25 ±
1 °C, using a Heto 21 DT-1 thermostat. One-milliliter samples
were taken at regular intervals to determine the imazalil con-
centration until the adsorption-desorption equilibrium was
reached. The last sample was taken after 24 h.

Experiments with deionized water
The screening of magnetic TiO2-based catalysts was first con-
ducted using a quartz cylindrical photoreactor containing
7.5 mL of 50 mg L−1 imazalil solution in deionized water
(DW). This configuration was used for the screening of cata-
lysts in order to spend a lower amount of each sample. The
experimental set-up is described elsewhere (Pastrana-
Martínez et al. 2012). These photocatalytic experiments were
performed using a Heraeus TQ 150 medium-pressure mercu-
ry-vapor lamp, with an irradiance of 33 mW cm−2 (at 4 cm
away from the photoreactor). A DURAN® glass cooling jack-
et with water recirculation was employed in order to operate in
the near-UV/Vis region (λ > 350 nm). The lamps were turned
on when the adsorption-desorption equilibrium was
established (i.e., after 30 min in dark).
Experiments with synthetic wastewater
In this set of experiments, 200 mL of synthetic wastewater
(SW) was treated in a 250 mL Pyrex glass batch reactor, using
1 g L−1 of bare TiO2 or 2 g L−1 of the magnetic TiO2-based
catalyst presenting the best performance in the catalyst screen-
ing experiments—a ratio TiO2:support equal to 1 corresponds
to 1 g L−1 of TiO2 in 2 g L−1 of catalyst, i.e., the load of TiO2
was always the same. Aeration was maintained using an
aquarium pump (EOLO AC3000 model: 2 L min−1) and con-
stant stirring at 450 rpm. A 60 W Philips Solarium HB175
lamp, equipped with four 15 W Philips CLEO fluorescent
tubes, was used as UV light source (broad emission spectrum
300–400 nm, with maximum at ~ 365 nm; 9 mW cm−2 of
average irradiation). Some experiments were performed by
adding H2O2. In all the performed experiments (with DW or
SW), the lamp was turned on after establishing the adsorption-
desorption equilibrium (i.e., after 30 min in dark). Aliquots
were taken to monitor the reaction and filtered using 0.45 μm
syringe filters before analysis.
Recovery of the magnetic TiO2-based catalysts
The magnetic TiO2-based samples were recovered using a
conventional magnet. The separation of the powders was de-
fined as appropriate as long as the turbidity of the solution was
similar to that determined for pure DW (i.e., around 0.8 NTU).
Analytical techniques
The concentration of imazalil was monitored by high-
performance liquid chromatography (HPLC), using a UV de-
tector (λ = 225 nm), a Supelco Discovery® C18 column
(25 cm × 4.6 mm ID, 5 μm particles) and an acetonitrile-
10 mM KH2PO4 solution (45:55) with 100 mg L−1 of sodium
1-octanesulfonate as mobile phase (adjusted to pH 3.0 with
Environ Sci Pollut Res
phosphoric acid). The detection and quantification limits for
imazalil were 0.05 and 0.15 mg L−1, respectively. The total
organic carbon (TOC) content was determined using a TOC
Shimadzu-L apparatus. A Heλios UV-Vis spectrophotometer
(Thermo Electron Corporation) was employed to determine
the H2O2 concentration. The method consists in the detection
of a yellow titanium (IV)-peroxide complex at 400 nm (Sellers
1980). The detection and quantification limits for H2O2 were
0.32 and 3.50 mg L−1, respectively. The total iron concentration
was estimated using the o-phenantroline colorimetric method,
following the standard method (ISO 6332:1988). Formation of
the corresponding orange Fe(II) complex was monitored via
UV-Vis spectroscopy at 510 nm. The detection and quantifica-
tion limits were 0.31 and 1.05 mg L−1, respectively.
Scanning electron microscopy (SEM) was performed using
a FEI Quanta 400FEG ESEM/EDAX Genesis X4M instru-
ment, equipped with energy dispersive X-ray spectroscopy
(EDS). A FTIR Thermo Scientific Nicolet iS10 instrument
was used in infrared spectroscopy studies (4000–400 cm−1).
