Materials Science & Engineering B 249 (2019) 114420

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Materials Science & Engineering B

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

Cobalt ferrites/activated carbon: Synthesis, magnetic separation and T

catalysis for potassium hydrogen persulfate
⁎
Huidong Chena,1, Yanting Yanga, , Junqi Weia,1, Jiankang Xub, Jing Lia, Panfeng Wanga,
Jingcai Xua, Yanbing Hana, Hongxiao Jina, Dingfeng Jina,b, Xiaoling Penga, Bo Honga,
⁎
Hongliang Gea, Xinqing Wanga,
a
College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, China
b
Quality and Technical Supervision Inspection Center of Yongkang, Jinhua 321300, China

A R T I C LE I N FO A B S T R A C T

Keywords: Magnetic cobalt ferrites (CoFe2O4)/activated carbon (AC) nanocomposites were prepared by the hydrothermal
Nanocomposites method, and then the catalysis for potassium hydrogen persulfate (PMS) to degrade methylene blue (MB) was
Advanced oxidation investigated. The results indicated that 9 wt% CoFe2O4 nanoparticles supplied the sufficient magnetic response
Adsorption for magnetic separation and activated PMS to generate SO4−% radicals. The pore-structures of AC could adsorb
Magnetic response
the residual MB in high concentration near CoFe2O4 catalysts, and promoted MB degradation with SO4−% ra-
Degradation
dicals. CoFe2O4/AC nanocomposites presented the good stability and reusability. It was proved that the sy-
nergistic effect of PMS and CoFe2O4/AC nanocomposites could greatly improve the MB removal to 100% at the
optimized conditions for 60 min.

1. Introduction conditions such as pH, formation of sludge residues, ineffective utili-

zation of quickly generated %OH and limited removal of organic carbon
Nowadays, water protection had become one of the most widely [10,11]. Due to the higher redox potential (2.5–3.1 V) at natural pH,
concerned problems in human society, and the high-concentration or- more selective for destruction of pollutants and longer-lived, SO4−% had
ganic in wastewater presented the largest threat to our water resources attracted the great interest for the degradation of the refractory or-
with the rapid development of economy. However, it was difficult to ganics, which could be generated by peroxymonosulfate (PMS) or
deal with the refractory organics with the relative molecular mass from persulfate (PS) during their activation [12,13]. Potassium hydrogen
several thousand to tens of thousands by the biological treatment persulfate (PMS, 2KHSO5·KHSO4·K2SO4), the mixture of persulfate (PS,
methods [1]. Compared with the traditional method, advanced oxida- S2O82−) and peroxymonosulfate (PM, HSO5−), was very stable in water
tion process (AOPs) had been developed to solve the above challenges solution both in acidic and alkaling conditions [14,15]. Up to now,
for the universality and presented the huge potential prospect in ap- there was a variety of methods for the generation of SO4−% by the
plication [2–4]. With the strong oxidative radicals, AOPs could degrade catalyzing to PMS, such as transition metal catalysis (e.g., Co2+, Fe2+,
the refractory organics to the low-toxic and non-toxic small molecules Mn2+, Ru3+), UV, electrochemistry method [16–20]. Each way had
in the reaction conditions of the high temperature, high pressure, already been reported by researchers in sewage treatment. Because of
electricity, sound, light irradiation and catalysts [5,6]. According to the the low production cost and high catalytic efficiency, transition metal
difference of radical-generation and reaction conditions, it was divided catalysis was widely used in catalyzing PMS [21–23]. For example,
into photochemical oxidation, catalytic wet oxidation, sonochemical Gong et al. [24] prepared Fe3O4/graphene nanocomposites as the het-
oxidation, ozone oxidation, electrochemical oxidation and Fenton oxi- erogeneous catalysts to activate PMS for degradation of methylene blue
dation [7–9]. (MB). Lin et al. [25] used cobalt hexacyanoferrate to prepare the
Owing to the high oxidizing ability, the sulfate radicals (SO4−%) and magnetic carbon/cobalt/iron nanocomposites to activate PMS, which
hydroxyl radicals (%OH) have been widely used in AOPs to degrade exhibited the higher catalytic activity than Co3O4. Deng et al. [16]
organic pollutants. The application of %OH was limited by many successfully synthesized spinel CoFe2O4 and MnFe2O4 ferrites to

