Fe3O4 Magnetic Nanoparticles: Characterization and Performance

Exemplified by the Degradation of Methylene Blue in the Presence of

Persulfate
Chang-Mao Hung, Chiu-Wen Chen, Yu-Zhe Jhuang, Cheng-Di Dong*
Department of Marine Environmental Engineering, National Kaohsiung Marine University, 142 Haijhuan Road,
Nanzih District, Kaohsiung City 81157, Taiwan

Abstract:
In this study, the oxidation of methylene blue (MB) over iron oxide magnetic nanoparticles (Fe3O4), which
effectively activates persulfate anions (S2O82−) to form sulfate free radicals (SO4−•), was explored. In addition,
the effect of the initial pH, sodium persulfate (Na2S2O8, PS) concentration, and Fe3O4 content on the
decolorization of MB was investigated. The results revealed that the decolorization rate increased when the
persulfate concentration increased from 0.03 to 0.12 g/L and the Fe3O4 content from 0.1 to 0.8 g/L. Therefore,
the Fe3O4 nanoparticles enhanced the decolorization of MB. The catalyst was analyzed using cyclic voltammetry
(CV), three-dimensional excitation-emission fluorescence matrix (EEFM) spectroscopy, and zeta potential
measurements. The CV spectra indicated that a reversible redox reaction may explain the high catalytic activity
of the catalyst. EEFM was used to evaluate the yield of a fresh Fe3O4 catalyst, and two peaks were observed at
EX/EM wavelengths of 230/300 nm and 270/300 nm. Furthermore, the structure and surface morphology of the
catalyst were characterized using X-ray diffraction (XRD) and environmental scanning electron microscopy
(ESEM)–energy dispersive spectroscopy (EDS), respectively. The XRD result confirmed the existence of Fe3O4
in the catalyst. ESEM was used to determine the Fe3O4 particle size, indicating a high degree of nanoparticle
dispersion.

Keywords: methylene blue (MB); sodium persulfate (Na2S2O8, PS); Fe3O4 nanoparticle materials; three-
dimensional excitation-emission fluorescence matrix (EEFM) spectroscopy.

Introduction or yield contaminated sludge or adsorbents that

In recent years, synthetic dye emission has
become a severe environmental problem worldwide,
involving the exposure of animals and human to
aqueous toxic chemical and hazardous materials (1-3).
Dyes with a complex aromatic molecular structure are
emitted through various processes, including those
used in leather and textile manufacturing and
pharmaceutical and food production (4). Synthetic
dyes can be converted to highly mutagenic and
carcinogenic compounds under ambient conditions
and are a potential public health and environmental
hazard (5). Hence, removing industrial dyes from waste
streams and controlling dye emissions are of global
concern. In recent years, several approaches have been
developed to biologically, physically, and chemically
treat dyes, and methods such as bio-degradation,
filtration, coagulation, ultraviolet-light irradiation,
ozonation, adsorption, and catalytic oxidation have
been used for removing dyes from water (6). However,
these approaches either result in phase transformation
*Corresponding author; E-mail: cddong@mail.nkmu.edu.tw
require further treatment to satisfy stringent discharge
regulations.
To overcome these drawbacks, the most
promising and widely used advanced water treatment
techniques for controlling dye effluents are sulfate-
radical-based (SO4–•) advanced oxidation processes
(AOPs) for oxidizing persulfate that produce a
powerful oxidizing species known as SO4–• (7,8). The
persulfate anion (S2O82−) is an oxidant that is highly
soluble in aqueous solutions and thermodynamically
more stable (E0 = 2.01 V) than H2O2 (E0 = 1.76 V);
however, direct reactions between persulfate and most
reductants are slow. When appropriately activated,
persulfate decomposes into a highly reactive species,
SO4–• (9), that SO4–• has a high redox potential (E0 =
2.6 V) near that of hydroxyl radicals (2.8 V), which
are strong one-electron oxidants that can degrade
contaminants. Generally, persulfate can be chemically
activated by transition metals (Mn+):
2  2
S2O8  M n  SO4  SO4  M ( n1)
(1)
This critical heterogeneous catalytic process has
attracted considerable attention in materials chemistry,

