Accepted Manuscript

Heterogeneous catalytic oxidation for the degradation of p-nitrophenol in aque-

ous solution by persulfate activated with CuFe2O4 magnetic nano-particles

Jun Li, Yi Ren, Fangzhou Ji, Bo Lai

PII: S1385-8947(17)30649-6
DOI: http://dx.doi.org/10.1016/j.cej.2017.04.104
Reference: CEJ 16858

To appear in: Chemical Engineering Journal

Received Date: 8 January 2017

Revised Date: 3 March 2017
Accepted Date: 22 April 2017

Please cite this article as: J. Li, Y. Ren, F. Ji, B. Lai, Heterogeneous catalytic oxidation for the degradation of p-
nitrophenol in aqueous solution by persulfate activated with CuFe2O4 magnetic nano-particles, Chemical
Engineering Journal (2017), doi: http://dx.doi.org/10.1016/j.cej.2017.04.104

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 Heterogeneous catalytic oxidation for the degradation of

p-nitrophenol in aqueous solution by persulfate activated with

CuFe2O4 magnetic nano -particles

Jun Li, Yi Ren, Fangzhou Ji, Bo Lai∗

Department of Environmental Science and Engineering, School of Architecture and Environment, Sichuan

University, Chengdu 610065, China

Abstract: To evaluate the heterogeneous degradation of p-nitrophenol (PNP) in

aqueous solution by catalytic oxidation process involving persulfate (PS) activated by

CuFe2O4 magnetic nano-particles, the CuFe2O4/PS system was investigated in this

study. CuFe2O4 magnetic nano-particles were synthesized with a sol-gel combustion

method and then used as heterogeneous catalysts for PS activation. First, effects of

CuFe2O4 dosage (0-40 g/L), PS dosage (0-10 mM), initial pH value (3.0-11.0) and

co-existing inorganic ions on the degradation of PNP in aqueous solution by

CuFe2O4/PS system were investigated comprehensively. In particular, the maximum

PNP removal (89%) and total organic carbon (TOC) removal (81%) were obtained

under the optimal conditions. Meanwhile, two control experiments (i.e., CuFe2O4

alone and PS alone systems) were carried out to confirm the performance in

CuFe2O4/PS system. Furthermore, the reasonable PNP degradation pathway was

proposed based on the intermediates detected by high performance liquid

chromatography (HPLC). Finally, the mechanism of the CuFe2O4/PS system was

∗
Corresponding authors. Tel./fax: +86 18682752302
E-mail address: laibo@scu.edu.cn (Bo Lai)
1 / 43
proposed thoroughly according to the characterization of catalyst, the analysis results

of metal leaching and radical scavenging studies. In a word, this study provides an

effective oxidative system for PNP removal by CuFe2O4/PS heterogeneous process at

ambient temperature.

Keywords: p-Nitrophenol; CuFe2O4 magnetic nano-particles; Persulfate; Degradation

pathway; Reaction mechanism

1. Introduction

Nitrophenols and their derivatives as the mutagenic and refractory aromatic

pollutants from industrial and agricultural wastewater have been paid attentions due to

their high toxicity and persistence in the environment. In particular, p-nitrophenol

(PNP) is an important organic chemical raw material and intermediate used in

manufacturing pesticides, dyestuffs, explosives, wood preservatives and rubber

chemicals[1]. As we all know, PNP poses a threat to both environment and the public.

For example, exposure to PNP can cause injury to blood cells, damage to the nervous

central system and mutagenic effects to the organisms. Consequently, it has been

notified as one of the priority pollutants according to U.S. EPA classification[2].

According to the above mentions, PNP has been chosen as the model pollutant in this

study.