⁎
Corresponding authors.
E-mail addresses: 14a0505087@cjlu.edu.cn (Y. Yang), wxqnano@cjlu.edu.cn (X. Wang).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.mseb.2019.114420
Received 26 February 2018; Received in revised form 10 June 2019; Accepted 7 September 2019
0921-5107/ © 2019 Elsevier B.V. All rights reserved.
H. Chen, et al. Materials Science & Engineering B 249 (2019) 114420

activate PMS, exhibiting the promising potential application to degrade 5 °C/min. The magnetic properties of the prepared sample were mea-
pharmaceuticals in water pollution. However, the application of metal sured by a vibrating sample magnetometer (VSM: LakeShore-7407, up
catalysts has been limited due to the disadvantages of the secondary to 1.5 T) at room temperature.
pollution, economical infeasibility and environmental toxicity [26,27].
Considering the secondary pollution for the transition metal catalysts, 2.4. Degradation of MB
the transition metal catalysts-based AOPs were limited for the waste-
water treatment in practical [28,29]. The degradation experiments for MB with AC and CoFe2O4/AC
In order to overcome the above disadvantages, the catalysts should nanocomposites were carried out at room temperature for the different
be loaded on the carriers [24,30,31], and then the metal catalysts could time. We mainly concerned the following three factors: MB con-
be separated after redox [32,33]. Owing to the high surface area and centration, dosing quantity of CoFe2O4/AC nanocomposites and PMS. A
excellent adsorptive capacity, activated carbon (AC) had become one of certain amount (0 g~0.06 g) of CoFe2O4/AC nanocomposites were put
wonderful adsorbents (economic cost, effectiveness, and environ- into glass vessels containing 100 mL MB (50 mg/L~200 mg/L) solution,
mental) for the removal of organic contaminants and heavy metal ions and then added PMS (0 mmol~3.5 mmol). After the degradation in the
from wastewater and could also act as the good catalyst carriers [34]. fixed time, AC was separated with cellulose filter paper and CoFe2O4/
Relevant reports indicated that a series of spinel ferrites (MFe2O4, AC nanocomposites were separated with an outer magnet from the
M = Zn, Co, Mn, Pd, Cd, Ni, Cr, Cu, Ag) catalysts could act as the ac- solution. The MB concentrations were determined by spectro-
tivation of PMS for the degradation of pollutants in sewage, which photometer (Shimadzu UV-3600) at 665 nm. The percentage MB re-
CoFe2O4 presented the highest catalytic performance and efficiency in moval efficiency (ŋ, %) were calculated with the equation following:
PMS excitation [35]. Furthermore, CoFe2O4 nanoparticles exhibited the η (%) = (C0 − Ce )/ C0 × 100 , in which ŋ was MB removal percent (%), C0
excellent magnetic performance, which usually was used as the mag- and Ce were the initial MB concentration and the MB concentration
netic mediums for the magnetic separation [30]. after adsorption with AC or degradation with CoFe2O4/AC nano-
Combining the advantages of AC and CoFe2O4 nanoparticles, composites.
CoFe2O4/AC nanocomposites were expected to possess the high cata-
lytic performance for PMS, excellent adsorptive properties and suitable 3. Results and discussion
magnetic response. In this paper, CoFe2O4/AC nanocomposites were
synthesized by the hydrothermal method, and then the activation for The XRD patterns of AC and the prepared CoFe2O4/AC nano-
PMS to degrade MB, the reusability and the magnetic response was composites were illustrated in Fig. 1. All peaks were normalized ac-
investigated in detail. The as-prepared samples were characterized and cording to the maximum peak. Two broad peaks at about 2θ = 25° and
discussed by X-ray diffraction (XRD), thermal gravity analysis (TGA) 43° were observed in AC, which indicated the existence of amorphous
and vibrating sample magnetometer (VSM). The influence of the con- carbon. The diffraction peaks of CoFe2O4/AC nanocomposites could be
tent of PMS and CoFe2O4/AC nanocomposites on the removal of MB perfectly indexed to the cubic spinel phase structure of CoFe2O4 (JCPDS
was investigated in detail, and the magnetic response and reusability of card No. 22-1086) with the space group Fd-3m (No.227) [36]. No other
CoFe2O4/AC nanocomposites was discussed. peaks of impurities were observed, implying the single CoFe2O4 spinel
phase in CoFe2O4/AC nanocomposites.
2. Materials and methods The components of AC and CoFe2O4/AC nanocomposites were dis-
cussed by TGA in Fig. 2. The TGA curve of AC presented the obvious
2.1. Materials two-step weight loss. The first gentle slope of the weight lost occurred
below 100 °C, which should be attributed to dehydration and deso-
Biological activated carbon (100 meshes) was provided by Xingyu rption of adsorbed gas. Owing to the decomposition of amorphous
Activated Carbon Co., LTD. (Zhejiang, China). All other chemicals, in- carbon, the second steep slope was observed from 400 °C to 560 °C, and
cluding cobalt nitrate [Co(NO3)2·6H2O], ferric nitrate [Fe(NO3)3·9H2O], the weight (2%) hardly changed above 560 °C. Similarly, the TGA curve
PMS (KHSO5·0.5KHSO4·K2SO4), sodium hydroxide (NaOH) and me- of CoFe2O4/AC nanocomposites also showed the similar two-step
thylene blue (MB), purchased from Hangzhou Chemical Co., LTD. weight loss, which the first gentle slope came from the dehydration and
(Zhejiang, China) were analytic grade. All solutions were prepared with desorption of gas. The second steep slope was observed from 320 °C to
deionized water. 470 °C due to the decomposition of the amorphous carbon. Compared