ISSN 1203-8407 © 2016 Science & Technology Network, Inc. J. Adv. Oxid. Technol. Vol. 19, No. 1, 2016 43
C-M Hung et al.
and the effectiveness of the active persulfate process
has been improved by using high-performance ferrous
ions, which potentially shorten the reaction time under
mild operating conditions.
2  2
S2O8  Fe 2  SO4  SO4  Fe 3
Typically, sulfate-radical-based AOPs selectively
produce carbon dioxide and involve the oxidation of
small molecules through aqueous phase oxidation.
Various types of catalysts that oxidize dye-
contaminated wastewater have been studied. For
example, Yan et al. (10) reported that the complete
removal of sulfamonomethoxine (SMM) through
degradation was achieved within 15 min by using 2.4
mmol/L Fe3O4 magnetic nanoparticles as the
heterogeneous activator of 1.2 mmol/L persulfate.
Nguyen et al. (11) used Fe2MnO4/AC-H catalysts to
oxidize methyl orange at pH 3.0 and found that
activated carbon can be treated with HNO3 to
functionalize the carbon surface through the formation
of carboxyl groups. Additionally, a recent study (12)
described the efficient catalytic oxidation of the azo
dye orange G (OG) in an aqueous stream achieved by
using a Fe2+/persulfate reagent in the temperature range
of 293–313 K at a pH of 3.5. The OG degradation
increased when the amount of Fe2+ and persulfate
increased. Yang and co-workers (13) reported the
persulfate oxidative degradation of the azo dye acid
orange 7 (AO7) in the presence of suspended granular
activated carbon (GAC) with a remarkable synergistic
effect in the GAC/sodium persulfate (PS) combined
system. Ghauch et al. (14) studied the thermal
discoloration of methylene blue (MB) by using an
efficient and affordable process involving activating
persulfate at 303–343 K to form powerful sulfate
radicals in an aqueous solution. They separated and
identified the main intermediates by using liquid
chromatography–mass spectrometry and proposed a
plausible degradation pathway for MB. Zhu et al. (9)
examined the oxidation of methyl orange in an aqueous
solution over core-shell Fe-Fe2O3 nanostructures
(FNs) and found that the conversion of methyl orange
reached 90% in 10 min in an FN/Na2S2O8 process. Lin
et al. (5) converted AO7 to sodium sulfanilamide and
1-amino-2-naphthol by using Fe3O4–catalyst–activated
peroxydisulfate in an electro/Fe3O4/PDS process.
They found that the Fe3O4 particles were stable and
reusable. Wang et al. (4) investigated the degradation
conversion of AO7 by using persulfate activated over
zero-valent iron catalysts in the presence of ultrasonic
irradiation. The results of the aforementioned studies
revealed the potential of persulfate reactivity to
degrade organic contaminants.
44 J. Adv. Oxid. Technol. Vol. 19, No. 1, 2016
Magnetite (Fe3O4) is a promising heterogeneous
catalyst because of its natural abundance, low-cost,
and environmentally friendly properties and can be
used as an activator of persulfate (15, 16). Recently,
applying magnetite to oxidize organic compounds in
(2) dye-contaminated wastewater has attracted considerable
interest (7). Fe3O4 improves the persulfate oxidation
properties by accelerating the degradation rate through
the formation of SO4–•. Moreover, to the best of our
knowledge, few studies have investigated using Fe3O4
for the catalytic liquid-phase oxidation of MB.
Accordingly, in the current study, a Fe3O4 catalyst was
used to oxidize MB, a brightly colored cationic
thiazine dye, in a sulfate-radical-based AOP process
under various conditions, and the effectiveness of the
catalyst was examined.
Excitation-emission fluorescence matrix (EEFM)
spectroscopy was used across a range of excitation
and emission wavelengths to effectively understand
catalyst characteristics during the catalytic process.
Thus, this study investigated the effect of various
parameters, such as Fe3O4 content, PS concentration
and pH, on a Fe3O4 nanoparticle catalyst, applied to
activate persulfate and oxidize MB, to establish the
optimal conditions for the catalytic system. Moreover,
the catalysts were characterized using cyclic
voltammetry (CV), zeta potential measurements, X-
ray diffraction (XRD), and environmental scanning
electron microscopy (ESEM)–energy dispersive
spectroscopy (EDS).
Materials and Methods
Materials and Chemicals
MB was purchased from Kojima Chemicals Co.
Ltd (Japan) and used without further purification.
Fe3O4 powders with particle sizes of 50–100 nm and a
Brunauer–Emmett–Teller surface area of 20–50 m2/g
were obtained from Alfa Aesar Co. (USA). PS
(Na2S2O8, 98%) was purchased from Showa Chemical
Industry Co. (Japan). All other reagents were of
analytical grade. Deionized water was used for solution
preparation in all experiments. Before each run, a
stock solution of MB was prepared with deionized
water and the initial concentration (C0) was maintained
