Environ. Process.

(2017) 4:169–182
DOI 10.1007/s40710-016-0199-2

O R I G I N A L A RT I C L E

Fenton-Like Degradation of Methylene Blue

by Ultrasonically Dispersed Nano Zero-Valent
Metals

Jiwan Singh 1 & Jae-Kyu Yang 2 & Yoon-Young Chang 3 &

Janardhan Reddy Koduru 4

Received: 21 August 2016 / Accepted: 17 November 2016 / Published online: 22 November 2016
# Springer International Publishing Switzerland 2016

Abstract This study investigated the methylene blue (MB) degradation via ultrasonically
dispersed nano zero-valent metals (NZVMs) under sono-advanced Fenton process. The
NZVMs were analyzed by Fourier transform infrared spectroscopy (FTIR), scanning electron
microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS).
The consequences of the NZVMs dose, the pH of solution, concentrations of MB and H2O2 on
the decolorization efficiency of MB were assessed by a sono-advanced Fenton process. The
degree of methylene blue degradation could be increased by increasing the amount of NZVMs
and the concentration of H2O2 up to certain limits. The methylene blue removal efficiency was
reduced from 100 to 75.2% with an increase in the pH from 2 to 6.75. The methylene blue
removal efficiency was also decreased slightly from 100 to 98.9% with increasing concentration
of the methylene blue from 10 to 80 mg/L. The degradation of methylene blue by ultrasonically
dispersed NZVMs was found to be suitably described by the pseudo-first-order kinetics. It was
found that the oxidation of methylene blue was triggered by hydroxyl radicals generated during
the sono-advanced Fenton process.

* Jiwan Singh
jiwansingh95@gmail.com
* Janardhan Reddy Koduru
reddyjchem@gmail.com

1
Department of Environmental Science, Babasaheb Bhimrao Ambedkar University,
Lucknow 226025, India
2
Ingenium College of Liberal Arts, Kwangwoon University, Seoul 139-701, Republic of Korea
3
Department of Environmental Engineering, Kwangwoon University, Seoul 139-701,
Republic of Korea
4
Graduate School of Environmental Studies, Kwangwoon University, Seoul 139-701,
Republic of Korea
170 Singh J. et al.

Keywords Nano zero-valent metals . Methylene blue . Ultrasound . Mechanism . Degradation .