In recent years, advanced oxidation processes (AOPs), including photocatalysis[3,

4], Fenton[5, 6], UV/Fenton[7] and ozonation[8] etc., have been garnered an

increasing number of attentions for the produce of hydrogen radicals (HO•) which is a

powerful oxidant with high redox potential (Eθ=2.8V). However, the above treatment

2 / 43
technologies have some drawbacks, such as the harsh pH condition, short life span,

produce of massive iron sludge and high cost. Nowadays, sulfate radical (SO4•-,

Eθ=2.6V), which is effective in degrading the organic pollutants and has relatively

longer viable period compared with HO•, has been widely used for the degradation of

hazardous compounds. It reacts with organic compounds primarily through electron

transfer with a second-order rate constant of 106–10 9 M-1 s-1[9]. In addition, due to its

selectivity, SO4•− is generally much more reactive than HO• for organic compounds

with unsaturated bond and aromatic constituents. Different methods of heat[10], UV

radiation[11], transition metal ion (Men+)[12] and base[13] have been applied to

activate peroxymonosulfate (PMS) and persulfte (PS) to form sulfate radicals. In

particular, persulfate is a common source of SO4•- due to its high solubility in aqueous

solution, stability in the environment and lower price in comparison to

peroxymonosulfate.

Recently, heterogeneous AOPs have obtained a comprehensive attention

compared with homogeneous AOPs for that they can be operated under mild

conditions and produce little iron sludge after treatment process. For last decades, iron

oxides (e.g., Fe3O4 and Fe2O3) were usually used as the catalyst in the heterogeneous

catalytic process since iron is the second most abundant element in the earth’s crust

[14-16]. However, the weak catalytic activity without other auxiliary energy supply

inhibits the performance of pollutants removal. Nowadays, the magnetic materials

have been extensively used for the treatment of refractory pollutants due to their

desirable stability, good separation and remarkable catalysis. With the further study of

3 / 43
heterogeneous catalyst, magnetic spinel-type ferrite particles with a general formula

MFe2O4 (M = Mn, Fe, Co, Ni, and Cu, etc.) have been used in several water treatment

applications[17, 18]. Nowadays, CuFe2O4 magnetic nano-particles, as an alternative

catalyst, have been the focus of attention. The material has been widely studied as the

catalyst for hydrogen production applied to fuel cell[19], H2O2 activation[20] and

ozonation[21]. In addition, the superiority of stable spinel structure of CuFe2O4

particles and reduced leaching of heavy metals from the solid phase[22] make it

popular among the heterogeneous catalysis research. It has been reported that the

bimetallic catalyst CuFe2O4 activated peroxymonosulfate (PMS) to generate SO4•- is a

promising technology for different pollutants removal. For instance, Guan et al.[23]

have observed that CuFe2O4 can be used to degrade atrazine with PMS as the

oxidation via the formation of hydroxyl and sulfate radicals. Zhang’s group[24] found

that CuFe2O4 can be used as a heterogeneous catalyst for the catalytic activation of

PMS to decompose 2-phenylbenzimidazole-5-sulfonic.

To our best knowledge, CuFe2O4 activating PS to degrade PNP in aqueous

solution is rarely reported. In this study, therefore, the CuFe2O4 magnetic

nano-particles, as the superior active and environment-friendly heterogeneous catalyst,

were used combining with PS to degrade PNP in aqueous solution. The objective of

this study were: (i) to investigate the effects of key parameters on the degradation of

PNP in aqueous solution and confirm the ability of CuFe2O4 for PS activation by two

control experiments; (ii) to determine the intermediates during the PNP degradation

quantitatively and establish a proposed pathway for PNP degradation; (iii) to explore

4 / 43
the activity and stability of CuFe2O4 in the recycling experiments; (iv) to identity the

main radicals in the CuFe2O4/PS system for PNP removal and illustrate the reasonable

degradation mechanism.

2. Materials and methods

2.1. Reagent

p-Nitrophenol (PNP, 99.0%), sodium persulfate (PS, ≥ 98.0%), cupric nitrate

[Cu(NO3)2•3H2O, ≥ 99.0%], ferric nitrate [Fe(NO3)3•9H2O, ≥ 98.5%], citric acid

(C6H8O7, ≥ 99.5%), ethanol (EtOH) and tert-butyl alcohol (TBA) from Chengdu

Kelong chemical reagent factory were used in the experiments. Other chemicals used

in the experiment were of analytical grade. Distilled water was used throughout the

whole experiment process. All solutions in the study were prepared by the distilled

water. CuFe2O4 magnetic nano-particles were synthesized with a sol-gel combustion

method which uses citrate as the complexing agent[25]. Details pertaining to the

preparation method are provided in the Supporting Information.