at 30 mg/L (0.08 mM). Furthermore, H2SO4 or NaOH
was used to adjust the initial pH (pH0) of an MB
solution.
Experimental Methods
The experimental setup included a 500 mL
cylindrical reactor containing 250 mL of a model dye
solution. All experiments were conducted at room
temperature (298 K). A mechanical stirrer, used to
C-M Hung et al.
maintain uniform suspension, was switched on when
persulfate and Fe3O4 powders were added to the
solution. At various time intervals, 2 mL of the liquid
was sampled and the absorbance was measured at 664
nm by using an ultraviolet spectrophotometer (Merck,
Spectroquant Vega 400, Germany). The decolorization
efficiency (η%) was calculated according to the
following equation: (%)  ( A0  A) / A0  100 ,
where A0 and A are the absorbance of the sample at
time instants 0 and t, respectively.
CV measurements were conducted at room
temperature by using an electrochemical analyzer (CH
Instrument, CHI 6081D, USA) and a three-electrode
electrochemical cell. The working electrode was a
glassy carbon electrode, and the samples were
scanned at a rate of 50 mV/s with potential cycling
between -0.2 and 1.2 V for each analysis. The counter
electrode was a platinum wire, Ag/AgCl (in saturated
KCl solution) was employed as the reference electrode,
and H2SO4 (0.5 M) was used as the electrolyte solution.
In this study, fluorescence excitation-emission
matrix (FEEM) spectroscopy was used to obtain
complete spectral characterization of the catalyst.
FEEM spectra were obtained using a luminescence
spectrophotometer (F-4500, Hitachi, Japan) with a
xenon lamp as the excitation source. The emission
spectra were plotted on the x-axis, and the excitation
spectra were plotted parallel to the y-axis. The widths
of all slits in both the excitation and emission
monochromators were 10 nm. The FEEM comprised
60 excitation and 60 emission spectra from 200 to 800
nm and provided discrete values for the fluorescence
intensity at 3600 excitation/emission wavelength
pairs. Spectral subtraction was performed to remove
the blank spectra of pure water. A zeta potential
analyzer (Zetasizer 2000HAS, Malvern, UK) was used
for determining the particle zeta potential. XRD
analysis was performed using a Diano-8536
diffractometer equipped with a CuKα radiation
source. During analyses, samples were scanned from
10° to 80° at a rate of 0.4°/min. We used an ESEM
system equipped with an energy-dispersive X-ray
spectrum analyzer (Quanta 200 FEG, FEI Company,
Czech Republic) to determine the morphology of the
catalyst. These aforementioned techniques yielded
information on the distribution of Fe3O4 nanoparticles
on the catalyst surface.
Results and Discussions
Effect of Different Parameters on
Decolorization of Methylene Blue
Figure 1 presents the results of experiments
conducted using Fe3O4 alone, PS alone, and both
1.0
Fe3O4
0.8 PS
Fe3O4/PS
0.6
C/C0
0.4
0.2
0.0
0 10 20 30 40 50
Time (min)
Figure 1. Plots of the decrease in the MB concentration (C/C0)
versus time for various processes. Experimental conditions:
reaction volume = 250 mL, T = 298 K, pH0 = 6.0, [MB] = 30
mg/L, [Na2S2O8] = 0.03 g/L, and [Fe3O4] = 0.1 g/L.
Fe3O4/PS. MB could not be effectively degraded when
only Fe3O4 was used, indicating the in effect
adsorption of MB under the investigated conditions.
Figure 1 shows that the conversion rate of MB
increased moderately (41%) after 9 min of treatment,
during which 0.03 g/L PS was added. The experimental
results revealed that the MB conversion rate increased
to 73% at a PS concentration of 0.03 g/L, a Fe3O4
concentration of 0.1 g/L, and an initial pH value of 6.0
at 298 K in the sulfate-radical-based AOP when Fe3O4
was used as the activator. This observation can be
explained as follows: in the Fe3O4/PS process, the
Fe3O4 may influenced the electron mass transfer of the
reacting species (MB and PS), thereby producing
SO4−• (5,7,14) through the chemical reaction expressed
in Eqs. (3) and (4). These SO4−• enhanced the
degradation of MB.
2  2
S2O 8 e   SO4  SO4 (3)
 2
MB  SO4  [ MB]  SO4 (4)
2−
S2O8 can be activated at the Fe3O4 surface through
electron transference to produce sulfate radicals that
increase the conversion yield. Thus, the combination
of S2O82− and Fe3O4 exerts a synergistic effect on the
decolorization of MB through oxidation. Recently,
Ghauch and his collaborators (17) used Fe0 as a PS
activator. The use of Fe0 caused iron corrosion
products to form in solution, thereby enhancing the
activation process. Yan et al. (10) observed iron ions
(Fe2++ Fe3+) and highly dispersed clusters in iron
oxide magnetic nanoparticles that were coupled to
persulfate. Therefore, using an appropriate metal
oxide in the persulfate system may effectively provide
reactive species. Furthermore, in the present study, as
the reaction proceeded, the degradation kinetics of
J. Adv. Oxid. Technol. Vol. 19, No. 1, 2016 45
C-M Hung et al.