Kinetic study

1 Introduction

At present, wastewater produced from industrial activity can contain organic compounds
(El-Qanni et al. 2016). Colors are extensively used in the chemical and textile industries
and are discharged into the environment, leading to water pollution (Zhang et al. 2015).
Dyes can be classified according to their structure as anionic and cationic (Al-Degs et al.
2008). The release of dye containing wastewater into water stream can affect the aesthetic
nature and also inhibit transmission of sunlight into water (Mall et al. 2006). Furthermore,
dyes can cause severe damage of human health such as dysfunction of kidney, reproduc-
tive system, liver, brain and central nervous system (Amin 2009). The complete removal
of dyes from wastewater is difficult due to the presence of aromatic rings in the structures
(Liu et al. 2012). Numerous technologies have been applied to treat wastewater. However,
suitable and ecofriendly techniques are necessary for the proper treatment of wastewater.
The application of nanoparticles has been considered as an emerging technology with the
potential to improve water purification efforts (Qu et al. 2013). Many types of metal-
based nanoparticles have been effectively applied as adsorbents or catalysts to remove
organic and inorganic contaminants from wastewater (Singh et al. 2013; Gómez-Pastora
et al. 2014; Singh et al. 2016a). The removal of methylene blue through a chemical
oxidation process, by applying nano-size materials, has been established as highly effec-
tive, because its size is small and its surface area is high. Nano zero-valent iron has been
utilized for the degradation of colors from wastewater (Wang et al. 2014; Weng and
Huang 2015).
The preparation of NZVMs through a liquid-phase reduction method is a very common
method used around the world (Fang et al. 2010). Many salts of various metals have been
applied for the synthesis of nano metallic particles (Xi et al. 2014). In place of the salts of
metals, the leaching liquor of automobile shredder residue (ASR) is very useful for the
synthesis of nano metallic particles. ASR contains high amounts of heavy metals such as
Zn, Cu, Mn, Fe and Ni with concentrations (in mg/kg) of 5571.3, 1957.1, 1068.8, 151,800 and
95.9, respectively (Singh et al. 2016a).
The advanced oxidation process may be referred as hydroxyl radicals generated process in
an aqueous medium for the purpose of attacking organic pollutants (Khokhawala and Gogate
2010; Singh et al. 2016a). Ultrasonic treatment of organic pollutants is also known as an
advanced oxidation process, and this can be used for the degradation of methylene blue (Weng
and Huang 2015) and phenols (Singh et al. 2016a). The application of an ultrasonic process
with catalysts in the presence of hydrogen peroxide rises the speed of the degradation of
organic pollutants though oxidation, with the development of less toxic or non-toxic interme-
diate compounds (Nikolopoulos et al. 2006). Extremely combative hydroxyl radicals are
created in a fluid medium due to cavitation (Chand et al. 2009).
In this study, NZVMs were recovered from the waste material such as ASR. The recovery
of NZVMs from the ASR reduces the hazardous properties of ASR. The degradation of
organic compound by advanced Fenton-like process, i.e. by NZVMs, is much faster than the
Fenton process due to the generation of more hydroxyl radicals. The application of NZVMs
for degradation has some limitations, such as the oxidation occurs under acidic condition. In
Degradation of Methylene Blue by Nano Zero-valent... 171

this condition small concentrations of metal ions can be entered in solution. However, this
problem can be solved by adding a quantity of lime.
Many studies have been carried out on degradation of methylene blue by Fe0 (Noubactep
2009), Fe0 aggregate in ultrasound enhanced advanced Fenton process (Weng and Huang
2015), cellulose modified nano zero-valent iron (Wang et al. 2015), nanoscale zero-valent iron
(nZVI) assembled on magnetic Fe3O4/reduced graphene oxide (Yang et al. 2015). However,
there is no study available on degradation of methylene blue by ultrasonically dispersed
NZVMs (recovered from ASR). Therefore, the objectives of the present study were: to
synthesize NZVMs from the leachate of ASR, to apply it in the degradation of methylene
blue, and to evaluate the ultrasound effects on the degradation of methylene blue.

2 Materials and Methods

2.1 Heavy Metal Extraction and Preparation of NZVMs

The heavy metal extraction process from ASR was carried out according to a method
established by Singh et al. (2016a). The detail experimental conditions are as follows: 1.0 M
of HNO3, 1 g of solid sample mixed with 10 mL of acidic solution, temperature of 303 K and
ultrasound power level of 500 W. To improve the heavy metals extraction from the ASR, an
ultrasonic generator (VCX-500, Sonics & Materials, Inc., USA) was used. Filter paper
(0.45 μm) was used to separate the extract. The synthesis of NZVMs from the extracted
solution was done at pH 7. 100 mL of the solution with the extracted metals was taken into a
500 mL beaker and the pH of the solution was then adjusted with 1.0 M of NaOH. The
preparation of the NZVMs was done according to the method established by Singh and Lee
(2015). 0.1 M solution of NaBH4 was added to the extracted solution at neutral pH via a
dropwise method using a burette. Subsequently, the solution was stirred using a magnetic
stirrer at temperature 25 ± 0.5 °C. The solution at neutral pH due to the addition of a reducing
agent became black which indicates that the metal ions have been converted into NZVMs. A
centrifuge was used to separate the synthesized NZVMs. The separated NZVMs were washed
with distilled water, followed by ethyl alcohol to eliminate the additional NaBH4. The NZVMs
were then dried at 50 °C in vacuum. Figure 1 shows the different steps of NZVMs synthesis
and its application for methylene blue degradation.