2.2. Preparation of CoFe2O4/AC nanocomposites

Typically, magnetic CoFe2O4/AC nanocomposites were fabricated

as the following. 5 mmol Co(NO3)2·6H2O and 10 mmol Fe(NO3)3·9H2O
were dissolved into 100 mL distilled water, then a certain amount of AC
were added into the above solution at room temperature. The molar
ratio of AC: Co: Fe was 200:2:1. After vigorous stirring for 24 h, 2 mol/L
NaOH solution was added drop wise to keep the pH value to 12. The
mixture solution was laid into a reaction kettle and hydrothermal
treated at 160 °C for 12 h. Finally, the prepared products were washed
until pH = 7 using the distilled water and separated by magnetic se-
paration technique, then the products were dried in an oven at 100 °C.

2.3. Characterization of CoFe2O4/AC nanocomposites

The phase structure of CoFe2O4/AC nanocomposites was char-

acterized by an XRD diffractometer (DX2700 China) with the Cu-Kα
radiation (λ = 1.54051 Å, step 0.02°) at 40 kV and 30 mA. Pyrolysis
process (TGA/DSC) of the as-prepared nanocomposites was tested by a
thermal balance instrument (SDT Q600, TA) in air with a heating rate of Fig. 1. XRD patterns of AC and CoFe2O4/AC nanocomposites.

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H. Chen, et al. Materials Science & Engineering B 249 (2019) 114420

detail and the reusability of CoFe2O4/AC nanocomposites was also

considered. In PMS and CoFe2O4/AC nanocomposites system for the
wastewater treatment, CoFe2O4 nanoparticles both acted as the mag-
netic mediums and activators for PMS to generate radicals. AC not only
was used to anchor CoFe2O4 nanoparticles, but also absorbed MB in
high concentration near CoFe2O4 nanoparticles to promote the de-
gradation of MB. PMS could generate radicals for the degradation of MB
via Eqs. (1)–(5) [39,40], where SO5−% possessed the much low oxi-
dizability (E0 = 1.1 V) [41]. Co2+ and Fe3+ activated PMS to form
SO4−% and SO5−% radicals according to Eqs. (1) and (2), while the
above formed Co3+ and Fe2+ also could catalyze PMS to SO4−% and
SO5−% radicals obeying Eqs. (3) and (4). With the reaction of OH¯ with
H+, SO4−% and SO5−% with MB, respectively, SO4−% radicals were
continually generated until PMS went out. Furthermore, SO4−% radicals
maybe react with H2O to form %OH radicals to degrade MB, which the
dominated role for the MB degradation was distinguished later.