Diffuse reflectance spectra were recorded for all samples on a
Varian Cary 5E spectrophotometer with integrating sphere and
the Kubelka–Munk function (F[R∞]) was applied to estimate
their corresponding band-gap energies. X-ray diffraction
(XRD) studies were carried out using a Siemens D-500 dif-
fractometer (Cu Kα, λ = 1.5432 Å). Crystallite sizes in the
different phases were estimated from the line broadening of
the corresponding XRD peaks by using the Scherrer equation.
BET-specific surface areas (SBET) were determined from N2
adsorption isotherms obtained at − 196 °C in a Quantachrome
NOVA 4200e apparatus. Thermogravimetric (TG) analysis of
materials containing rGO were performed by treating the sam-
ple in air from 50 to 900 °C (20 °C min−1) using a STA 490
PC/4/H Luxx Netzsch thermal analyzer. In addition, point of
zero charge (pHPZC) measurements were performed by pH
equilibrium employing 150 mg of the photocatalytic material
dispersed in 50 mL of a 0.01 M NaCl solution. The pH was
adjusted between 2 and 12 using 0.1 M HCl and 0.1 M NaOH
solutions (Rivera-Utrilla et al. 2001).
Results and discussion
Catalyst characterization
The as-synthesized magnetic TiO2-based materials were
brown, as inferred from a red-shift of the optical absorption
in comparison to pure TiO2 (not shown) (Lucas et al. 2013).
The bandgap energies estimated from Kubelka-Munk analysis
ranged between 2.80 and 2.96 eV, following the general trend:
EST > Fe3O4-EST > rGO-MN-EST > SiO2@Fe3O4-EST (see
Fig. S1). Their specific surface areas (SBET) were quite similar
(ca. 15 m2 g−1). The pHPZC were slightly lower for the mag-
netic TiO2-based materials (pHPZC ≈ 5.6–6.2), compared to
Environ Sci Pollut Res

bare TiO2 (EST, pHPZC ≈ 6.2), indicating that the surface of of water (Al-Abadleh and Grassian 2002) and the narrow band
the magnetic materials is slightly more acidic than that of bare at 1640 cm−1 was attributed to H–O–H bending mode (ν2).
TiO2. The plots for the pHPZC of TiO2 (EST) (a), magnetic The relative intensities between these bands changed depend-
SiO2@Fe3O4 (b), and SiO2@Fe3O4-EST (c) are shown in Fig. ing on the temperature used in the synthesis. The thermal
S2. Representative SEM micrographs of Fe3O4-EST-1-200, treatment induced agglomeration of the powders and this
SiO2@Fe3O4-EST-1-200, and rGO-MN-EST-1-200 treated could be evidenced by a decrease in the intensity of the band
under N2 atmosphere are shown in Fig. 1a–c, respectively
(higher magnifications shown in insets). Aggregated TiO2 par-
ticles can be observed. In the case of rGO-MN-EST-1-200,
some unusual uncovered platelets of the carbon material can
be also observed (Fig. 1c inset). TG analysis (Fig. S3) re-
vealed 18% of carbon content in the rGO-MN-EST material.
FTIR spectra of the magnetic TiO2-based catalysts treated
at 200 and 450 °C under N2 atmosphere are shown in Fig. 2.
The broad vibrational band between 3650 and 3000 cm−1 in-
cludes asymmetric (ν3) and symmetric (ν1) stretching modes

Fig. 1 SEM images of the magnetic catalysts: a rGO-MN-EST-1-200, b

Fe3O4-EST-1-200 y, and c SiO2@Fe3O4-EST-1-200, annealed at 200 °C Fig. 2 FTIR spectra of a Fe3O4/TiO2, b SiO2@Fe3O4/TiO2, and c rGO-
under N2 atmosphere MN/TiO2 annealed at 200 and 450 °C under N2 atmosphere
 Environ Sci Pollut Res

at 3650–3000 cm−1 in Fig. 2a, b, which suggests a relatively
low concentration of adsorbed water molecules on the catalyst
surface (Santiago et al. 2015). By close inspection of Fig. 2a,
i.e., in the spectrum of Fe3O4-EST-1-450, it cannot be con-
cluded that sulphate ions are chemisorbed onto the catalyst, at
least in a significant concentration (characteristic band at
1100 cm−1), but an intense band at 1383 cm−1 is observed.