1.0
1.0 (a)
pH 3.0
pH 6.0
pH 9.0
0.01 g/L
0.8
0.8 0.03 g/L
0.09 g/L
0.12 g/L
0.6 0.6
C/C0

0.4 0.4

0.2
0.2

C/C0
0.0
0 10 20 30 40 50 0.0
1.0
Time (min)
(b)
Figure 2. Effect of the initial pH on the MB degradation.
Experimental conditions: reaction volume = 250 mL, T = 298 K, 0.8 0.01 g/L
[MB] = 30 mg/L, [Na2S2O8] = 0.03 g/L, and [Fe3O4] = 0.1 g/L. 0.03 g/L
0.09 g/L
0.6 0.12 g/L
MB during persulfate oxidation over a Fe3O4 catalyst
could be explained by mass-transfer-controlled first-
0.4
order kinetics, which can be determined from a linear
plot of ln(C/C0) versus the reaction time t; the rate
constants (k) were 0.014 and 0.029 min-1 for PS and 0.2

the Fe3O4/PS process, respectively. Hence, activating

persulfate by using Fe3O4 is a more rapid method of 0.0
0 10 20 30 40 50
degrading MB.
Figure 2 presents plots showing the effect of the Time (min)

initial pH on the decolorization of MB over the Fe3O4
catalyst in the Fe3O4/PS process. The experiments
demonstrated that this effect was appreciable at pH0
values near 6.0. Moreover, the removal of MB was
suppressed at pH0 9.0 and 3.0. The difference in color
removal at different pH0 values suggests that the rate
of the MB reaction in the persulfate catalytic
oxidation system depended on the pH value. This
dependence was confined to the duration during which
sulfate radicals generated in the Fe3O4/PS process
reacted with H2O or OH– to produce hydroxyl radicals
that reduced the solution pH. Acidic conditions
enhance the dissolution of iron powder by producing
more Fe(II). Thus, more sulfate radicals can be
formed by Fe(II) through the catalytic activation of
persulfate. However, excessive Fe(II) can act as
scavengers of sulfate radical. In other words,
 2
Fe 2  SO4  SO4  Fe 3
Under alkaline conditions, more hydroxyl radicals
are generated from sulfate radicals according to the
following reaction:
 2
SO4  OH   SO4  OH
However, the oxidation potential of the hydroxyl
radical may decrease with an increase in the pH. In
addition, the scavenging reaction between the sulfate
Figure 3. Effect of the persulfate concentration on the MB
degradation of (a) Na2S2O8 and (b) Na2S2O8 + Fe3O4.
Experimental conditions: reaction volume = 250 mL, T = 298 K,
[MB] = 30 mg/L, pH0 = 6.0, and [Fe3O4] = 0.1 g/L.
radical and the hydroxyl radical is enhanced at a high
pH (5). In other words,
 2
SO4  OH  SO4  H   0.5O2 (7)
Accordingly, the Fe3O4/PS process can apparently
be performed using a wide range of initial pH values,
from 3.0 to 9.0. Because pH0 6.0 was the natural pH
of the MB solution, it was used in the subsequent
experiments.
Figure 3 shows the PS concentration effect for the
using PS alone and both Fe3O4/PS on MB
decomposition. The decolorization rate of MB
increased slowly when only the PS concentration
(5)
increased from 0.01 to 0.12 g/L (Fig. 3a). The total
conversion efficiency of MB was 84% at a PS
concentration of 0.12 g/L (2.0 mM) and a Fe3O4 dose
of 0.1 g/L (0.4 mM) (Fig. 3b). The [MB]0/[PS]0 molar
ratio was 0.04. A higher PS concentration causes an
(6) increased degradation of MB. In addition, a sufficient
amount of persulfate produces adequate SO4−• to
enhance the activation activity of Fe3O4, thus leading
to the enhanced degradation of MB (9). The