Co2+ + HSO5− → Co3+ + SO4−% + OH¯ (1)

Fig. 2. TGA curves of AC and the CoFe2O4/AC nanocomposites.
Fe 3+
+ HSO5− → Fe 2+
+ SO5−% +H +
(2)
−
with AC, the mass percent of the implanted CoFe2O4 nanoparticles was Co 3+
+ HSO5 → Co 2+
+ SO5−% + H +
(3)
deduced to be about 9% in CoFe2O4/AC nanocomposites. Owing to the
Fe2+ + HSO5− → Fe3+ + SO4−% + OH¯ (4)
catalysis of CoxFey alloys reduced by amorphous carbon, the tempera-
ture of the decomposition of the amorphous carbon for CoFe2O4/AC SO4−% + H2O → SO42− + H+ + %OH (5)
nanocomposites was lower to about 100 °C than that of AC. According
to the previous work [30], CoFe2O4/AC nanocomposites should possess The removal of MB with the different content of CoFe2O4/AC na-
the high surface area of about 1100 m2/g−1, which should present the nocomposites and PMS were investigated in detail. The influence of the
excellent adsorptive performance for the MB adsorption. concentration of PMS on the removal of MB was discussed firstly and
The magnetic response of CoFe2O4/AC nanocomposites was ana- the result was given in Fig. 4, in which the CoFe2O4/AC was 0.04 g and
lyzed by VSM and the hysteresis loop was shown in Fig. 3. Saturation the concentration of MB was 100 mg/L in 100 mL aqueous solution.
magnetization (Ms) of CoFe2O4/AC nanocomposites was 5.6 emu·g−1, Without PMS, the MB removal percent was about 35% for the adsorp-
which was enough for the magnetic separation technique. Ms of the as- tion of CoFe2O4/AC nanocomposites. CoFe2O4/AC nanocomposites
prepared magnetic CoFe2O4/AC nanocomposites was higher than could absorb MB in higher concentration near catalysts for the higher
others’, and the 23 wt% Fe3O4-doped AC nanocomposites only pre- surface area, which promoted the degradation of MB in the higher
sented Ms of 2.78 emu·g−1 [37,38]. In this way, CoFe2O4/AC nano- concentration of SO4−% generated with PMS and CoFe2O4 nano-
composites possessed the enough magnetic response with as few as particles. MB could be removed rapidly with the introduction of PMS.
possible CoFe2O4 nanoparticles, which ensured the highest adsorptive The removal of MB increased with PMS content up to 1.5 mmoL with
performance of CoFe2O4/AC nanocomposites. The magnetic response the value of 100%. When PMS was excessive, the excessive SO4−% or
%
was also investigated by an outer magnet with the surface magnetic OH would produce SO5−% with less reactivity according to the Eqs. (7)
field 1800 Oe, and the experimental photos in the inset of Fig. 3 re- and (8) [42]. Therefore, the degradation by PMS and adsorption with
vealed that the sample could be easily separated within 1 min com- AC both contributed to the removal of MB in the CoFe2O4/AC and PMS
pletely. system.
From the above analysis, CoFe2O4/AC nanocomposites with the SO4−% + HSO5− → SO5−% + HSO4− (7)
spinel phase structure presented the high surface area and excellent
%
magnetic response. In the following, the catalysis of CoFe2O4/AC na- OH + HSO5− → SO5−% + H2O (8)
nocomposites for PMS to degrade MB with AOPs was investigated in

Fig. 4. MB removal curves versus CoFe2O4/AC nanocomposites with 1.5 mmol

Fig. 3. VSM curves of CoFe2O4/AC nanocomposites. PMS.

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H. Chen, et al. Materials Science & Engineering B 249 (2019) 114420

