Chemical Engineering Journal 301 (2016) 1–11

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Catalytic degradation of diethyl phthalate in aqueous solution by

persulfate activated with nano-scaled magnetic CuFe2O4/MWCNTs
Xiaoling Zhang, Mingbao Feng, Ruijuan Qu, Hui Liu, Liansheng Wang, Zunyao Wang ⇑
State Key Laboratory of Pollution Control and Resources Reuse, School of Environment, Nanjing University, Nanjing, Jiangsu 210023, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

CuFe2O4/MWCNTs were prepared and

characterized.

Kinetics and mechanisms of DEP
degradation by CuFeO4/MWCNTs
were systematically studied.

The degradation pathways of DEP by
CuFe2O4/MWCNTs in persulfate
system were proposed.

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

Article history: Diethyl phthalate (DEP), a plasticizer widely used in chemical industry, has been classified as an endo-
Received 31 January 2016 crine disruptor. Therefore, it is urgent to develop methods for degradation of DEP to minimize its ecolog-
Received in revised form 16 April 2016 ical risk. In this study, copper ferrite decorated multi-walled carbon nanotubes magnetic nanoparticles
Accepted 18 April 2016
(CuFe2O4/MWCNTs MNPs) were prepared by sol–gel combustion method as catalysts for the degradation
Available online 30 April 2016
of DEP. The catalysts were characterized by scanning electron microscope, transmission electron micro-
scope, Fourier transform infrared spectroscopy, nitrogen gas uptake, X-ray diffraction, and X-ray photo-
Keywords:
electron spectroscopy. Catalytic degradation of DEP by persulfate (PS) was investigated with various
Diethyl phthalate
Persulfate
influencing factors including catalyst loading, PS concentrations, temperature and pH. Furthermore, the
CuFe2O4/MWCNTs CuFe2O4/MWCNTs MNPs showed high catalytic activity, stability and recyclability in DEP removal.
Sulfate radicals Especially, leaching of metal ions from reused CuFe2O4/MWCNTs was negligible (concentration < 0.4%),
indicating the resistance to oxidation. The electron paramagnetic resonance analysis confirmed that
the addition of CuFe2O4/MWCNTs into PS system can accelerate the generation of OH and SO 4 , and
the quenching experiments further certified the catalytic reaction was predominated by SO 4 . The degra-
dation intermediates were identified and the pathways were proposed. Overall, this study provides prac-
tical knowledge for DEP removal by CuFe2O4/MWCNTs activated PS at ambient temperature.
Ó 2016 Elsevier B.V. All rights reserved.

1. Introduction

Phthalate esters (PAEs) are a category of organic compounds

⇑ Corresponding author at: State Key Laboratory of Pollution Control and
Resources Reuse, School of the Environment, Xianlin Campus, Nanjing University,
Nanjing, Jiangsu 210023, PR China.
E-mail address: wangzy@nju.edu.cn (Z. Wang).
widely used as additives to improve the durability and flexibility
of polymeric materials [1]. Diethyl phthalate (DEP), a low-
molecular-weight PAE, has a wide variety of applications in agri-
cultural, industrial, and domestic applications; especially it is used
as plasticizers [2]. Due to the lack of covalent bonding with the