2.2 Degradation of Methylene Blue by NZVMs

Sono-advanced Fenton process reactions were performed in a glass reaction vessel (250 mL)
with thin and indented bottom for ensuring efficient energy transmission using an ultrasonic
generator. The ultrasonic generator was equipped with a titanium probe with 13 mm diameter,
capable of operating continuously at a fixed frequency and power of 20 kHz and 500 W,
respectively. Sonication of the methylene blue solution was carried out in air. 100 mL of a
methylene blue solution at different concentrations were added to glass beaker containing
appropriate amounts of NZVM particles and suitable concentration of H2O2 was then added.
The effects of different initial methylene blue concentrations (10, 20, 40 and 80 mg/L) on the
methylene blue degradation process was studied under the following test conditions: pH 3.0;
NZVMs dose 0.10 g/L; concentration of H2O2 100 mM; ultrasound power 500 W. The effect
of different values of pH (2.0, 3.0, 4.0, 5.0 and 6.75) on methylene blue degradation process
172 Singh J. et al.

Fig. 1 Flow chart of the NZVMs preparation process and its application for methylene blue removal

was studied under the following test conditions: methylene blue concentration 20 mg/L;
NZVMs dose 0.10 g/L; concentration of H2O2 100 mM; and ultrasound power 500 W. The
effect of the different doses of NZVMs (0.05, 0.10, 0.15 and 0.20 g/L) on the methylene blue
degradation process was studied under the following test conditions: methylene blue concen-
tration 20 mg/L; pH 3.0; concentration of H2O2 100 mM; ultrasound power 500 W.
The effect of different concentrations of H2O2 (25, 50, 100 and 150 mM) on methylene blue
degradation process was studied under the following test conditions: methylene blue concen-
tration 20 mg/L; pH 3.0; NZVMs dose 0.10 g/L; ultrasound power 500 W. The samples were
collected after reaction times of 5, 10, 15, 20, 25 and 30 min. The samples were filtered
through 0.25 μm filter paper and the residual methylene blue concentrations were then
analyzed. The degradation rate of methylene blue by the NZVMs was also measured without
the addition of H2O2 under ultrasonic irradiation. All tests were done at least three times.
The degradation of methylene blue by ultrasonically dispersed NZVMs was verified by a
pseudo-first-order reaction (Singh et al. 2016a):
lnðCt =C0 Þ ¼ −kt ð1Þ
where C0 signifies the starting concentration of methylene blue (mg/L) and Ct is the concentra-
tion of methylene blue at time t (min). Additionally, k is the pseudo-first-order constant (min−1).

2.3 Analysis

The heavy metal concentrations in the ASR were determined by a method of Singh et al.
(2016b). Approximately 1.0 g ASR sample was digested with 20 mL of an acid mixture
(HCl:HNO3 3:1) in a closed Teflon vessel and then heated at 150 °C for 8 h using a
temperature controlled hot plate. All samples were filtered through filter paper (0.45 μm)
and samples were kept at 4 °C before the analysis. Inductively coupled plasma atomic
Degradation of Methylene Blue by Nano Zero-valent... 173

emission spectroscopy (ICP-AES) (Perkin Elmer Inc.-Optima 2000 DV) was used to analyze
heavy metal concentrations in the solutions.
The methylene blue concentration was measured by a UV–visible spectrophotometer (UV
1601, Shimadzu). A maximum wavelength (λmax) of 665 nm was selected to analyze all
samples. A pH meter (Orion 3 Star, Thermo Scientific) was used to measure the solution pH.
The NZVMs were studied by a scanning electron microscope (SEM; S–4300CX, Hitachi,
Japan). X-ray photoelectron spectroscopy (XPS) (Escalab–210 electron spectrophotometer,
Spain) was used to analyse different forms of metals existing in the NZVMs. To determine the
different functional groups of NZVMs, a Fourier-transform infrared spectrophotometry (FTIR)
analysis was performed using a model ISF 66/S spectrophotometer, Bruker. The crystalline
structure of the NZVMs before and after as methylene blue degradation was analyzed by X-ray
diffraction (XRD) using a model Rigaku D/Max-2500 X-ray diffractometer (Japan).
Analysis of variance (ANOVA) was used to assess the significance of results and p < 0.05 was
considered to be statistically significant difference. Origin Pro software was used for Statistical
analysis of data.