Fig. 5. MB removal curves versus PMS with 0.05 g CoFe2O4/AC nanocompo-

sites.
Fig. 7. Cycling runs for the removal of MB in the CoFe2O4/AC/PMS system.
Reaction conditions: MB = 100 mg/L; PMS = 1.5 mM; catalyst = 0.4 g/L.
The influence of the content of CoFe2O4/AC on the degradation of
MB was given in Fig. 5, in which the PMS was fixed at 1.5 mmoL in
100 mL MB (100 mg/L) solution. Without CoFe2O4/AC nanocompo- in the optimized conditions (MB = 100 mg/L; PMS = 1.5 mM and cat-
sites, the degradation of MB with PMS was only about 25% in 60 min. alysts = 0.4 g/L). After each recovery, CoFe2O4/AC nanocomposites
The removal of MB increased greatly with the CoFe2O4/AC content for were collected by an external magnet and washed with ethanol and
the introduction of CoFe2O4/AC nanocomposites. This should be at- deionized water for several times, and then dried at 90 °C for the next
tributed to the catalysis of Co2+ and Fe3+ for PMS to generate oxyra- experiment. The results of recycling test for the MB degradation with
dicals. The removal of MB enhanced greatly at the first 15 min, and MB CoFe2O4/AC nanocomposites and PMS were shown in Fig. 7. Only a
could be 100% removal for 0.04 g, 0.05 g and 0.06 g CoFe2O4/AC slight decrease in the catalytic activity of CoFe2O4/AC for the PMS to
within 60 min. From the above analysis, the optimized conditions for removal MB was observed, and the MB removal maintained as high as
the MB degradation with CoFe2O4/AC nanocomposites and PMS was about 96% after four continuous cycles. The weakly decrease of re-
0.04 g CoFe2O4/AC and 1.5 mmoL PMS in solution. To determine the moval efficiency in CoFe2O4/AC and PMS system could be attributed to
ceiling MB concentration of degradation, MB concentration was con- the negligible loss of CoFe2O4 MNPs and the decay of active catalytic
trolled at 50 mg/L, 100 mg/L, 150 mg/L and 200 mg/L, and other re- sites caused by oxidation-reduction reaction from the catalyst surface
action conditions for MB degradation were kept as 0.04 g CoFe2O4/AC [16]. Therefore, it could be concluded that the as-prepared CoFe2O4/AC
and 1.5 mmol PMS in Fig. 6. It was obvious that the removal rate of MB nanocomposites represented the excellent reusability in dyes degrada-
decreased gradually with the increase of MB concentration from 50 mg/ tion.
L to 200 mg/L. When the MB concentration was higher than 150 mg/L There were three kinds of radicals such as SO4−%, SO5−% and %OH
and 200 mg/L, MB could not be completely degraded for the in- from PMS and CoFe2O4/AC nanocomposites in solution. Owing to the
sufficient PMS. low oxidizability compared with SO4−% and %OH, SO5−% was ignored in
Furthermore, the repeatability of CoFe2O4/AC nanocomposites was MB degradation [43]. In order to reveal the mechanism of MB de-
very important for the practical application. The stability and recycl- gradation with PMS and CoFe2O4/AC nanocomposites, ethanol and t-
able of CoFe2O4/AC nanocomposites to activate PMS was investigated butanol (TBA) were chosen as two kinds of radical scavengers to verify
the dominant role of SO4−% and %OH in this reaction. Ethanol reacted
with both SO4−% and %OH at high rates. While the influence of TBA on
%
OH was much higher than that of SO4−%, which was widely used as the
radical scavengers for %OH [44,45]. The degradation of MB with PMS
and CoFe2O4/AC nanocomposites with two quenching agents (0.1 M)
was shown in Fig. 8. As shown, MB could be completely removed in
60 min without radical scavengers, and the degradation of MB de-
creased to about 82% and 43% for the introduction of TBA and ethanol,
respectively. With the same amount of ethanol and TBA, ethanol owned
the higher suppression on the removal of MB in PMS and CoFe2O4/AC
nanocomposites, indicating the dominant role of SO4−% in MB de-
gradation. Thus, PMS generated the SO4−% radicals with the catalysis of
CoFe2O4/AC nanocomposites for MB degradation mainly according to
Eqs. (1)–(4).