http://dx.doi.org/10.1016/j.cej.2016.04.096
1385-8947/Ó 2016 Elsevier B.V. All rights reserved.
2 X. Zhang et al. / Chemical Engineering Journal 301 (2016) 1–11
host materials and the relatively high water solubility, DEP can
readily enter the aquatic environment. DEP has already been
detected in wastewater, surface water and drinking water, leading
to increased exposure of organisms to this pollutant [3,4]. As an
endocrine disrupting chemical, DEP can interfere with the body’s
endocrine system, causing disease in both humans and wildlife.
In this sense, it is urgent to develop effective treatment methods
to remove DEP from aquatic environment.
In recent years, various methods have been applied to treat
PAEs pollutants including biotransformation [5], adsorption [6]
and advanced oxidation processes (AOPs) such as Fenton oxidation
[7], ozone oxidation [8], UV photolysis [9] photocatalytic oxidation
[10] and catalytic oxidation by magnetically reusable spinel ferrite
catalysts [11–13]. However, DEP is resist to biodegradation and
photolytic degradation, owing to the existence of benzene car-
boxylic group and the lack of light reaction at wavelengths
>300 nm [14]. At present, Sulfate radicals (SO 4 ) based AOPs are
increasingly used for the abatement of refractory compounds like
polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbon
(PAHs), etc. [15]. The highly reactive SO
4 can be generated by acti-
vation of persulfate (PS) via heat [16], metal ions (e.g., Fe2+, Co2+,
Cu2+) [17,18], and metal oxides (Fe3O4, CuO) [19,20].
Thermal activation of PS needs large amount of energy to heat
tons of water to reach the desired temperature, which significantly
increases the cost of water treatment. The catalytic activation of PS
by dissolved metal cations is challenged with the recycle of cata-
lysts and the possible secondary contamination of water. More-
over, the metal leaching cannot be absolutely neglected.
Therefore, it is necessary to prepare a recyclable and highly stable
catalyst to produce SO-4 in water treatment. CuFe2O4, a spinel fer-
rite, has been suggested as an effective catalyst in peroxymonosul-
fate (PMS) activation for oxidation of organic pollutants [21–23].
Meanwhile, CuFe2O4, nanoparticles has been used as a catalyst
for photocatalytic degradation of 4-Chlorophenol and for catalytic
oxidation of benzylic alcohols into carbonyl compounds [24,25].
However, the mechanism of PS activation by CuFe2O4 catalyst
has not been explored.
Multi-walled carbon nanotubes (MWCNTs) have unique prop-
erties, including large surface area, high stability and large
mechanical strength, which make MWCNTs suitable to be the sup-
porting materials for catalyst loading. Meanwhile, the advantages
of spontaneous redox reactions between MWCNTs and metal oxi-
des have been recognized in the literature [26,27]. The excellent
electrical conductivity of MWCNTs can not only help to stabilize
the active intermediate but also facilitate the catalytic processes
involving electron transfer.
To improve the degradation efficiency of DEP in PS system, the
novel catalysts CuFe2O4/MWCNTs were prepared through the sol–
gel combustion method and applied to active PS to generate SO
4 .
Compared to other preparation methods, the sol–gel combustion
method can effectively facilitate the mixing of different cations
in the complex solutions [28]. The synthesized CuFe2O4/MWCNTs
MNPs combined the advantages of CuFe2O4 and MWCNTs, and
are expected to be efficient in the catalytic activation of PS at room
temperature. Moreover, the effects of other key factors like catalyst
dosage, PS concentration, solution temperature, and solution pH on
the degradation rate were also investigated.
2. Materials and methods
2.1. Chemicals
DEP (CAS NO. 84-66-2, purity 99%) was purchased from Ling-
feng Chemical Reagent Co., Ltd. (Shanghai, China). Persulfate
(purity P 99.5%) was obtained from Nanjing Chemical Reagent
Co., Ltd. (Nanjing, China). Cupric nitrate [Cu(NO3)23H2O, purity
99%], ferric nitrate [Fe(NO3)39H2O, purity > 98.5%], citric acid
(C6H8O7, purity > 99.5%), sodium hydroxide (NaOH, purity 98%),
analytical grade ethanol (EtOH) and tert-butyl alcohol (TBA) were
purchased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai,
China). 5,5-Dimethyl-1-pyrrolidine N-oxide (DMPO) was supplied
by Aladdin Reagent (Shanghai, China). Methanol and formic acid
used in the high-performance liquid chromatography (HPLC) mea-
surement were of HPLC grade and obtained from Merck (Darm-
stadt, Germany). Carboxyl-functionalized multi-walled carbon
nanotubes (MWCNTs–COOH, purity > 95%, outside diameter 20–
40 nm) were purchased from Shenzhen Nanoport Co., Ltd. (Shen-
zhen, China). Ultrapure water (>18.2 MX cm) was prepared by a
Milli-Q Plus system (Millipore, Bedford, USA).
2.2. Preparation of CuFe2O4/MWCNTs MNPs
The sol–gel combustion method [29] was used to prepare
CuFe2O4/MWCNTs MNPs catalysts. The mass ratio of CuFe2O4 to
MWCNTs–COOH was optimized as 2:1. Specifically, 4.8 g Cu
(NO3)23H2O (0.02 mol), 16.2 g Fe(NO3)39H2O (0.04 mol) and
2.4 g MWCNTs–COOH were added into aqueous solution and
mixed thoroughly by ultrasonic (5 min). After stirring at 60 °C for
2 h, the citric acid (0.06 mol) was added. The obtained mixed solu-
tion was stirred at 60 °C (2 h) and then the homogeneous solution
was placed in water bath (90 °C) to wipe off water. The resulting