The band at 1383 cm−1 has been attributed to nitrate (NO3−)
species adsorbed on the catalyst surface (Stählin and Oswald
1971; Yang and Finlayson-Pitts 2001), and it was significantly
weaker for the other two materials (Fig. 2b, c). Furthermore, in
Fig. 2b, an additional broad band is observed at ~ 1100 cm−1,
which was assigned to the characteristic Si–O–Si stretching
mode of SiO2 (Miaomiao et al. 2010).
The XRD patterns of magnetic TiO2-based catalysts are
shown in Fig. 3a, b (Fe3O4-EST), Fig. 3c, d (SiO2@Fe3O4-

Fig. 3 XRD patterns of magnetic catalysts annealed at 450 °C under either air or N2 atmosphere, as indicated. Legend: black circle anatase, ◯ white
circle rutile, I hematite (α-Fe2O3), black square magnetite (Fe3O4), X maghemite (γ-Fe2O3)
Environ Sci Pollut Res
EST), and Fig. 3e, f (rGO-MN-EST) for samples treated at
450 °C under air (Fig. 3a, c, e) or N2 (Fig. 3b, d, e) atmo-
sphere. XRD analysis revealed similar peak ratios of anatase
(70–80%) and rutile (20–30%) TiO2 polymorphs in all sam-
ples. Magnetite (Fe3O4), maghemite (γ-Fe2O3), and hematite
(α-Fe2O3) can be detected in the samples treated at 450 °C.
No crystalline Fe-containing phases other than magnetite
(Fe3O4) were observed in the catalysts treated at 200 °C (not
shown). Several studies have reported the significant influ-
ence of the treatment temperature on the phase transforma-
tions taking place in Fe-Ti-O materials. The formation of γ-
Fe2O3 may result from oxidation of magnetite according to
Eq. 1 (Laurent et al. 2008). This process can take place at
ambient temperature (Haneda and Morrish 1977), although
the optimum formation temperature of γ-Fe2O3 is within
375–400 °C (Lepp 1957). Likewise, α-Fe2O3 may be formed
from oxidation of γ-Fe2O3 or Fe3O4 at 375–550 or 550–
575 °C, respectively (Eqs. 2–3) (Lepp 1957). Finally, Fe3O4
can also be transformed into γ-Fe2O3 under acidic conditions,
according to Eq. 4.
1 screened with 50 mg L−1 of imazalil aqueous solution (natural
2 Fe3 O4 þ O2 → 3 Fe2 O3ðγ Þ
2 pH0 3.8), as described in the BExperiments with deionized
Fe2 O3ðγÞ → Fe2 O3ðαÞ
4 Fe3 O4 þ O2 → 6 Fe2 O3ðαÞ
Fe3 O4 þ 2Hþ →Fe2 O3ðγ Þ þ Fe2þ þ H2 O
XRD data indicate that calcination of Fe3O4-EST samples
at 450 °C in air (Fig. 3a) instead of N2 (Fig. 3b) resulted in
complete oxidation of magnetite (Fe3O4) to hematite (α-
Fe2O3) for the Fe3O4-EST sample, where both TiO2 and
Fe3O4 are in direct contact. On the other hand, oxidation into
hematite was only partial for rGO-MN-EST (Fig. 3e) and it
did not take place for SiO2@Fe3O4-EST (Fig. 3c). This sug-
gests that rGO and SiO2 acted as barrier layers, hindering the
oxidation of Fe3O4. The formation of hematite involved a
color change as well as the loss of magnetic properties of the
Table 1 Fraction of magnetic
crystalline phases present in the Catalyst
magnetic catalysts
EST-1023t
rGO-MN-EST-1-450-air
Fe3O4-EST-1-450-air
SiO2@Fe3O4-EST-1-450-air
rGO-MN-EST-1-450-N2
Fe3O4-EST-1-450-N2
SiO2@Fe3O4-EST-1-450-N2
SiO2@Fe3O4-EST-1-200-N2
a
The magnetic support contains around 18–20% rGO (experimental value)
b
The magnetic support contains around 14% SiO2 (theoretical value)
material, in agreement with other reports (Cornell and
Schwertmann 2003). Table 1 summarizes the fractions of
magnetic crystalline phases estimated for the magnetic cata-
lysts, assuming that 50% of the catalyst is a magnetic material
(1:1 ratio). Thus, thermal treatment in N2 prevents the forma-
tion of hematite and the presence of SiO2 or rGO additionally
prevents the formation of maghemite under such inert atmo-
sphere, the Fe-containing phase being assigned to magnetite.