4. Conclusions

Magnetic CoFe2O4/AC nanocomposites were synthesized by the

hydrothermal method, which presented the good magnetic response
with Ms of 5.6 emu·g−1. It was proved that the synergistic effect of PMS
Fig. 6. The optimum MB concentration of CoFe2O4/AC nanocomposites and and CoFe2O4/AC nanocomposites could greatly increase the MB re-
PMS. moval to 100% at the optimized conditions for 60 min. The adsorption

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H. Chen, et al. Materials Science & Engineering B 249 (2019) 114420

J. 310 (2017) 41–62.

[6] Y. Liu, X. He, Y. Fu, et al., Degradation kinetics and mechanism of oxytetracycline
by hydroxyl radical-based advanced oxidation processes, Chem. Eng. J. 284 (2016)
1317–1327.
[7] L.M. Zhang, M. Qin, Y.K. Yu, et al., Preparation of ternary Pt–NiO–ZnO hybrids and
investigation of its photocatalytic performance toward methyl orange, J. Mater.
Sci.-Mater. Electron. 30 (2019) 5158–5169.
[8] A.J. Jafari, B. Kakavandi, N. Jaafarzadeh, et al., Fenton-like catalytic oxidation of
tetracycline by AC@Fe3O4 as a heterogeneous persulfate activator: Adsorption and
degradation studies, J. Ind. Eng. Chem. 45 (2017) 323–333.
[9] M.R. Heidari, R.S. Varma, M. Ahmadian, et al., Photo-Fenton like catalyst system:
activated carbon/CoFe2O4 nanocomposite for reactive dye removal from textile
wastewater, Appl. Sci.-Basel 9 (2019) 963.
[10] H.X. Zhang, H.R. Li, Z.J. Wang, et al., Synthesis of magnetic CoFe2O4 nanoparticles
and their efficient degradation of diclofenac by activating persulfate via formation
of sulfate radicals, J. Nanosci. Nanotechnol. 18 (2018) 6942–6948.
[11] Y. Yang, J. Pignatello, J. Ma, W. Mitch, Effect of matrix components on UV/H2O2
and UV/S2O8(2−) advanced oxidation processes for trace organic degradation in
reverse osmosis brines from municipal wastewater reuse facilities, Water Res. 89
(2016) 192–200.
[12] Z. Wang, W. Qiu, S.-Y. Pang, et al., Further understanding the involvement of Fe(IV)
in peroxydisulfate and peroxymonosulfate activation by Fe(II) for oxidative water
treatment, Chem. Eng. J. 371 (2019) 842–847.
[13] L. Jie, Z. Zhao, P. Shao, F. Cui, Activation of peroxymonosulfate with magnetic
Fe3O4-MnO2 core-shell nanocomposites for 4-chlorophenol degradation, Chem.
Eng. J. 262 (2015) 854–861.
Fig. 8. Influence of different radicals quenchers on the removal of MB in the
[14] H. Hussain, I.R. Green, I. Ahmed, Journey describing applications of oxone in
CoFe2O4/AC/PMS system. Reaction conditions: MB = 100 mg/L; synthetic chemistry, Chem. Rev. 44 (2013) 3329–3371.
PMS = 1.5 mM; catalyst = 0.4 g/L. [15] X. Ao, W. Liu, Degradation of sulfamethoxazole by medium pressure UV and oxi-
dants: peroxymonosulfate, persulfate, and hydrogen peroxide, Chem. Eng. J. 313
(2017) 629–637.
of AC and degradation with PMS both contributed to the MB removal. [16] C. Tan, N. Gao, D. Fu, et al., Efficient degradation of paracetamol with nanoscaled
Herein, PMS supplied SO4−% to degrade MB and AC as the magnetic magnetic CoFe2O4 and MnFe2O4 as a heterogeneous catalyst of peroxymonosulfate,
Sep. Purif. Technol. 175 (2017) 47–57.
carriers could adsorb the residual MB in high concentration near cat-
[17] S. Verma, S. Nakamura, M. Sillanpää, Application of UV-C LED activated PMS for
alysts. CoFe2O4 acted as the catalysts for PMS and magnetic medium, the degradation of anatoxin-a, Chem. Eng. J. 284 (2016) 122–129.
which could separate CoFe2O4/AC nanocomposites easily by magnetic [18] V. Romero, S. Acevedo, P. Marco, et al., Enhancement of Fenton and photo-Fenton
processes at initial circumneutral pH for the degradation of the β-blocker meto-
separation from solution. Furthermore, the removal of MB was as high
prolol, Water Res. 88 (2016) 449–457.
as about 96% after four cycles, indicating the good stability and reu- [19] M. Ahmadi, F. Ghanbari, S. Madihi-Bidgoli, Photoperoxi-coagulation using acti-
sability. These results indicated that PMS and CoFe2O4/AC nano- vated carbon fiber cathode as an efficient method for benzotriazole removal from
composites was regarded as promising technologies in the fields of dye aqueous solutions: Modeling, optimization and mechanism, J. Photochem.
Photobiol. A s322–323 (2016) 85–94.
degradation in practice. [20] C. Lyu, D. He, Y.M. Chang, et al., Cobalt oxyhydroxide as an efficient heterogeneous