nitrate–citrate–MWCNTs complex gel were calcined at 400 °C
(typically) under nitrogen atmosphere (2 h) to get rid of the citric
acid, and the desired metal oxide product was formed.
2.3. Characterization of CuFe2O4/MWCNTs
A Quanta 200 scanning electron microscopic (SEM) instrument
(FEI, Netherlands) was used to observe the surface morphology of
CuFe2O4/MWCNTs MNPs. Transmission electron microscopy (TEM,
JEM-200CX) was performed using a JEOL 3000F field emission TEM.
X-ray powder diffraction (XRD) measurement was carried out on a
X’TRA X-ray diffractometer (ARL, Switzerland, k = 1.5406 Å, Cu Ka
radiation) at room temperature. X-ray photo-electron spectroscopy
(XPS, Al K-Alpha, Thermo Fisher Scientific, USA) with monochro-
matic Al Ka radiation at 1486.71 eV was employed to identify
the oxidation states of metals (Cu and Fe). Fourier-transform infra-
red (FT-IR) spectra were conducted on a FT-IR spectrometer with
OPUS Vertex 70 software 5.0 (Bruker Optics Inc.). The nitrogen
gas uptake isotherms were measured by Micromeritics ASAP
2020 (Micromeritics, USA) and the specific surface areas (SSAs)
were calculated based on Brunauer–Emmett–Teller (BET) model.
The magnetic properties (M–H curve) were measured by an ADE
4HF vibrating sample magnetometer at 300 K. The metal cations
released from the degradation process were measured by a Solar
M6 atomic absorption spectrophotometer (AAS, Thermo Fisher Sci-
entific, USA).
2.4. Catalytic degradation
The catalytic degradation experiments were performed in
150 mL batch reactors at 25.0 ± 0.2 °C, and the initial pH was set
at 7.0 ± 0.2. After 50 mL of DEP solutions (5 mg/L) were transferred
into the reactors, a pre-specified amount of PS and CuFe2O4/
MWCNTs were added to initiate the reaction. At pre-specified time
intervals (0, 5, 10, 15, 20, 25, 30 min), 0.4 mL of aqueous sample
was taken and quenched by 0.1 mL NaNO2 (0.02 mol/L). The influ-
ences of catalyst dosages on the catalytic degradation of DEP were
evaluated in a same way. The samples were all filtered through
0.22 lm filter for HPLC analysis.
 X. Zhang et al. / Chemical Engineering Journal 301 (2016) 1–11
The DEP catalytic degradation reactions described above were
repeated for five cycles to evaluate the recyclability of CuFe2O4/
MWCNTs catalyst. After each catalytic run, the catalyst was col-
lected by magnet, and washed by ultrapure water until the super-
natant was nearly neutral. Then, the catalyst was desiccated at
60 °C under vacuum. The recycled catalyst was used for subse-
quent catalytic runs under the same experimental conditions.
In addition, to determine the role of radical species formed in
the catalytic system, two series of quenching tests were carried
out by using TBA and EtOH as the radical scavengers, respectively.
All experiments were conducted in triplicate, and the mean values
were reported.
2.5. Analytical methods
DEP concentrations were analyzed by HPLC (Agilent, USA 1200)
with a C18 reversed phase column (Zorbax Eclipse XDB-C18
4.6 mm  150 mm, particle size 5 lm, Agilent, USA) and a UV
detection wavelength of 228 nm. The mobile phase used for HPLC
analysis was methanol/water (0.3% acetic acid) at a ratio of 70:30
(v/v) and the flow rate was set at 1.0 mL/min. The injection volume
was 20 lL and elution time was 4.5 min for all samples. The cali-
bration curve, measured in the concentration range of 1–25 mg/L,
showed a good linear correlation for DEP (R2 = 0.999) and the
detection limit (S/N = 3) of DEP was calculated as 0.052 mg/L. The
degradation intermediates of DEP were identified by the solid
phase extraction–liquid chromatography–mass spectrometry
(SPE–LC–MS). An ion-chromatograph system (ICS-1000, Dionex,
USA) was applied to quantify the three carboxylic acids (formate,
acetate and oxalate) generated from the DEP oxidation. Detailed
information was provided in Supporting Information (SI) Text S1.
Fig. 1. (a) SEM and (b) TEM images of CuFe2O4/MWCNTs and (c) FT-IR spectra of samples (CuFe2O4, CuFe2O4/MWCNTs and recycle CuFe2O4/MWCNTs) calcined at 400 °C.
3
Total organic carbon (TOC) of the reaction solutions were mea-
sured using a Shimadzu TOC-5000 total organic carbon analyzer
(Shimadzu, Kyoto, Japan). Based on the modified method of Liang
et al. [30], PS concentration was measured by a UV–vis spectropho-
tometer (Persee, Beijing, China) at 400 nm.
For radical measurements, electron paramagnetic resonance
(EPR) experiments were conducted on a Bruker EMX-10/12 spec-
trometer (Bruker, Bremen, Germany) with DMPO (80 mmol/L) as
a spin-trapping agent. PS and/or catalyst were added at pH
7.4 ± 0.1. After 1 min of reaction, samples were taken and analyzed
at room temperature.
3. Results and discussion
3.1. Characterization of CuFe2O4/MWCNTs catalysts
To confirm the loading of CuFe2O4 MNPs onto MWCNTs, SEM
images were measured with the samples calcined at 400 °C
(Fig. 1a). It was obviously seen that the surface of the MWCNTs
were attached a string of particles, probably due to the presence
of CuFe2O4. This phenomenon was similar to the result of a previ-
ous study [31]. Furthermore, the TEM image in Fig. 1b exhibited
that CuFe2O4 MNPs grew regularly on the MWCNTs surface with
diameters ranging from 0 to 25 nm (Fig. S2). Meanwhile, most of
the CuFe2O4 MNPs were strung by MWCNTs, indicating the suc-
cessful preparation of designed material. Although the products
were repeatedly washed by water in the catalytic runs, almost all