Moreover, the crystallite sizes of the magnetic phases, namely
magnetite and maghemite, ranged between 10 and 20 nm, as
roughly estimated from Scherrer analysis. It has been sug-
gested that the magnetic force of these materials increases
with the crystallite size (Mascolo et al. 2013), although this
seems to be the case only up to 10 nm, the limiting crystallite
size for magnetic saturation (Smolensky et al. 2013). Since
hematite was detected in some samples treated in air, those
treated with N2 were selected for catalytic studies.
Photocatalytic activity in deionized water
The photocatalytic activity of the magnetic catalysts was
ð1Þ
ð2Þ water^ section. The materials studied in these experiments
were those treated under N2 atmosphere at 200 °C (Fig. 4a)
ð3Þ and 450 °C (Fig. 4b), since the thermal treatment in air affect-
ð4Þ ed their magnetic properties, as explained before. The first set
of catalysts used in these experiments contained a 1:1 ratio of
TiO2:support. The catalyst load in these tests was 2 g L−1 (i.e.,
1 g L−1 of TiO2 content in the aqueous solution). Table 2
shows the concentration of imazalil adsorbed (Qe, mgIMZ
g cat −1 ) on the catalyst surface (equilibrium—i.e., after
30 min in dark). The material prepared with rGO and treated
at 200 °C was the only one presenting a high adsorption of
imazalil during the dark period (19.01 mgIMZ gcat−1). The
adsorption of imazalil was much lower (4.72 mgIMZ gcat−1)
when the same material was treated at 450 °C, maybe because
some of the few uncoated platelets of the carbon material are
not stable at the higher temperature.
% Magnetite % Maghemite % Hematite
– – –
48–49a – 32–33a
– – 100
86b – –
80–82a – –
83.5 16.5 –
86b – –
86b –
 Environ Sci Pollut Res

Fig. 4 Photocatalytic degradation

of imazalil in the presence of
magnetic catalysts annealed at
200 °C (left) or 450 °C (right)
under N2 atmosphere. The
activity of pure TiO2 (EST-1023t)
has been included as reference

The highest photocatalytic activity for degradation of
imazalil was obtained with bare TiO 2 (EST-1023t).
However, this photocatalyst is not magnetic. Regarding
the magnetic TiO2-based catalysts, a modest photocatalytic
activity was observed for the materials treated at 450 °C
(Fig. 4b), in comparison to those treated at 200 °C (Fig.
4a). This can be attributed to the poisoning of the catalyst
surface by adsorbed nitrate species in the case of Fe3O4-
EST-1 treated at 450 °C, as discussed above in the interpre-
tation of FTIR data. Moreover, in the case of rGO-MN-EST-
1-450, the treatment at the higher temperature can affect the
stability of rGO that is expected to be stable at 200 °C
(Pastrana-Martínez et al. 2012), possibly explaining why
the higher adsorption of imazalil was only observed for
the material treated at 200 °C (Table 2), as discussed before.