catalyst of peroxymonosulfate activation for oil-contaminated soil remediation, Sci.
Declaration of Competing Interest Total Environ. 680 (2019) 61–69.
[21] Y. Feng, D. Wu, Y. Deng, et al., Sulfate radical-mediated degradation of sulfadiazine
by CuFeO2 rhombohedral crystal-catalyzed peroxymonosulfate: synergistic effects
The authors declare that they have no known competing financial and mechanisms, Environ. Sci. Technol. 50 (2016) 3119–3127.
interests or personal relationships that could have appeared to influ- [22] J. Liu, Q. Yang, D. Wang, et al., Enhanced dewaterability of waste activated sludge
by Fe(II)-activated peroxymonosulfate oxidation, Bioresource Technol. 206 (2016)
ence the work reported in this paper. 134–140.
[23] Y.C. Hong, J.L. Peng, X.G. Zhao, et al., Efficient degradation of atrazine by CoMgAl
Acknowledgments layered double oxides catalyzed peroxymonosulfate: optimization, degradation
pathways and mechanism, Chem. Eng. J. 370 (2019) 354–363.
[24] X.-B. Gong, Degradation of dye wastewater by persulfate activated with Fe3O4/
The research was funded by National Natural Science Foundation of graphene nanocomposite, J. Water Reuse Desal. 6 (2016) 553–561.
China (Nos. 51402276 and U1809216) and Foundation of Science and [25] K. Lin, B. Chen, Prussian blue analogue derived magnetic carbon/cobalt/iron na-
nocomposite as an efficient and recyclable catalyst for activation of
Technology Department of Zhejiang Province (Nos. 2017C33078 and
Peroxymonosulfate, Chemosphere 166 (2017) 146–156.
2016C31113). [26] H.D. Chen, J.K. Xu, J.Q. Wei, et al., Mesoporous CoFe2O4 nanowires: nanocasting
synthesis, magnetic separation and enhanced catalytic degradation for cipro-
Appendix A. Supplementary data floxacin, J. Phys. Chem. Solids 132 (2019) 138–144.
[27] Y. Ji, D. Kong, J. Lu, et al., Cobalt catalyzed peroxymonosulfate oxidation of tet-
rabromobisphenol A: kinetics, reaction pathways, and formation of brominated by-
Supplementary data to this article can be found online at https:// products, J. Hazard. Mater. 313 (2016) 229–237.
doi.org/10.1016/j.mseb.2019.114420. [28] W. Oh, Z. Dong, T. Lim, Generation of sulfate radical through heterogeneous cat-
alysis for organic contaminants removal: current development, challenges and
prospects, Appl. Catal. B 194 (2016) 169–201.
References [29] S. Naim, A. Ghauch, Ranitidine abatement in chemically activated persulfate sys-
tems: assessment of industrial iron waste for sustainable applications, Chem. Eng. J.
288 (2016) 276–288.
[1] M. Cheng, G. Zeng, D. Huang, et al., Hydroxyl radicals based advanced oxidation
[30] J. Xu, P. Xin, Y. Gao, et al., Magnetic properties and methylene blue adsorptive
processes (AOPs) for remediation of soils contaminated with organic compounds: a
performance of CoFe2O4/activated carbon nanocomposites, Mater. Chem. Phys.
review, Chem. Eng. J. 284 (2016) 582–598.
147 (2014) 915–919.
[2] M. Qin, K.J. Lin, Q. Shuai, et al., Facile synthesis of 2D single-phase Ni0.9Zn0.1O and
[31] X.J. Chen, P.F. Wang, J.C. Xu, et al., Magnetic separation and adsorptive perfor-
its application in decolorization of dye, J. Mater. Sci.-Mater. Electron. 29 (2018)
mance for methylene blue of mesoporous NiFe2O4/SBA-15 nanocomposites, Adv.
9740–9744.
Powder Technol. 28 (2017) 2087–2093.
[3] K.J. Lin, M. Qin, X.G. Geng, et al., ZnCo2O4 nanorods as a novel class of high-
[32] A. Tadjarodi, M. Salehi, M. Imani, Innovative one pot synthesis method of the
performance adsorbent for removal of methyl blue, Adv. Powder Technol. 29
magnetic zinc ferrite nanoparticles with a superior adsorption performance, Mater.
(2018) 1933–1939.
Lett. 152 (2015) 57–59.
[4] Y.Q. Bao, M. Qin, Y.K. Yu, et al., Facile fabrication of porous NiCo2O4 nanosheets
[33] D. Zhang, D. Xu, Y. Ni, et al., A facile one-pot synthesis of monodisperse ring-shaped
with high adsorption performance toward Congo red, J. Phys. Chem. Solids 124
hollow Fe3O4, nanospheres for waste water treatment, Mater. Lett. 123 (2014)
(2019) 289–295.
116–119.
[5] F. Ghanbari, M. Moradi, Application of peroxymonosulfate and its activation
[34] K.L. Jin, X.J. Chen, J.C. Xu, et al., Hard-templating synthesis and enhanced pho-
methods for degradation of environmental organic pollutants: review, Chem. Eng.
tocatalysis of mesoporous titanium dioxides nanoparticles, Funct. Mater. Lett. 11