nanoparticles were still found on the surface of carbon nanotubes,
which indicated the strong interaction between MWCNTs and
CuFe2O4 MNPs. Thus, the catalysts can be used in subsequent
degradation experiments to improve the efficiency of DEP removal.
4 X. Zhang et al. / Chemical Engineering Journal 301 (2016) 1–11
Fig. 1c showed the FT-IR spectra of CuFe2O4 and CuFe2O4/
MWCNTs MNPs before and after recycle. The absorption band
around 570 cm1 in the FT-IR spectra verified the formation of
FeO bond with tetrahedral geometry in spinel-type complexes
[29,32–34]. Meanwhile, the absorption band at 480 cm1 was
attributed to the stretching vibration of Cu–O in the octahedral
compounds [35]. The presence of these characteristic peaks veri-
fied the existence of Fe3+ and Cu2+ in tetrahedral and octahedral
coordination environment, respectively [36]. The presence of car-
boxylic groups on MWCNTs was confirmed by C@O vibration peak
observed at 1700 cm1 in both as-synthesized and recycled sam-
ples. This means that the carboxylic groups remained after anneal-
ing and catalytic reaction, which is very important for the catalyst
to preserve the hydrophilicity and high dispersibility.
Nitrogen uptake isotherms of fresh CuFe2O4/MWCNTs and recy-
cled catalysts were displayed in Fig. 2. It should be noted that the
quick uptake at high pressure indicated the meso-pore nature of
these materials which was critical for free mass transportation of
oxidants and substrates. The specific surface areas (SSAs) of CuFe2-
O4, CuFe2O4/MWCNTs and the reused CuFe2O4/MWCNTs, calcu-
lated by the BET model, were 0.069, 40 and 38 m2/g, respectively.
The SSA of CuFe2O4/MWCNTs has no significant change after
reused by five times, indicating the highly stable skeleton and pore
structure of CuFe2O4/MWCNTs during the reaction. The nanocom-
posites displayed much higher SSA than pure CuFe2O4 due to the
highly porous nature of MWCNTs frameworks (measured
215 m2/g), which shown that MWCNTs were excellent supporting
materials for catalyst loading.
The XRD patterns of MWCNTs, CuFe2O4, as-synthesized CuFe2-
O4/MWCNTs MNPs and reused CuFe2O4/MWCNTs were shown in
Fig. 3. For CuFe2O4, the XRD pattern showed three intense diffrac-
tion peaks at 2h angle of 29.8°, 35.9°, and 62.5°, respectively. These
results were consistent well with the tetragonal spinel CuFe2O4
(JCPDS: 34-0425) [29]. These broad peaks indicated the nano-
sized nature of the CuFe2O4 particles [23]. For as-synthesized
CuFe2O4/MWCNTs MNPs, the peaks at 2h = 29.8°, 32.4°, 35.1°,
35.9°, 43°, 50.5°, 54.1°, 56°, and 62.5° corresponds to the diffraction
of cubic phase CuFe2O4, from planes (1 1 2), (1 0 3), (2 1 1), (2 0 2),
(0 0 4), (2 2 0), (3 1 2), (1 0 5), and (2 2 4), respectively [37–39]; the
other peaks were related to tetragonal CuFe2O4 [40]. The diffraction
peaks of CuFe2O4/MWCNTs MNPs were much narrower than bare
CuFe2O4, indicating the particle aggregation during annealing.
Before decoration, the main broad diffraction peak assigned to
MWCNTs (2h = 26°) [29] were also observed in CuFe2O4/MWCNTs,
indicating that the structures of MWCNTs were not destroyed dur-
ing the synthesis treatments. However, this peak became unobvi-
ous, which can be due to the much weaker diffraction intensity of
MWCNTs than CuFe2O4. Compared to MWCNTs, the characteristic
Fig. 2. Nitrogen adsorption–desorption isotherms of (a) CuFe2O4/MWCNTs and (b) reused CuFe2O4/MWCNTs (the insets of the graphs are BET surface area plots).
diffraction peaks of CuFe2O4 appeared in CuFe2O4/MWCNTs MNPs,
suggesting the successful synthesis of CuFe2O4/MWCNTs catalysts.
No additional peaks were observed in the XRD pattern of reused
CuFe2O4/MWCNTs catalysts after five cycles, showing that the
structure and component of the catalyst remained almost
unchanged after oxidation reaction.
The M–H curves of CuFe2O4 (Fig. S3), fresh CuFe2O4/MWCNTs
and reused CuFe2O4/MWCNTs Fig. 4a showed that the saturation
moment were about 30, 12 and 12 emu/g, respectively. The satura-
tion magnetization of CuFe2O4/MWCNTs was less than CuFe2O4,
which attributed to lower mass percentage of magnetic active
material in CuFe2O4/MWCNTs. The similar value of saturation mag-
netization of fresh CuFe2O4/MWCNTs and reused sample indicated
the high stability of the catalysts. Furthermore, an external mag-
netic field was applied to verify the magnetism of CuFe2O4/
MWCNTs. As showed in Fig. 4b, the catalysts were collected on
one side by the magnet and the suspension became clear. The good
magnetism of CuFe2O4/MWCNTs can assist to recycle the catalyst
by magnet.
The XPS spectra of CuFe2O4/MWCNTs MNPs were obtained in
order to understand the roles of Fe and Cu played for PS activation.
First, the results in Fig. 5 confirmed the presence of both Cu and Fe
elements in the nanocomposites. In the high resolution XPS spectra
of fresh CuFe2O4/MWCNTs (Fig. 5d and e), the peaks of Cu 2p3/2 and
Fe 2p3/2 individually appeared at 934.001 and 712.301 eV referring
to Cu(II) and Fe(III) [41]. Tetragonal CuFe2O4 were known to have a
spinel structure with virtually complete inversion [42]. Interest-
ingly, according to the deconvolution of envelop Fig. 5b and c, Cu
(I) and Fe(II) were found for a certain proportion, which was due
to the partial reduction of Cu(II) and Fe(III) on the surface of the
used catalysts. These results suggested that the catalytic activity