In any case, the best performing magnetic TiO2-based ma-
terial was the core-shell SiO2@Fe3O4-EST catalyst, in par-
ticular that treated at 200 °C. Its photocatalytic performance
is quite similar to that obtained with bare TiO2 and having as
benefit that can be magnetically separated from treated wa-
ter. The comparatively high efficiency of SiO2@Fe3O4-
EST-1 was attributed to the presence of SiO2, acting as a
barrier layer between TiO2 and Fe3O4. It has been suggested
that Fe3O4 may act as a charge recombination center and,
thus, hamper the overall photocatalytic process (Beydoun
Table 2 Concentrations of imazalil adsorbed (over catalyst mass) on
the catalyst surface (equilibrium) and iron leaching after the
photocatalytic process
Catalyst Qe (mgIMZ·gcat−1) FeT leaching (mg L−1)
EST-1023t 1.47 – (SiO2@Fe3O4-EST-1.5-200-N2) was used in the experiments
rGO-MN-EST-1-200 19.01 0.52
Fe3O4-EST-1-200 3.92 5.01
SiO2@Fe3O4-EST-1-200 4.50 3.09
rGO-MN-EST-1-450 4.72 0.25
Fe3O4-EST-1-450 4.50 3.11
SiO2@Fe3O4-EST-1-450 4.69 2.01
et al. 2000). The presence of SiO2 would avoid the flow of
photogenerated charge pairs toward the magnetic core
(Chen et al. 2001).
Regarding the iron leached to the solution at the end of the
photocatalytic process (Table 2), the magnetic TiO2-based cat-
alysts Fe3O4-EST-1-200-N2 and Fe3O4-EST-1-450-N2 lead to
higher concentrations of iron (5.01 and 3.11 mg L−1, respec-
tively), as expected, followed by the samples prepared with
SiO2@Fe3O4 (3.09 and 2.01 mg L−1 for SiO2@Fe3O4-EST-1-
200-N2 and SiO2@Fe3O4-EST-1-450-N2, respectively) and
finally, by the samples prepared with the rGO-MN support
(i.e., 0.52 and 0.25 mg L−1 for rGO-MN-EST-1-200-N2 and
rGO-MN-EST-1-450-N2, respectively). Taking into consider-
ation these results and that magnetic samples prepared with
SiO2@Fe3O4 showed the best photocatalytic activity (Fig. 4),
an optimization approach was considered using the magnetic
SiO2@Fe3O4 support treated at 200 °C under N2 atmosphere
(SiO2@Fe3O4-EST-x-200). Photocatalysts with different
TiO2:support ratios (SiO2@Fe3O4-EST-1-200, SiO2@Fe3O4-
EST-1.5-200, and SiO2@Fe3O4-EST-2-200) were tested un-
der the same conditions described above (50 mg L−1 of
imazalil solution in deionized water DW, pH 3.8, and catalyst
load of 2 g L−1).
As shown in Fig. 5, the activity of these catalysts seems to
slightly increase with the TiO2 loading in the composite,
reaching and overpassing the imazalil removal obtained with
bare TiO2 after 60 min. However, it was also observed that the
use of the highest TiO2 load (SiO2@Fe3O4-EST-2-200-N2)
resulted in free TiO2 that cannot be magnetically recovered
from the solution, as indicated by an increase in turbidity (22
NTU) compared to that of the original solution (0.8 NTU). For
this reason, the material with intermediate TiO2:support ratio
with the synthetic wastewater (BPhotocatalytic activity with
synthetic wastewater^ section). Moreover, the Fe leached with
SiO2@Fe3O4-EST-1.5-200-N2 after 60 min of photocatalytic
treatment was lower (1.61 mg L−1) than that observed for the
equivalent 1:1 system (3.09 mg L−1). It should be noted that the
maximum dissolved iron concentrations allowed for water re-
use for irrigation or for the disposal of wastewaters are 2 or
Environ Sci Pollut Res
Fig. 5 Photocatalytic degradation of imazalil using a range of
SiO2@Fe3O4:TiO2 ratios: 1:1, 1:1.5, and 1:2, labeled as SiO2@Fe3O4-
EST-1-200, SiO2@Fe3O4-EST-1.5-200, and SiO2@Fe3O4-EST-2-200,
respectively, in the figure. The activity of pure TiO2 (EST-1023t) has
been included as reference
10 mg L−1, respectively (data from the Canary Islands and
Spanish legislation).