46 J. Adv. Oxid. Technol. Vol. 19, No. 1, 2016

C-M Hung et al.
decomposition of MB over the Fe3O4/PS process
increased with the amount of sulfate radicals because
of an increased direct electron transfer between the
components of the Fe(III)/Fe(II) redox pair (7,16).
Consequently, the increased PS concentration increased
the production of SO4−• and provided a strong driving
force for oxidation. The oxidation reaction can also be
explained by the synergistic effect of Fe3O4 materials
and SO4−•. However, after 18 min of reaction, the
decolorization efficiency was almost the same as that
for PS concentrations from 0.03 to 0.12 g/L,
indicating that the amount of SO4−• produced was
sufficient for achieving decolorization. Compared
with the situation in Fig.1, in which the rate of MB
conversion increased moderately (41%) after 9 min of
treatment (during which 0.03 g/L of PS was added),
the conversion after 18 min of reaction in the
Fe3O4/PS process was nearly 60%. A higher PS
concentration (>0.12 g/L) may not enhance MB
oxidation because of chain termination between
sulfate radicals. In this decolorization system, MB
constituents exhibited a considerable influence and led
to the gradual reduction of PS of experimental run.
The treated sample had over 70% of the PS still
remaining at an initial PS dose of 0.03 g/L in treated
sample during 45 min of experimental run. The results
indicated that adequate PS must be available because
it is the source of the SO4−• responsible for the
degradation of MB. Therefore, low PS consumption is
required for achieving an acceptable reaction
stoichiometric efficiency, which is necessary for
driving the reaction until MB removal is complete
(18). This finding was similar to that of Wang et al.
(4), who experimented on the persulfate oxidation of
AO7 in wastewater.
Figure 4 shows the effect of Fe3O4 on the MB
removal efficiency as a function of time in the
Fe3O4/PS process. Generally, the degradation of MB
increased sharply when the Fe3O4 increased from 0.1
to 1.6 g/L. Specifically, Figure 4 shows that using 1.6
g/L of Fe3O4 as an activator for the effective
degradation of MB yielded a maximum conversion
rate of 70%. This rate can be attributed to the presence
of a sufficient quantity of Fe(II), which serves as an
electron donor, for catalytically decomposing persulfate
anions (19). However, the MB degradation rate
increased slightly when the Fe3O4 dose was increased
to 2.4 g/L, and a further increase in the reaction time
little affected the decolorization rate. This is because
the excess Fe3O4 may have reduced PS consumption,
and the produced Fe(II) could have scavenged SO4−•
through the reaction expressed in Eq. (3). Moreover, a
high Fe(II) dose could cause SO4−• quenching, thereby
1.0
0.1 g/L
0.8
0.8 g/L
1.6 g/L
2.4 g/L
0.6
C/C0
0.4
0.2
0.0
0 10 20 30 40 50
Time (min)
Figure 4. Effect of iron oxide addition on the MB degradation.
Experimental conditions: reaction volume = 250 mL, T = 298 K,
[MB] = 30 mg/L, pH0 = 6.0, and [Na2S2O8] = 0.03 g/L.
decreasing the reaction stoichiometric efficiency after
the formation of S2O82− and Fe(III). This observation
is consistent with previously reported results (10).
Characterization of Methylene Blue for Types of
Fe3O4
Figure 5 shows the electrochemical behavior of
freshly prepared and used Fe3O4 catalysts. The CV
plot reveals that the freshly prepared Fe3O4 catalyst
had a higher reversible redox capacity and oxidation
current density than did the used Fe3O4 catalyst; the
well-marked state was at 0.55 and 0.61 V for the
freshly prepared and used Fe3O4 catalysts, respectively.
This reversible redox ability of the fresh catalyst could
explain its high activity. By contrast, the used Fe3O4
catalyst produced negligible oxidation–reduction
currents in the potential window. Lambrou et al. (20)
showed that Fe3O4 had the most active phase in the
catalytic reaction because Fe3O4 strongly promotes
oxygen storage. This finding suggests that Fe3O4 can
promote PS activation during MB oxidation.
Furthermore, the generation of Fe3O4 species was
evidenced by the reduction peaks near 0.6 V (21,22).
Therefore, MB is believed to have been adsorbed onto
the surface of the catalyst before the oxidation–
reduction cycle reaction commences at the iron oxide
active sites.
To further elucidate the reactive properties of the
catalyst, EX/EM plot positions obtained from the
EEFM of the fluorescence spectrometer were used to
generate effective data for the preliminary estimation
of the catalyst properties. Figure 6a shows the
fingerprint of the three-dimensional EEFM for a fresh
Fe3O4 nanoparticle; two significant excitation/emission
plots were generated at 230/300 and 270/300 nm.
Figure 6b shows the fingerprint of the EEFM for the
J. Adv. Oxid. Technol. Vol. 19, No. 1, 2016 47
C-M Hung et al.