of CuFe2O4/MWCNTs MNPs should involve single electron transfer
mechanism in metal centers (vide infra).
3.2. DEP degradation by PS activated with CuFe2O4/MWCNTs
3.2.1. The comparison to several kinds of catalysts
To comprehensively evaluate the catalytic degradation perfor-
mance of DEP by CuFe2O4/MWCNTs, a series of side-by-side exper-
iments were performed using different catalysts (MWCNTs, Fe3O4,
CuFe2O4, Fe3O4/MWCNTs and CuFe2O4/MWCNTs) and two
different reaction conditions (adsorption and degradation). As
shown in Fig. 6a, DEP was totally eliminated in the presence of
CuFe2O4/WMCNTs in 30 min, whereas CuFe2O4 and MWCNTs
caused 33% and 69% removal of DEP, respectively. Meanwhile, PS
without the presence of any catalyst (control experiment) resulted
in only 10% DEP removal during the same time. Compared with
 X. Zhang et al. / Chemical Engineering Journal 301 (2016) 1–11
Fig. 3. XRD patterns of the samples (CuFe2O4, MWCNTs, CuFe2O4/MWCNTs, and
reused CuFe2O4/MWCNTs) calcined at 400 °C.
Fig. 4. (a) M–H hysteresis loops of fresh CuFe2O4/MWCNTs and recycled CuFe2O4/
MWCNTs after being used five times at 300 K, (b) magnetic characterization of
CuFe2O4/MWCNTs via an external magnetic field.
benchmark catalyst Fe3O4 and Fe3O4/MWCNTs reported previously
[43], our catalyst performed more than 60% and 20% faster in DEP
removal, respectively (Fig. S4a). Furthermore, the adsorption of
DEP by MWCNTs, CuFe2O4 and CuFe2O4/MWCNTs was measured
as 39%, 18% and 19%, respectively. We noted that the adsorption
5
effect of CuFe2O4/MWCNTs was less than half of MWCNTs, which
is very important for full recovery of the catalyst in practical use.
Considering the fast degradation rate and the limit amount of
adsorption, the novel catalyst CuFe2O4/MWCNTs is promising for
improving the degradation efficiency of DEP in PS system.
Furthermore, CuFe2O4/MWCNTs prepared with different mass
ratios of CuFe2O4 to MWCNTs had different catalytic performance
for the degradation of DEP (Fig. S4b). The degradation of DEP by
CuFe2O4/MWCNTs (1:1, 2:1, 4:1, 8:1) was measured as 43%,
100%, 57% and 31%, respectively. Apparently, CuFe2O4/MWCNTs
(2:1) had the highest catalytic potential. CuFe2O4/MWCNTs (4:1,
8:1) had more ratio of CuFe2O4, which was easily vulnerable to
agglomeration and lower the SSA of the catalyst, resulting in the
low catalytic activity. Meanwhile, the higher ratio of MWCNTs
was more conducive to the adsorption but degradation, accounting
for the low degradation of CuFe2O4/MWCNTs (1:1). Thus, CuFe2O4/
MWCNTs (2:1) were selected for the following experiment.
3.2.2. Effect of catalyst doses on DEP removal
The degradation of DEP at different catalyst doses (50, 100,
200 mg/L) were investigated in this study, which were shown in
Fig. 6b. As seen, the degradation efficiency of DEP was improved
with CuFe2O4/MWCNTs dosage increasing from 50 to 200 mg/L.
In this concentration range, the adsorption of DEP by the catalysts
was also improved. To be specific, the adsorption amounts onto
CuFe2O4/MWCNTs were increased largely from 15% to 30%, as the
degradation efficiency in 30 min increased from 75% at 50 mg/L
to 100% at 100 mg/L catalyst. The enhanced degradation efficiency
at higher catalyst dosage was largely attributed to the improved
availability of active sites in the solution, which would react with
PS to generate more SO 4 [44]. Thus, it is inferred that the active
sites on CuFe2O4/MWCNTs surface were still not totally occupied
by PS at the dose of 100 mg/L CuFe2O4/MWCNTs. Because the
degradation efficiency increased with the enhancing concentra-
tions of PS and then the radical scavenging ability of PS was also
increased [23]. The high adsorption capacity of catalysts was also
observed by Hu et al. [11] when they used Fe3O4/MWCNTs as cat-
alysts to degrade 17a-methyltestosterone. In general, the opti-
mized catalyst dosage is achieved at high DEP degradation rate
with minimum physical adsorption. Based on our results,
100 mg/L was selected as the optimal catalyst dosage and used in
the following experiments.
3.2.3. Effect of PS concentrations
It has been reported that the concentration of PAEs in plastic
and paint industry wastewater is about 10-100 mg/L [45]. To
explore the potential of using PS for the treatment of industrial
wastewater, the influence of initial PS concentrations on DEP
degradation was studied at three ratios of DEP to PS concentrations
(1:50, 1:100 and 1:200). As shown in Fig. 6c, the removal of DEP
was accelerated with decreasing the DEP to PS ratio. To be specific,
the degradation rate of DEP after 25 min was 59% at the ratio of
1:50, while DEP was removed 94% at the ratio of 1:100 and com-
pletely at the ratio of 1:200 during the same time period. It is pro-
posed that the generation of more SO 4 contributes to the more
rapid degradation of DEP at higher PS concentration. Similar results
were also obtained by Wang et al. [46]. However, the removal rate
of DEP was not proportional to the PS concentration, possibly due
to the quenching of SO 4 by self-coupling reaction [47] or residual
PS [48].
3.2.4. Effect of initial solution pH
The pH of the reaction solution was another important param-
eter influencing the oxidation of organic contaminants by PS [46].
Therefore, the impacts of pH (3–11) on DEP removal were evalu-
ated. As shown in Fig. 6d, the efficiency of DEP degradation
6 X. Zhang et al. / Chemical Engineering Journal 301 (2016) 1–11