3 Results and Discussion

3.1 Characterization of NZVMs

SEM and XRD analysis of NZVMs has been published in our previous study (Singh et al.
2016a). SEM analysis of NZVMs shows that the synthesized particles were not spherical.
Nanoparticles showed clumping may be due to magnetic interaction between the Fe nanopar-
ticles. The size of the NZVMs were less than 50 nm. The XRD results represent the changes in
the diffraction patterns of the NZVMs. The diffraction peak (2θ=30.8) may signify FeO,
Fe2O3, Cu2O, or ZnO. The average size of the nanoparticles was calculated at 4.3 nm from the
XRD widening of the peak using the Scherrer formula.
As shown in Fig. 2a, the FTIR spectra of the NZVMs were determined before and after the
reaction. Band peaks at 977.7 and 1388.8 cm−1 were also observed on the surfaces of the
NZVMs; there was evidence of M-O stretching associated to MO, M2O3 and M3O4, repre-
sentative of the availability of metal oxides on the surfaces of the NZVMs (Zha et al. 2014;
Singh et al. 2016a). The FTIR spectra of the NZVMs showed broad bands at 3306.2 cm−1
allocated to the hydroxyl group (O-H). The peaks at 1640.8, 1388.8 and 977.7 cm−1 are
assigned to C = O bonds (Singh et al. 2011). After the degradation of methylene blue, the peaks
of these bands shifted from 3306.2 to 3219.8 cm−1, from 1640.81 to 1655.3/1612.5 cm−1, from
1388.8 to 1403.3 cm−1 and from 977.7 to 1057.6 cm−1, which was expected to correspond to
M-O stretching and was representative of the NZVMs being moderately corroded after
degradation (Zha et al. 2014). A new peak was also observed at 797.6 cm−1, after the sono-
advanced Fenton process of the methylene blue, corresponding to Fe-O stretching pertaining to
Fe2O3/Fe3O4 (Zha et al. 2014). Furthermore, few new bands at 3522.7 and 1612.5 cm−1 were
observed after the sono-advanced Fenton process. These bands may stem from the degraded
products of methylene blue.
Figure 2b presents the results of the analysis of the survey spectra by XPS, representing the
various elements (e.g., C, O, Fe, Cu, Zn, Mn etc.) which exist on the surfaces of the NZVMs.
The C 1 s peak identified at 283.5 eV may represent C-C or C-H bonds (Haeberle et al. 2013;
Kim et al. 2014). The O 1 s peak at 530.2 eV was ascribed to the availability of a hydroxyl unit
174 Singh J. et al.

Fig. 2 FTIR spectra of the NZVMs (a); and XPS analysis results of the NZVMs (b) before and after the reaction