Photocatalytic activity with synthetic wastewater
Considering the results obtained in the previous experiments,
the photocatalytic activity of the optimized SiO2@Fe3O4-
EST-1.5-200-N2 sample was studied in the treatment of
imazalil in a synthetic solution simulating the typical fruit
postharvest wastewater from agriculture. These experiments
followed the procedure described in the BExperiments with
synthetic wastewater^ section and they were carried out under
different pH conditions. The pHPZC of the bare TiO2 and core-
shell SiO2@Fe3O4-EST-1.5-200 materials were 6.2 and 5.6,
Fig. 6 (Left) Photocatalytic
degradation of imazalil in
simulated wastewater (SW) under
different pH conditions and
(right) corresponding
mineralization rates after
illumination during 120 min
respectively. The experiments were performed at natural pH,
pH0 = 4.2 (pH of the as-prepared SW) and also at neutral pH
conditions (pH = 7.0). Under neutral conditions, the pH was
continuously monitored and adjusted (within ± 0.5) whenever
required, using either H2SO4 or NaOH, in order to avoid its
decrease during the experiment.
Figure 6a, b shows the photocatalytic degradation of imazalil
and the corresponding mineralization rate (i.e., TOC reduction),
respectively, obtained when varying the pH (4.2 and 7.0). The
concentration of imazalil adsorbed (Qe, mgIMZ gcat−1) on the
catalyst surface (t = 0 min) and the concentration of iron leached
(FeT leached, mg L−1) are gathered in Table 3. As expected, an
overall hampering of the imazalil photocatalytic degradation
and mineralization was observed in synthetic wastewater SW
at pH0 = 4.2 (i.e., in the absence of H2O2), likely due to poison-
ing of the catalyst surface by adsorbed inorganic ions (Santiago
et al. 2014). It is worth noting that the efficiency of the magnetic
catalyst—based on imazalil removal—was better than that of
bare TiO2 under these pH conditions (pH0 4.2). This could be
partially due to the higher adsorption of imazalil obtained with
the magnetic catalyst, as shown in Table 3 (0.90 and 4.24
mgIMZ gcat−1 for EST-1023t and SiO2@Fe3O4-EST-1.5-200-
N2, respectively), but also to a higher resistance of this catalyst
to interfering species, such as inorganic ions, at such pH (prob-
ably as consequence of its lower pHPZC).
At pH 7.0 (above the pHPZC of the catalysts), a total con-
version of imazalil was obtained with bare TiO2 after 60 min
(Fig. 6a). Under these conditions, the process is not hindered
by the presence of inorganic ions in solution, while the mag-
netic catalyst is slightly less active. Regarding the mineraliza-
tion, a TOC reduction of 70% was observed with bare TiO2 at
pH 7.0, whereas a TOC reduction of only 20% was obtained
with SiO2@Fe3O4-EST-1.5-200-N2 (Fig. 6b). Overall, Fig. 6a
shows that the magnetic catalyst has the best performance at
natural pH (avoiding consumption of chemicals for pH adjust-
ment), but the reaction by-products resulting from imazalil

Table 3 Concentrations of
imazalil adsorbed (over catalyst Catalyst
mass) after adsorption-desorption
equilibrium (30 min) and iron
leaching after the photocatalytic
treatment of 50 mg L−1 imazalil in EST-1023 t
SW solution for 150 min SiO2@Fe3O4-EST-1.5-200
SiO2@Fe3O4-EST-1.5-200 + H2O2
degradation are very refractory to degradation at such condi-
tions (Fig. 6b).
Regarding the Fe leached to the solution (3.53 mg L−1)
with SiO2@Fe3O4-EST-1.5-200-N2 after the photocatalytic
treatment at pH0 4.2 (Table 3), it indicates that the magnetic
substrate is not completely protected by SiO2. This was con-
firmed by SEM (Fig. 7). Interestingly, no leaching was ob-
served at pH 7.0. This could be eventually due to iron speci-
ation with pH, i.e., precipitate forms predominate at neutral
pH. The presence of Fe ions may impact on the photocatalytic
activity of TiO2 since these species compete for electrons with
adsorbed oxygen, decreasing the production of oxidizing spe-
cies; they may also form iron hydroxides on the catalyst sur-
face. In addition, Fe ions absorb UV light, screening light
from the catalyst at high concentrations (Sclafani et al. 1991;
Butler and Davis 1993). Nevertheless, beneficial effects due to
the presence of Fe3+ ions have been reported under pH < 3.5
and below 0.39 mg L−1 levels (Lopez-Muñoz et al. 2007).