Fig. 5. (a) Wide survey XPS spectrum, (b) Cu 2p and (c) Fe 2p XPS envelop of used catalyst, (d) Cu 2p and (e) Fe 2p XPS envelop of fresh CuFe2O4/MWCNTs MNPs.

decreased from 100% to 28% when pH was increased ranging from
3.0 to 11.0. This result was largely consistent with the study of Pu
et al. [49,50], who reported that acidic condition was more suitable
for the degradation of orange G and flumequine in PS system. SO 4
was the major active species under acidic conditions [51] and more
efficient elimination of DEP at lower pH can be explained by the
increasing rate of SO
4 generation as pH decreasing [52,16]. While
under basic conditions, OH turned out to be the predominant rad-
ical [51]. The radical interconversion reactions between SO 4 and
 
OH generated inert products (such as SO2 4 , HSO4 and oxygen)
[9], which reduced the concentration of active species leading to
sluggish degradation of organic contaminates [16]. Moreover, the
higher reactivity of SO 
4 than OH [52] towards DEP also con-
tributed to the more effective DEP removal in acidic conditions.
3.2.5. Effect of temperature
The effect of temperature (25, 30, 35 and 40 °C) on DEP removal
in PS system was shown in Fig. 7a. The results indicated that DEP
was completely removed after 25 min at 40 °C, while 87% DEP
was removed at 25 °C and 96% removed at 30 °C during the same
time. Thus, heat activation was beneficial to achieve efficient
removal of DEP. Similar results were also obtained in the PS oxida-
tion of methyl tert-butyl ether [53], flumequine [50] and dimethyl
phthalate (DMP) [46]. Control experiments without PS addition at
25 °C showed less than 6% loss of DEP after 30 min, indicating that
loss of DEP through adsorption by the reactors and/or evaporation
was insignificant.
Furthermore, the remaining DEP fraction (C/C0) versus reaction
time was simulated as pseudo-first-order kinetics, which was
 X. Zhang et al. / Chemical Engineering Journal 301 (2016) 1–11
Fig. 6. (a) Various catalysts (MWCNTs, CuFe2O4, CuFe2O4/MWCNTs), (b) the catalyst dosages, (c) the molar ratio of [DEP] to [PS] and (d) pH on the effect of DEP removal
efficiency. The initial DEP concentration was 5 mg/L.
consistent with previously reported PS-based system for degrada-
tion of organic contaminants [54]. The rate constant was
0.0797 min1 (R2 = 0.99) at 25 °C, 0.1146 min1 (R2 = 0.94) at
30 °C, 0.1472 min1 (R2 = 0.97) at 35 °C, and 0.1768 min1
(R2 = 0.94) at 40 °C. According to Van’t Hoff equation, the negative
slope showed in Fig. 7a inset indicated that the catalytic reaction
process was endothermic and the activation energy (Ea) was calcu-
lated as 52.6 kJ mol1 (R2 = 0.99).
3.3. Reusability and stability of CuFe2O4/MWCNTs MNPs
The DEP catalytic degradation experiments were conducted for
five cycles to evaluate the reusability of the CuFe2O4/MWCNTs
MNPs catalysts, where the recycled catalysts were used for subse-
quent catalytic runs under the same experimental conditions. As
shown in Fig. 7b, the removal efficiency remained at 87% and the
recovery yield of the catalyst after five runs measured 0.48 mg (ini-
tial 0.50 mg) after five cycles, suggesting the high activity of CuFe2-
O4/MWCNTs maintained during the recyclability test. Similar
results were also observed by Ding et al. [23], who reported that
CuFe2O4 had high catalytic activity and could be reused in degrada-
tion of tetrabromobisphenol A at ambient temperature.
Moreover, to evaluate the leaking of copper and iron ions from
CuFe2O4/MWCNTs MNPs into the solutions during the recycle
experiments, the reaction solutions were analyzed by AAS. As indi-
cated in Fig. S5a, the concentration of leaked copper and iron
cations was measured to be lower than 0.4 mg/L. The leaking effect
was suppressed as increasing the number of reaction runs and
7
finally became undetectable after five cycles due to the detection
limit of AAS instrument, which demonstrated the high stability
of CuFe2O4/MWCNTs MNPs in the catalytic process. Furthermore,
to evaluate the effect of metal ions leakage on the DEP removal,
0.4 mg/L of Cu2+ and Fe3+, which was the highest concentration
of leached metal ions, were used to degrade DEP under standard
condition (Fig. S5b). The degradation efficiency of metal ions was
less than 10% within 30 min while the DEP was completely elimi-
nated by CuFe2O4/MWCNTs under the same condition, indicating
the metal–ion-catalyzed homogeneous reaction only contributing
a small proportion of catalytic degradation of DEP. Similarly, Hu
et al. [11] reported that the leached iron from Fe3O4/MWCNTs
was less soluble and had very weak catalytic activity.
3.4. The activation mechanism of CuFe2O4/MWCNTs catalysts
To elucidate the reaction mechanism, EPR experiments were
conducted to monitor the types of radicals generated during the
oxidation of DEP. Strong signals of both OH and SO
4 radicals were
observed and presented in Fig. 7c. Furthermore, the signals of
DMPO radical adducts in CuFe2O4/MWCNTs catalyzed PS system
were much stronger than pure PS system, especially for SO 4 ,
which indicated that the generation of SO4 was significantly facil-
itated by the addition of CuFe2O4/MWCNTs into PS system. The
much stronger signals of DMPOOH adducts than DMPOSO4
adducts was attributed to the fast transformation of DMPOSO4
adducts to DMPOOH adducts via nucleophilic substitution [51].
8 X. Zhang et al. / Chemical Engineering Journal 301 (2016) 1–11