on the surfaces of the NZVMs (Dwivedi et al. 2015). This peak was shifted at
532.3 eV and the peak intensity was reduced after the degradation, and is representing
the metal oxides that contributed to the reaction. Heavy metals existed as MOs, and
MCO3, where M represents metals. Heavy metals also existed in elemental states. The
binding energies (BE) of Cu were found to be approximately 977.5 eV. This peak
intensity was reduced after the reaction of Cu0 with MB, indicating that Cu0 was
converted to Cu+/Cu2+ (Dong et al. 2014). The BE of Fe 2p was found to be
711.6 eV; this peak may be allotted to Fe oxides, signifying that the exteriors of the
NZVMs were bound with a film of Fe oxide (Liu et al. 2015). This peak intensity was
decreased after the degradation, approving that oxides of Fe participated in the meth-
ylene blue degradation process. The BE of the Zn 2p spectra before the reaction
demonstrates a peak at 1019.5 eV, close to the BEs of ZnO (1022 eV) (Morozov et al. 2015).
This peak did not appear after the reaction, confirming an important alteration during the
reaction. The BE of the Mn 2p before the reaction displays a peak at 652.6 eV; this peak may
represent MnO and MnO2 (Ilton et al. 2016). Conversely, this peak was not found after the
degradation, which shows that the oxides of Mn contributed to the reaction.

3.2 Degradation of Methylene Blue by NZVMs

3.2.1 Effect of NZVMs Dose on Methylene Blue Degradation

Figure 3 shows the effect of different NZVMs doses (0.05, 0.10, 0.15 and 0.20 g/L) on the
removal of methylene blue (experimental conditions: pH of 3.0, methylene blue concentration
of 20 mg/L; H2O2 concentration of 100 mM; reaction time of 30 min; ultrasound power of
500 W). The degradation of methylene blue was improved from 98.8 to 99.8% with an
increase of the amount of NZVMs from 0.05 to 0.10 mg/L at a reaction time of 30 min due
to the availability of many reaction sites when increasing the NZVMs dose (Fang et al. 2010).
Conversely, upon an addition of more nanoparticles, the methylene blue degradation effec-
tiveness was reduced slightly, possibly due to the scavenging effect of hydroxyl radicals and
the tramping of NZVMs in the system (Xu and Wang 2011). The pseudo-first-order reaction
rate constant (k) and correlation coefficient (R2) at different quantities of NZVMs are specified
in Table 1. When the quantity of NZVMs was increased from 0.05 to 0.10 g/L, the value of k
Degradation of Methylene Blue by Nano Zero-valent... 175

Fig. 3 Effects of the different doses

of NZVMs on the methylene blue
degradation process (experimental
conditions: methylene blue
concentration 20 mg/L; pH 3.0;
concentration of H2O2 100 mM;
ultrasound power 500 W)

was improved from 0.14 to 0.20 min−1 (inset of Fig. 4a). The value of k was reduced with a
further increase of the amount of NZVMs. The best dose of NZVMs was 0.10 g/L and was
selected for subsequent methylene blue degradation. The results of methylene blue degradation
were found significantly different from each other when changing dose of NZVMs (likelihood
ratio F = 7.47, probability p < 0.05).

3.2.2 Effect of pH on Methylene Blue Degradation

The pH value of the solution is an important factor that affects the degradation of methylene
blue in the NZVM system (Zhao et al. 2010). The solution pH shows an important part that
affects oxidation power in the sono-advanced Fenton process, because it controls the specia-
tion of metal ions and governs the generation of hydroxyl radicals (Weng and Huang 2015).
The pH values of the methylene blue solution were maintained at 2, 3, 4, 5 and 6.75 with a

Table 1 The kinetic results for MB degradation by ultrasonically dispersed NZVMs under sono-AFP

NMPs dose (g/L) C0 (MB) (mg/L) Initial pH H2O2 conc. (mM) k (min−1) R2

0.05 20 3.0 100 0.1423 0.9871

0.10 20 3.0 100 0.2027 0.9433
0.15 20 3.0 100 0.1787 0.9565
0.20 20 3.0 100 0.1423 0.9319
0.10 20 2.0 100 0.1819 0.8213
0.10 20 4.0 100 0.0846 0.9486
0.10 20 5.0 100 0.0819 0.9402
0.10 20 6.75 100 0.0359 0.8639
0.10 10 3.0 100 0.2105 0.9294
0.10 40 3.0 100 0.1760 0.9065
0.10 80 3.0 100 0.1190 0.8673
0.10 20 3.0 0 0.0862 0.9615
0.10 20 3.0 25 0.1849 0.9559
0.10 20 3.0 50 0.2530 0.9697
0.10 20 3.0 150 0.2255 0.9591
176 Singh J. et al.