5
H. Chen, et al. Materials Science & Engineering B 249 (2019) 114420

(2018) 1850077. the commercial azo-dye Orange II mediated by Co3O4/Raschig rings in the presence
[35] I. Ibrahim, I. Ali, T. Salama, et al., Synthesis of magnetically recyclable spinel ferrite of oxone, J. Mol. Catal. A 272 (2007) 11–19.
(MFe2O4, M= Zn Co, Mn) nanocrystals engineered by sol gel-hydrothermal tech- [41] Z.H. Wang, R.X. Yuan, Y.G. Guo, et al., Effects of chloride ions on bleaching of azo
nology: high catalytic performances for nitroarenes reduction, Appl. Catal. B 181 dyes by Co2+/oxone regent: kinetic analysis, J. Hazard. Mater. 190 (2011)
(2016) 389–402. 1083–1087.
[36] M. Qin, Q. Shuai, G.L. Wu, et al., Zinc ferrite composite material with controllable [42] Y. Feng, J. Liu, D. Wu, et al., Efficient degradation of sulfamethazine with CuCo2O4
morphology and its applications, Mater. Sci. Eng. B 224 (2017) 125–138. spinel nanocatalysts for peroxymonosulfate activation, Chem. Eng. J. 280 (2015)
[37] M. Rayaroth, C. Lee, U. Aravind, et al., Oxidative degradation of benzoic acid using 514–524.
Fe0- and sulfidized Fe0-activated persulfate: a comparative study, Chem. Eng. J. 315 [43] C. Tan, N. Gao, Y. Deng, et al., Radical induced degradation of acetaminophen with
(2017) 426–436. Fe3O4 magnetic nanoparticles as heterogeneous activator of Peroxymonosulfate, J.
[38] L. Ai, H. Huang, Z. Chen, et al., Activated carbon/CoFe2O4, composites: facile Hazard. Mater. 276 (2014) 452–460.
synthesis, magnetic performance and their potential application for the removal of [44] A. Babuponnusami, K. Muthukumar, A review on Fenton and improvements to the
malachite green from water, Chem. Eng. J. 156 (2010) 243–249. Fenton process for wastewater treatment, J. Environ. Chem. Eng. 2 (2014)
[39] N. Yang, S. Zhu, D. Zhang, S. Xu, Synthesis and properties of magnetic Fe3O4-ac- 557–572.
tivated carbon nanocomposite particles for dye removal, Mater. Lett. 62 (2008) [45] P. Xie, J. Ma, W. Liu, et al., Removal of 2-MIB and geosmin using UV/persulfate:
645–647. contributions of hydroxyl and sulfate radicals, Water Res. 69 (2015) 223–233.
[40] Z. Yu, M. Bensimon, D. Laub, et al., Accelerated photodegradation (minute range) of