Since Fe-species were found in treated SW at pH0 4.2, a
heterogeneous photo-Fenton experiment was performed at
this pH using 2 g L−1 of the SiO2@Fe3O4-EST-1.5-200-N2
catalyst and an excess of H2O2 (307 mg L−1), for the degra-
dation of 50 mg L−1 imazalil in SW. The addition of H2O2
clearly increased the imazalil removal within 60 min (Fig. 6a)
as well as its mineralization after 120 min of irradiation (Fig.
6b), in comparison with the non-assisted H2O2 treatment. The
enhanced mineralization is due to a parallel photo-Fenton re-
action that takes place when H2O2 is added into the system.
Fig. 7 SEM/EDS micrograph of the SiO2@Fe3O4-EST-1.5-200 catalyst
Environ Sci Pollut Res
Qe (mgIMZ·gcat−1) FeT leaching (mg·L−1)
pH0 4.24 pH 7 pH0 4.24 pH 7
0.90 13.03 0 0
4.24 17.44 3.53 0
4.62 – 3.51 –
Other experiments were carried out following the degradation
of 50 mg L−1 imazalil in SW medium at pH0 4.2, using either
1 g L−1 of Fe3O4, 2 g L−1 of SiO2@Fe3O4, or 2 g L−1 of
SiO 2@Fe3O 4-EST-1.5-200-N2 in the presence of H 2O2
(Fig. 8), in order to check the effect of each catalyst constituent.
Interestingly, the complete degradation of imazalil was only ob-
served when using the SiO2@Fe3O4-EST-1.5-200-N2 catalyst.
The consumption of H2O2 was lower than 10 mg L−1 when using
the magnetic supports alone (i.e., in the absence of TiO2) but
hydrogen peroxide was fully depleted in the presence of TiO2.
In order to understand why the degradation of imazalil
takes place only when TiO2 is present, the leaching of iron
was further studied for these catalysts (2 g L−1) at different pH
values (2.5, 3.0, and 4.2), in this case using DW under strong
stirring for 60 min (Table 4) under dark or irradiation condi-
tions, but in the absence of H2O2. Regarding the experiments
in the dark, the amount of iron species in solution correlated
with increasing acidic conditions and Fe leaching only hap-
pened at pH ≤ 3.0. The coating of SiO2 over Fe3O4 may in
somehow prevent Fe leaching, but only up to pH 3.0. In the
case of the Fe3O4-EST-1.5-200-N2 sample under irradiation,
Fe leaching occurred independently of the pH conditions and
the Fe concentrations were significantly higher, but the SiO2
layer decreased the leaching at pH 4.2. Since leaching was not
observed under dark, it seems that under irradiation the
photogenerated electrons in TiO2 can transfer into the Fe3O4
Fig. 8 Degradation of imazalil in simulated water at pH0 4.2 using
different catalysts (2 g L−1) with additional 307 mg L−1 H2O2
Environ Sci Pollut Res

Table 4 Fe leaching from magnetic catalysts as a function of pH and consecutive cycles. Moreover, the concentration of Fe leached
UV illumination
was between 1.61 and 1.77 mg L−1 in 90 min, i.e., below the
Catalyst FeT leaching (mg L−1) thresholds established for wastewater disposal or even water
reuse for irrigation.
pH0 2.5 pH0 3 pH0 4.2

Fe3O4/Dark 3.45 1.08 0

SiO2@Fe3O4/Dark 3.43 0.48 0 Conclusions
Fe3O4-EST-1.5-200-N2/Dark 0.77 0.42 0
Fe3O4-EST-1.5-200-N2/UV 10.38 7.61 3.03
SiO2@Fe3O4-EST-1.5-200-N2/UV – – 1.23
phase, with subsequent release of Fe2+ groups to the medium.