Fig. 4 Kinetic study of methylene blue degradation by NZVMs under the sono-advanced Fenton process with
different parameters: NZVMs dose (a); pH values (b); initial concentration of methylene blue (c); and concen-
tration of H2O2 (d)

0.1 M HCl and 0.1 N NaOH. Figure 5 shows the influence of various pH values on the methylene
blue degradation by NZVMs (experimental conditions: initial methylene blue concentration of
20 mg/L; NZVMs dose of 0.10 g/L; concentration of H2O2 of 100 mM; reaction time of 30 min;
ultrasound power level of 500 W).
The highest methylene blue degradation percentage was attained at a pH 2.0, and the
degradation efficiency of methylene blue was found to be approximately 100% after a reaction
time of 30 min. However, the lowest methylene blue degradation percentage was observed at the
natural pH of the solution (pH 6.75) with degradation percentage of 75.2%. The methylene blue
degradation rate was reduced with a rise of the pH value from 2.0 to 6.75. This can be attributed

Fig. 5 Effects of different pH

values on the methylene blue
degradation process (experimental
conditions: MB concentration
20 mg/L; NZVMs dose 0.10 g/L;
concentration of H2O2 100 mM;
and ultrasound power 500 W)
Degradation of Methylene Blue by Nano Zero-valent... 177

to the decay of H2O2 with the reduced catalytic activity of the NZVMs (Babuponnusami and
Muthukumar 2012). The k and R2 values for the removal of methylene blue by NZVMs at
various pH values are presented in Table 1. The value of k increased from 0.1819 to
0.2027 min−1 when the pH was changed from 2.0 to 3.0; however, upon an additionally rise
in the pH, the k value was reduced (inset of Fig. 4b). The changes in the methylene blue
degradation rate with a change of the pH of the solution were found to be significant (F = 8.70,
p < 0.001).

3.2.3 Effect of Initial Methylene Blue Concentration on Methylene Blue Degradation

Figure 6 exhibits the consequence of different initial methylene blue concentrations on the
degradation of methylene blue by NZVMs (experimental conditions: NZVMs dose of 0.10 g/
L; pH of 3.0; H2O2 concentration of 100 mM; reaction time of 30 min; ultrasound power of
500 W). The degradation effectiveness of methylene blue was decreased from 100 to 98.9%
with an increase of the methylene blue concentration from 10 to 80 mg/L in 30 min of reaction
time. This result stems from the rapid covering of the active surfaces of the NZVMs by the
methylene blue molecules at a high concentration, resulting in a decrease in the production of
hydroxyl radicals in the reaction (Xu and Wang 2011). The residual concentration of methy-
lene blue was found to be zero at reaction times of 30, 40, 50, and 60 min for initial methylene
blue concentrations of 10, 20, 40 and 80 mg/L, respectively. The values of k and R2 for various
methylene blue concentrations are presented in Table 1. When the methylene blue concentra-
tion was raised from 10 to 80 mg/L, the k value decreased from 0.2027 to 0.1190 min−1 (inset
of Fig. 4c). The changes in methylene blue degradation for various initial concentrations of
methylene blue were found statistically significant (F = 7.09, p < 0.001).

3.2.4 Effect of the Concertation of H2O2 on Methylene Blue Degradation

Figure 7 shows the influence of various concentrations of H2O2 on the methylene blue
degradation rate (test conditions: NZVMs dose of 0.10 g/L; pH of 3.0; initial methylene blue
concentration of 20 mg/L; degradation time of 30 min; ultrasound power of 500 W). The
degradation of methylene blue was very slow with NZVMs (without addition of H2O2) due to
the inadequate generation of hydroxyl radicals during the degradation. The degradation
efficiency of methylene blue was increased greatly from 92.6 to 100% with an increase in

Fig. 6 Effects of different initial

methylene blue concentrations on
the methylene blue degradation
process (experimental conditions:
pH 3.0; NZVMs dose 0.10 g/L;
concentration of H2O2 100 mM;
ultrasound power 500 W)
178 Singh J. et al.