(a) Fresh
2 (b) Used
Current (mA)

-2

-4

-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

Potential (V)

Figure 5. CV profiles in a 0.5 M H2SO4 solution for the Fe3O4

nanoparticle used for degrading MB at a scan rate of 50 mV/s (a)
before and (b) after the catalytic test.

Fe3O4 catalyst after the activity test; two substantial

excitation/emission plots at 290/300 and 270/384 nm
were observed. The emission wavelength of the used
Fe3O4 nanoparticle increased remarkably to 384 nm
because of effective electron transfer from the excited
state to the Fe3O4 nanoparticle conduction band. This
result is similar to that reported by Alveroğlu et al.
(23), who determined that magnetite nanoparticle
wavelengths were 380 and 405 nm in an emission
spectrum. These excitation/emission plots can be
described by considering the metal-enhanced
fluorescence effect, in which fluorescence is
associated with iron and ionic iron species of Fe3O4
during the catalytic reaction. Moreover, the observed
changes in the excitation/emission plots may be
attributable to the presence of surface functional
groups and surface energy traps that become emissive
upon stabilization as a result of surface passivation
after the activity test (24).
The particle zeta potential is a crucial physical
property of a catalyst. Figure 7 displays the variation
of the zeta potential for freshly prepared and used
catalysts. The variation reveals that the surface charge
of the catalyst changed during exposure to the
catalytic oxidation environment. The mean particle
zeta potential changed from -35.6 mV for the freshly
prepared Fe3O4 catalyst to -20.9 mV for the reacted
Fe3O4 catalyst. The zeta potential changed inappreci-
ably, even after decolorization through persulfate
addition. The weak electrostatic repulsion between the
surface charges of a solid particle and the tendency of
the particles to flocculate after a catalytic reaction
may explain the experimental results.
Figure 8 shows the XRD pattern of the fresh and
used catalysts; the catalyst changed during exposure to
the catalytic environment. Furthermore, the XRD
Figure 6. Contour plots of the excitation–emission fluorescence
matrix for the Fe3O4 nanoparticle used for degrading MB (a)
before and (b) after the catalytic test.
analysis confirmed the existence of the Fe3O4 state in
the catalyst. The XRD patterns of the freshly prepared
Fe3O4 and used Fe3O4 after the Fe3O4/PS process were
somewhat similar. The dominant Fe3O4 diffraction
peaks detected at 2θ values of approximately 18.4o,
30.3 o, 35.6 o, 37.3 o, 43.3 o, 53.6 o, 57.2 o, 62.8 o, 71.1 o,
and 74.2o were related to the (111), (220), (311),
(222), (400), (422), (511), (440), (620), and (533)
planes, respectively. Thus, the diffraction peaks of
nanoparticles corresponded with those of Fe3O4
confirming the high crystallinity of the samples. This
result is consistent with those of Yan et al. and Dong
et al. (10,25). The results of the XRD analysis
indicated that Fe3O4 active sites were formed on the
Fe3O4 catalyst. Therefore, MB was adsorbed on the
surface of the catalyst before undergoing a catalytic
reaction at the Fe3O4 active sites. On the basis of XRD
patterns, the crystal size of the particles can be
evaluated by using the following Debye–Scherrer
equation:

48 J. Adv. Oxid. Technol. Vol. 19, No. 1, 2016

C-M Hung et al.
8e+5
(a) Fresh
(b) Used
6e+5
Total Counts
4e+5
2e+5
0
-200 -100 0 100
Zeta Potential (mV)
Figure 7. Zeta potential of the Fe3O4 nanoparticle on the MB
degradation (a) before and (b) after the catalytic test.
D  K /(  cos  )
where K is the Scherrer factor (0.89), λ is the X-ray
wavelength (0.15418 nm), β is the peak full width at
half-maximum (FWHM), and θ is the Bragg
diffraction angle. According to the most intense peak
(311), the average size of the particles was calculated
to be 26.9 nm.
Figure 9 presents ESEM-EDS images showing the
surface morphology changes of the Fe3O4 nanoparticle
catalyst. These data provide crucial information
regarding the surface structure of the catalyst during
the MB oxidation reaction. ESEM observations of the
nanoparticles indicated that the Fe3O4 catalyst formed
small spherical particles. Furthermore, these experi-
mental results confirm that the dispersion of the
catalyst increased the efficiency of the MB catalysis.
Figure 9a presents a more crystalline catalyst surface
compared with that in Figure 9b. The small crystal
phases may explain the high activity of the catalysts;
the catalysts were nearly nanoscale in size (approxi-
mately 80 nm) and exhibited high dispersion.
Specifically, disaggregated phases formed when the
catalyst surface aged or was poisoned because of
plugging, implying that the porosity of the particles
changed (Figure 9b). EDS provided evidences of the
presence of iron species in the catalyst. Moreover, the
elemental-composition analysis of the test catalyst
surfaces revealed that the leaching of metal ions from
the Fe3O4 catalyst varied slightly. For the Fe3O4
catalyst, the elemental percentage of Fe atoms was
70%–67% and that of O atoms was 30%–33%. Less
iron and more oxygen were observed after the PS
chemical activation test, possibly because the MB
oxidation was caused by PS on the surface of Fe3O4
(14). Fe3O4 emerged from the catalyst, which likely
exposed the active site on the nanoparticle surface.
●
● Fe3O4
● ●
●
(a) Fresh
●
Intensity
● ● ●
● ●
●
● ● (b) Used
●
●
● ● ● ● ●
200
10 20 30 40 50 60 70 80
2θ
Figure 8. XRD pattern of the Fe3O4 nanoparticle used for
degrading MB (a) before and (b) after the catalytic test.
(8)
The performance of the Fe3O4 catalyst was poor
mainly because of iron corrosion, which caused
nanoparticles to agglomerate on the catalyst surface.
In future studies, recycling experiments using Fe3O4
catalysts should be systematically conducted.
Conclusions
The results of this study indicated that in a
solution with an MB concentration of 30 mg/L, a PS
concentration of 0.03 g/L, a Fe3O4 dosage of 0.1 g/L,
and an optimal initial pH of 6.0, MB can be
decolorized in 45 min. The decolorization rate can be
substantially enhanced by using a combination of
Fe3O4 and sulfate radicals. Overall, the Fe3O4 nano-
particle catalyst was crucial in the MB catalytic
process. CV curves revealed the reversibility of the
redox, which may explain the high activity of the
catalyst. According to a fluorescence spectrometry
evaluation, a fresh Fe3O4 nanoparticle catalyst yielded
fluorescence plots at 230/300 nm and 270/300 nm,
which were identified at room temperature. Moreover,
the loss of activity of the Fe3O4 nanoparticle catalyst
was attributed to either the over-oxidation of the
catalyst surface or the inhibition of the surface by
reaction intermediates. Specifically, while past studies
have suggested that the role of Fe3O4 is confirmed to
providing active sites for the reaction during a catalytic
run, in the current study, the Fe3O4 nanoparticle
catalyst was involved in the persulfate oxidation of
MB. Furthermore, according the experimental data,
the Fe3O4 nanoparticles performed favorably in
environmental treatment applications involving the
removal of MB, and are therefore expected to be useful
for improving industrial plant effluents to satisfy
increasingly stringent regulations on azo dyes discharges
and for achieving environmental sustainability. In the
J. Adv. Oxid. Technol. Vol. 19, No. 1, 2016 49
C-M Hung et al.
Figure 9. ESEM–EDS photographs of the Fe3O4 nanoparticle used for degrading MB (a) before and (b) after the catalytic test.
future, we intend to use a mass spectrometer analyzer
to identify intermediate transformation products and
final products in the oxidation reaction of MB over
Fe3O4/PS systems.
Acknowledgments
The authors would like to thank the National
Science Council of the Republic of China, Taiwan, for
financially supporting this study under Contract Nos.
MOST 103-2221-E-022-001-MY3 and 103-2221-E-
022-002-MY3. The author is also grateful to Prof. W. L.
Lai of the Department of Environmental Resource
Management, Tajen University of Science and
Technology, for his support and discussions, and to
Prof. C. P. Huang of the University of Delaware for
his valuable comments on the initial version of this
manuscript.
References
(1) Juang,Y.; Nurhayati, E.; Huang, C.; Pan, J.R.;
Huang, S. Sep. Purif. Technol. 2013, 120, 289-295.
50 J. Adv. Oxid. Technol. Vol. 19, No. 1, 2016
(2) Hsieh, W.P.; Pan, J.R.; Huang, C.; Su, Y.C.; Juang,
Y.J. Sci. Total Environ. 2010, 408, 672-679.
(3) Hou, Y.; Qu, J.; Zhao, X.; Lei, P.; Wan, D.; Huang,
C. Sci. Total Environ. 2009, 407, 2431-2439.
(4) Wang, X.; Wang, L.; Li, J.; Qiu, J.; Cai, C.; Zhang,
H. Sep. Purif. Technol. 2014, 122, 41-46.
(5) Lin, H.; Zhang, H.; Hou, L. J. Hazard. Mater. 2014,
276, 182-191.
(6) Yang, A.; Huang, C.; Wei, B.; Zhang, Z. Water Sci.
Technol. 2014, 695, 1094-1100.
(7) Xu, X.R.; Li, S.; Hao, Q.; Liu, J.L.; Yu, Y.Y.; Li,
H.B. Int. J. Environ. Bioener. 2012, 1, 60-81.
(8) Tsitonaki, A.; Petri, B.; Crimi, M.; Mosbaek, H.;
Siegrist, R.L.; Bjerg, P.L. Critical Reviews in
Environ. Sci. Tech. 2010, 40, 55-91.
(9) Zhu, L.; Ai, Z.; Ho, W.; Zhang, L. Sep. Purif. Tech.
2013, 108, 159-165.
(10) Yan, J.; Lei, M.; Zhu, L.; Anjum, M.N.; Zou, J.;
Tang, H. J. Hazard. Mater. 2011, 186, 1398-1404.
(11) Nguyen, T.D.; Phan, N.H.; Do, M.H.; Ngo, K.T. J.
Hazard. Mater. 2011, 185, 653-661.
C-M Hung et al.