These results are in agreement with those published in litera-
ture for other TiO2@Fe3O4 photocatalysts (Beydoun et al.
2002; Álvarez et al. 2010; Zhan et al. 2014).
Catalyst reuse
The magnetic supports aimed at the simple recovery and reuse
of the catalysts, avoiding complex processes to filter the
suspended particles or complicated fabrication approaches to
immobilize these catalysts. The straightforward recovery of
the SiO2@Fe3O4-EST-1.5-200-N2 sample was demonstrated
using a simple magnet (Fig. S4). The reuse of these particles
was studied during the degradation of imazalil in SW at pH0 =
4.2 and it was observed that the magnetic catalyst can be used
at least over 3 cycles without efficiency lost. Figure 9 shows
data for studies carried out in the presence of H2O2, as this was
the system that exhibited best results (see BPhotocatalytic ac-
tivity with synthetic wastewater^ section). The adsorption of
imazalil on the catalyst surface (in the dark adsorption-
desorption period), the mineralization of this organic pollut-
ant, and the amount of iron leached are similar in the three
Fig. 9 Cycle degradation of imazalil in simulated water (SW) at pH0 4.2
using the SiO2@Fe3O4-EST-1.5-200-N2 catalyst (2 g L−1)
The core-shell SiO2@Fe3O4-EST material prepared with a
TiO2:support ratio of 1.5 presents the best compromise be-
tween the photocatalytic activity (complete degradation of
imazalil), magnetic separation, and Fe leached in DW spiked
with imazalil. The optimum catalyst was that treated at 200 °C
under N2 atmosphere. The other materials treated at 450 °C
(under N2) exhibited lower photocatalytic activity due to cat-
alyst surface modifications (e.g., poisoning by adsorbed ni-
trate species, as revealed by FTIR, or poor rGO stability).
Moreover, magnetite is completely oxidized to hematite (and
the magnetic properties are lost) under air atmosphere when
the catalyst is based on TiO2 and Fe2O3 only. Partial iron-
phase transformations were also identified by X-ray diffrac-
tion in the case of rGO-MN. Fe leaching was observed
(3.53 mg L−1) with the best performing photocatalyst in the
treatment of imazalil when spiked in the synthetic wastewater
at natural pH and, thus, added H2O2 increased both imazalil
degradation and mineralization, which can be explained by
parallel photo-Fenton reactions resulting from the lixiviation
of iron. Therefore, in comparison with bare TiO2, the magnet-
ic catalyst can be easily separated from treated water and pre-
sents a higher photocatalytic activity in the absence of H2O2.
However, leaching was observed and, thus, the photo-Fenton
process is also an option for the treatment of imazalil, but in
this case H2O2 is needed.
Acknowledgements The Ministry of Economy and Competitiveness
(MINECO), Government of Spain, is thanked for funding of the
NANOBAC project (IPT-2011-1113-310000) and co-funding, together
with the European Regional Development Fund (ERDF) for the
Infrastructure Project 2010-3EUNLP10-3E-726. DES would like to thank
the University of Las Palmas de Gran Canaria (ULPGC) for funding
(PhD Grant Program) and the Spanish Ministry of Science and
Innovation (MICINN) for its financial support through the PhD
Studentship BES-2010-036537. This research was also partially support-
ed by Project POCI-01-0145-FEDER-006984–Associate Laboratory
LSRE-LCM funded by FEDER through COMPETE2020–Programa
Operacional Competitividade e Internacionalização (POCI), and by na-
tional funds through FCT–Fundação para a Ciência e a Tecnologia, the
Strategic Funding UID/Multi/04423/2013 through national funds provid-
ed by FCT–Foundation for Science and Technology and European
Regional Development Fund (ERDF), in the framework of the pro-
gramme PT2020. The authors also thank the Canarian fruit postharvest
companies for their collaboration. AMTS and LMPM acknowledge the
FCT Investigator Programme (IF/01501/2013 and IF/01248/2014), with
financing from the European Social Fund and the Human Potential
Operational Programme. LMPM also acknowledges the MINECO and
the European Social Fund for a Ramon y Cajal research contract (RYC-
2016-19347).

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