Fig. 7 Effects of different

concentrations of H2O2 on the
methylene blue degradation
process (experimental conditions:
methylene blue concentration
20 mg/L; pH 3.0; NZVMs dose
0.10 g/L; ultrasound power
500 W)

the H2O2 concentration from 0 to 50 mM, because of generation of numerous hydroxyl

radicals (Xu and Wang 2011). The methylene blue degradation was observed rapid at
50 mM of H2O2. However, upon further increase in the concentration of H2O2, the degradation
efficiency was reduced; this might be due to recombination of hydroxyl radicals and scaveng-
ing effect of H2O2 (Babuponnusami and Muthukumar 2012).
The values of k and R2 for the different concentrations of H2O2 are specified in Table 1. The
k value was enhanced from 0.0862 to 0.2530 min−1 with an increase in the initial concentration
of H2O2 from 0 to 50 mM; however, the k values were decreased at high concentration of
H2O2 (inset of Fig. 4d). The changes in the methylene blue degradation efficiency at various
concentrations of H2O2 were found to be statistically significant (F = 5.31, p < 0.001).

3.2.5 Synergistic Effects of Combined Sonication with Fenton Reagent

The methylene blue degradation percentage was observed about 100% with NZVMs, when
combined with ultrasound power and H2O2 (Fig. 8). The degradation efficiency of methylene
blue by NZVMs with a combination of H2O2 and ultrasound power shows great potential for
methylene blue degradation in a very short time as compared to combination of the NZVMs/
ultrasound (92.6%) or NZVMs/H2O2 (53.3%) or H2O2/ultrasound (65.9%). The oxidation of
methylene blue with either ultrasound power with H2O2 or in the absence of H2O2 (NZVMs/
ultrasound) required more sonication time to attain sufficient methylene blue degradation. In
the ultrasound/H2O2 system, the methylene blue removal efficiency was low (65.9%) at
30 min of degradation time. However, in the NZVMs/ultrasound system, the methylene blue
degradation rate was observed about 92.6%. This low removal of methylene blue occurred due
to the insufficient quantity of hydroxyl radicals produced in the sono-advanced Fenton
process. In the NZVMs/ultrasound/H2O2 system, the support of ultrasound power, significant-
ly improved solubility of metal ions from the NZVMs during the reaction, and enhanced the
methylene blue degradation efficiency to 100%.

3.3 Possible Mechanisms for the Degradation of Methylene Blue by NZVMs

The degradation of methylene blue by hydroxyl radicals is one of the most common mech-
anisms for the degradation of methylene blue under sono-advanced Fenton process. Many
hydroxyl radicals are generated in the reaction between NZVMs and H2O2 (Fang et al. 2010;
Degradation of Methylene Blue by Nano Zero-valent... 179

Fig. 8 Methylene blue removal efficiency under different experimental conditions (concentration 20 mg/L;
pH 3.0; dose 0.10 g/L)

Cheng et al. 2015). Under ultrasonic power, a pressure pulse is produced during the break-
down of a solo cavity resulting in a great rate of generation of hydroxyl radicals (Chand et al.
2009). Furthermore, the methylene blue degradation rate was greatly increased by NZVMs
with the addition of H2O2. Sono-catalysis process produces hydroxyl radicals in the presence
of H2O2 (Eq. 2) and H2O2 may form due to the recombination of hydroxyl radicals (Eq. 3).
ÞÞÞÞÞÞ
H2 O2 → 2OH o ð2Þ