(12) Xu, X.R.; Li, X.Z. Sep. Purif. Tech. 2010, 72, 105- (20) Lambrou, P.S.; Efstathiou, A.M. J. Catal. 2006,
111. 240, 182-193.
(13) Yang, S.Y.; Yang, X.; Shao, X.T.; Niu, R.; Wang, (21) Wu, F.; Huang, R.; Mu, D.; Wu, B.; Chen, S. ACS
L.L. J. Hazard. Mater. 2011, 186, 659-666. Appl. Mater. Interfaces 2014, 6, 19254-19264.
(14) Ghauch, A.; Tuqan, A.M.; Kibbi, N.; Geryes, S. (22) Karunakaran, C.; Jayabharathi, J.; Sathishkumar, R.
Chem. Eng. J. 2012, 213, 259-271. Spectrochim. Acta Part A. 2013, 110, 151-156.
(15) Si, S.; Kotal, A.; Mandal, T.K.; Giri, S.; Nakamura, (23) Alveroğlu, E.; Sözeri, H.; Baykal, A.; Kurtan, U.;
H.; Kohara, T. Chem. Mater. 2004, 16, 3489-3496. Şenel, M. J. Mater. Sci. 2013, 1037, 361-366.
(16) Tang, S.C.N.; Lo, I.M.C. Water Res. 2013, 4, 2613- (24) He, X.; Liu, Y.; Li, H.; Huang, H.; Liu, J.; Kang, Z.;
2632. Lee, S.T. J. Colloid Inter. Sci. 2011, 356, 107-110.
(17) Ghauch, A.; Ayoub, G.; Naim, S. Chem. Eng. J. (25) Dong, Y.C.; Ma, R.G.; Hu, M.J.; Cheng, H.;
2013, 228, 1168-1181. Tsang, C.K.; Yang, Q.D.; Li, Y.Y.; Zapien, J.A. J.
(18) Ayoub, G.; Ghauch, A. Chem. Eng. J. 2014, 256, Solid State Chem. 2013, 201, 330-337.
280-292.
(19) Anotai, J.; Masomboon, N.; Chuang, C.L.; Lu, M. Received for review February 16, 2015. Revised manuscript
C. Water Sci. Tech. 2011, 63, 1434-1440. received July 7, 2015. Accepted July 14, 2015.

J. Adv. Oxid. Technol. Vol. 19, No. 1, 2016 51