Fig. 7. (a) Effects of solution pH on the degradation of DEP, (b) recyclability of CuFe2O4/MWCNTs MNPs for DEP removal, (c) EPR spectra in PS and CuFe2O4/MWCNTs/PS
systems (DMPO concentration 80 mmol/L), and (d) the effect of quenchers (TBA and EtOH) on DEP removal. Reaction conditions: initial DEP concentration 5 mg/L,
temperature 25.0 ± 0.4 °C, initial pH 7.0 ± 0.2, catalyst dosage 100 mg/L, the molar ratio of DEP to PS 1:100.

 
To further identify the types of radicals generated and the major S2 O2
8 þ H2 O ! HSO5 þ HSO4 ð2Þ
reactive radicals dominating the degradation reaction, EtOH and
TBA were added into reaction solution as the radical quenching
agents. Alcohols with or without a-hydrogen have different reac-  Cu3þ þ HSO5 ! Cu2þ þ SO
5 þH
þ
ð3Þ
tivity with radical species. EtOH (with a-hydrogen) reacts with 2+
 In general, Cu is the critical catalytic center to activate PS.
OH (1.2  109–2.8  109 M1 s1) or SO 7 7
4 (1.6  10 –7.7  10 -
Basically, PS can react with Cu2+ to produce Cu3+ and SO 4 (Eq.
M s ) at comparable rates, while TBA (without a-hydrogen)
1 1
(1)), which dominated the oxidation of DEP proved by quenching
has 1000-fold higher rate constant with OH ((3.8–7.6)  108 - 
tests and EPR analysis. On the other hand, S2O2
8 can produce HSO5
mol L1 s1) than with SO 4 ((4.0–9.1)  105 mol L1 s1) [55].
by hydrolysis under acidic condition (Eq. (2)). Recovery of Cu2+
Therefore, EtOH was used to scavenge both radicals, and TBA was
center was achieved by the reduction of Cu3+ by either HSO 5 (Eq.
used to selectively quench OH.
(3)) or DEP. It should be noted that the reaction between in situ
As exhibited in Fig. 7d, DEP was absolutely decomposed in
generated Cu3+ and DEP [56] was another possible mechanism
30 min when no quenching agent was added. In the presence of
for enhanced DEP removal.
50 mM TBA, the DEP removal rate was decreased by 24% during
the same time period, owing to the quenching of OH. However,
by changing TBA with EtOH, the DEP removal rate was decreased  Cu2þ þ HSO5 ! Cuþ þ SO
5 þH
þ
ð4Þ
by 72%. The larger rate decreasing in DEP removal by EtOH than
by TBA suggested that the primary radical species generated dur-
ing the activation of PS were SO   Fe3þ þ HSO5 ! Fe2þ þ SO5  þHþ ð5Þ
4 , even though OH was also
involved in this process. Similar findings were reported in both
thermo- and CuFe2O4 activated PS systems, in which SO 4 domi-
 Fe3þ þ  Cuþ ! Fe2þ þ  Cu2þ ð6Þ
nated the degradation of flumequine [50] and tetrabromobisphe-
+ 2+
nol A [23], respectively. Interestingly, Cu and Fe were found in the recycled CuFe2O4/
According to the results of EPR and quenching experiments, the MWCNTs catalyst by XPS analysis. The similar results were
mechanism of DEP degradation in CuFe2O4/MWCNTs catalyzed PS reported by Ding’s group when they explored the effective activa-
system was proposed as follows: tion of HSO5 by CuFe2O4 nano-particles. They attributed this phe-
nomenon to the reactions between HSO 5 and initial metal ions
 Cu2þ þ S2 O2
8 ! Cu
3þ
þ SO 2
4 þ SO4 ð1Þ
(Cu2+ and Fe3+). Although oxidizing of HSO5 by Cu
2+
or Fe3+ is ther-
 X. Zhang et al. / Chemical Engineering Journal 301 (2016) 1–11 9

modynamically unfavorable, the reactions were still possible to [57] and then took part in electron transfer reaction in the oxida-
take place at highly reactive metal center in defects or oxygen tion of organic pollutants [58], and (2) highly electronic conductive
vacancies since CuFe2O4 particles were nanoscaled. MWCNTs facilitated the electron transfer between metal ions to
regenerate the catalytic centers.
 Cuþ þ HSO5 ! Cu2þ þ SO
4 þ OH