OHo þ OHo →H2 O2 ð3Þ

where ‘))))))’ represents the ultrasound waves.
Ultrasonic power improves the corrosion of NZVMs and uninterruptedly releases consid-
erable numbers of metal ions. Sufficient concentration of metal cations (Mn+) and H2O2 are
required to stimulate Fenton reactions (M here implies metal).). Therefore, ultrasonic irradia-
tion strongly improved the sono-advanced Fenton process. Previous research reported that
metals other than Fe are also feasible as active species for catalytic wet peroxide oxidation, and
thus, stated that metals have two conceivable oxidation states, e.g., Mn+ and M(n+1)+ (Ribeiroa
et al. 2016; Singh et al. 2016a). It is believed that initially the NZVMs are corroded in the
presence of the ultrasound wave and the H2O2 wave under acidic conditions, oxidizing M0 to Mn+
(Eqs. 4 and 5). The oxidized metals (Mn+) then further react with H2O2 in the sono-advanced
Fenton process to generate hydroxyl radicals and M(n+1)+, as described by Eq. (6) (Ribeiroa et al.
2016). In the presence of ultrasound waves, complex redox reactions occur, leading to the
formation of hydroperoxyl radicals, and these radicals react with M(n+1)+ and reduced to Mn+
ions (Eq. 7) (Chand et al. 2009). The creation of sufficient concentration of hydroxyl radicals is
the main cause of methylene blue degradation, as described in Eq. (8).
ÞÞÞÞÞÞ
M0 → Mn þ2e− ð4Þ

M0 þ nHþ →Mnþ þ nH2 ð5Þ

180 Singh J. et al.

Mnþ þ H2 O2 →Mðnþ1Þþ þ OHo þ OH− ð6Þ

Mðnþ1Þþ þ HO2 o →Mnþ þ O2 þ Hnþ ð7Þ

OHo þ methylene blue→Intermediate products þ CO2 þ H2 O ð8Þ

where, M is the metal, n is the number of valences, O denotes the oxides, ‘))))))’ represents the
ultrasound waves, and x and y correspondingly represent the number of moles.

4 Conclusions

The present study demonstrated that NZVMs are highly efficient for methylene blue degra-
dation with the effect of H2O2 and ultrasonic power. The process is affected by the solution
pH, the NZVMs dose, the concentration of H2O2, the initial concentration of methylene blue
and the ultrasonic power. Increases of the pH and the initial concentration of methylene blue
decreased the decolorization efficiency; however, an increase of the NZVMs dose and the
concentration of H2O2 increased the methylene blue degradation efficiency of the sono-
advanced Fenton process. An excess concentration of H2O2 showed a scavenging effect,
which decreased the methylene blue removal efficiency.
The highest methylene blue removal rate achieved was 100% with a reaction time of
30 min (experimental conditions: a dose of NZVMs of 0.10 g/L; a concentration of H2O2 of
50 mM; a methylene blue concentration of 20 mg/L; and a pH of 3.0). The highest concen-
tration of methylene blue (80 mg/L) was removed at 60 min of reaction time. The pseudo-first-
order kinetics was appropriate for the degradation of methylene blue by NZVMs. The value of
the rate constant k was raised with an increase of the NZVM dose to 0.10 g/L, while for further
increase of this dose, the k value was reduced. The values of k were decreased with an increase
of the initial concentration of methylene blue from 10 to 80 mg/L. The degradation efficiency
of methylene blue by NZVMs with a combination of H2O2 and ultrasound was found to be
100% in 30 min of reaction time as compared to combination of the NZVMs/ultrasound
(92.6%) or NZVMs/H2O2 (53.3%) or H2O2/ultrasound (65.9%). This study demostrates that
methylene blue can be removed successfully by a sono-advanced Fenton process at a reaction
time of 30 min.

Acknowledgments The present research was conducted with the support of a research grant from Kwangwoon
University in 2016. This work was also supported by the Korean Ministry of the Environment as part of the
BGAIA project^ (2014000550003).

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