ð7Þ Compared with Cu-based PS activation not relying on sulfate
radical generation [59,60], our activation mechanism is different.
 Cuþ þ S2 O2
8 ! Cu
2þ
þ SO4  þSO2
4 ð8Þ In the non-sulfate radical generation system, approximately 0.16
equivalent (to 2,4-DCP) of PS (2% of the total PS dosage) can be
 Fe2þ þ HSO5 ! Fe3þ þ SO4  þOH ð9Þ decomposed without presence of 2,4-DCP. However, in our system,
10 equivalent (to DEP) of PS (10% of the total PS dosage) can be
 Fe2þ þ S2 O2
8 ! Fe
3þ
þ SO 2
4 þ SO4 ð10Þ decomposed without presence of DEP. This phenomenon indicated
that our catalysts can activate PS leading to its decomposition not
+ 2+
More importantly, Cu and Fe can be oxidized by and S2O2
8 relying on the presence of DEP. In other words, our system
HSO5 , which not only were the additional pathways to generate involved outer orbital electron transfer reaction to activate PS,
SO
4 but also brought the metal centers back to the initial oxida- which is not the same as the CuBi2O4 system for BTZ degradation.
tion state for the next catalytic cycle.
SO
4 þ DEP ! degraded products ð12Þ
3.5. Oxidation products and pathways
SO 2 þ
4 þ H2 O ! SO4 þ H þ HO

ð13Þ
Oxidation products of the DEP degradation by PS were con-
 firmed by ion chromatography system (Fig. S6a), and were
OH þ DEP ! degraded products ð14Þ
observed by the LC–TOF–MS in the negative mode with MS2 Scan.
SO
4was the major active oxidant in the degradation system A total of four intermediates were identified by LC–TOF–MS and
and reacted with DEP achieving the full degradation (Eq. (12)). In their MS data and proposed structures were shown in Figs. S7, S8
addition, the formation of OH, which was detected by EPR, can and Table S1. In most cases, the results of high resolution mass
be attributed to reaction between SO 4 and water (Eq. (13)). Con- measurements matched well with the proposed molecular formu-
sidering the 23% less of degradation of DEP with selective OH las (Table S1) (<3 ppm error), which provided solid supports for the
quencher (Fig. 7d), the degradation activity of OH cannot be structural assignments. Although the data on DEP oxidation inter-
neglected (Eq. (14)), even though small portion of SO 4 was mediates by PS are lacking, some references can be found in several
quenched as well. recent degradation studies to facilitate the products identification
At last, it should be pointed out that MWCNTs were not only the [61–63]. Specifically, the four products with the precursor ion at
frameworks for loading of CuFe2O4. Two more advantages for the m/z 237.0761, 181.0136, 193.0509 and 165.0187 were identified.
presence of MWCNTs in the catalyst are: (1) MWCNTs activated Typical fragment losses like OH, COOH, and C2H5 were observed
PS to generate reactive species through non-radical mechanisms from the MS2 analysis.

Fig. 8. Proposed reaction pathways for the DEP oxidation by PS. Reaction conditions: initial DEP concentration 5 mg/L, temperature 25.0 ± 0.4 °C, initial pH 7.0 ± 0.2, catalyst
dosage 100 mg/L, the molar ratio of DEP to PS 1:100.
10 X. Zhang et al. / Chemical Engineering Journal 301 (2016) 1–11
According to the chemical structures of the identified oxidation
intermediates and earlier references on the DEP removal, two pos-
sible transformation pathways of DEP were proposed (Fig. 8). On
the one hand, DEP was attacked by OH to form the hydroxylated
product (P1, m/z 237.0761), and P2 at m/z 181.0136 was subse-
quently generated by hydrolysis. On the other hand, DEP under-
went sequential hydrolysis and oxidative decarboxylation in the
catalytic reaction, producing P3 at m/z 193.0509 and phthalic acid
(P4, m/z 165.0187) successively. Furthermore, relative high con-
centration of oxalate was detected in reaction solution (Fig. S6a),
while formate and acetate were not detected probably due to their
instability. During the DEP oxidation process, the TOC removal was
measured to reflect the mineralization of DEP (Fig. S6b). The results
indicated that TOC reduction proceeded much more slowly than
did the degradation of DEP. After 30 min, DEP was completely
decomposed, but the TOC removal was approximately 23%. Some
small molecular carbolic acids were produced during the oxidation,
which can account for this phenomenon. The products were trans-
ferred to small molecular carboxylic acids by oxidative ring open-
ing and they were further oxidized to CO2 and H2O.
4. Conclusions
CuFe2O4/MWCNTs was synthesized by loading CuFe2O4 on
carboxylic-acid-functionalized MWCNTs and fully characterized.
Notably, compared to bare MWCNTs and CuFe2O4, CuFe2O4/
MWCNTs MNPs can effectively decompose DEP at ambient tem-
perature, showing the high catalytic performance of the compos-
ites. CuFe2O4/MWCNTs MNPs were stable in the catalytic process
and can be reused for five times with good catalytic performance.
Furthermore, the study of degradation kinetics showed that the
degradation rate improved with the catalyst loading, PMS dosages,
temperature, and solution pH increasing to a large extent. EPR and
quenching experiments proved that SO 4 was the major radical
species to degrade DEP. Based on these results, CuFe2O4/MWCNTs
showed promising potential of applications in aqueous purification
and pollution control due to their good stability and reusability.
The intermediate products were identified, and their degradation
pathways were proposed. Moreover, the systematic studies of cat-
alytic mechanism provide the fundamental understanding of the
treatment of DEP contaminated water with CuFe2O4/MWCNTs at
room temperature, which is of significance to design new catalysts
for advanced oxidation process.
Acknowledgements
This research was financially supported by the National Natural
Science Foundation of China (Nos. 21577063, 21377051) and the
Major Science and Technology Program for Water Pollution Control
and Treatment of China (No. 2012ZX07506-001).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.cej.2016.04.096.
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