2.2. Experimental procedures

PNP stock solution (50 mg/L) was prepared by simple dissolution in distilled

water. 150 mL solution of PNP was transferred into 250 mL beaker and the pH value

of PNP aqueous solution was adjusted with 0.1 M sulfuric acid or sodium hydroxide

solution. The reactions were initiated after adding the desired amount of CuFe2O4

nano-particles and PS into the reactor synchronously. The experiment was performed

at 25 ± 2 ◦C by water batch heating and mixed by a mechanical stirrer (300 rpm).

During the reaction process, aqueous samples were withdrawn with syringe at

5 / 43
designated sampling time and immediately filtered through a PTFE syringe filter disc

(0.45 µm). Firstly, effects of key parameters (i.e., CuFe2O4 dosage, PS dosage, initial

pH and co-existing inorganic ions) on the degradation of PNP were investigated

thoroughly by batch experiments. And then, two control experiments were setup to

confirm the performance of CuFe2O4/PS system for PNP removal. Furthermore, PNP

removal, UV-Vis spectra, TOC removal and the degradation products of PNP were

analyzed, respectively. Furthermore, in order to test the stability and reusability of the

CuFe2O4 particles, 5 recycling experiments were done. In addition, two sets of

quenching experiments were carried out to determine the main radical species in the

CuFe2O4/PS process. All experiments were performed in tripartite, and all data in the

figures were averaged value of 3 replicate samples and the error bars represented

standard deviation of the means.

2.3. Analytical methods

Details pertaining to analytical methods in this study are provided in the

Supporting Information.

3. Results and discussion

3.1. Parameters optimization

3.1.1 Effect of CuFe2O4 dosage

Effects of different CuFe2O4 dosages (0, 5, 10, 15, 20, 25, 30, 35, 40 g/L) on the

degradation of PNP in aqueous solution were evaluated thoroughly. Fig. 1(a) shows

that the PS without CuFe2O4 could only oxidize small amount of PNP (17%).

Furthermore, the addition of slight CuFe2O4 (5 g/L) caused the degradation efficiency

6 / 43
of PNP promote to 39% abruptly compared with the PS alone system. The above

consequences confirmed that CuFe2O4 could be used as catalyst to activate PS.

Afterwards, the degradation efficiency of PNP enhanced continuously from 39% to 89%

with the CuFe2O4 dosage increasing from 5 g/L to 30 g/L. The result can be attributed

to the following aspects: (i) the total surface area and active sites on the surface of

CuFe2O4 nano-particles increased with the increasing CuFe2O4 dosage. The growing

surface area and active sites are favorable to activate PS and generate the radicals (i.e.,

SO4•- and HO•), which effectively improve the degradation of PNP[26]; (ii) the

adsorption ability enhanced with the increasing CuFe2O4 dosage which could be

helpful for the removal of PNP in a certain extent; (iii) with the increase of CuFe2O4

dosage, a few of copper and iron (hydr)oxides (i.e., CuO, FeO, Fe2O3 and FeOOH)

(see Fig. 6) deposited on the surface of CuFe2O4 could also activate PS to produce

radicals[27, 28]. However, a further increase of CuFe2O4 dosage from 30 g/L to 40 g/L

did not further increase the degradation efficiency of PNP. That was because the

amounts of active sites on the surface of 30 g/L CuFe2O4 have been sufficient with PS

dosage of 10 mM and the adsorption/desorption equilibrium has been achieved

between PNP and CuFe2O4 nano-particles[25]. Therefore, the optimum CuFe2O4

dosage was selected as 30 g/L in the following experiments.

3.1.2 Effect of PS dosage

Effects of different PS dosages (0, 2, 5, 7, 8, 9, 10 mM) on the degradation of PNP

in aqueous solution were investigated. Fig. 1(b) shows that the adsorption effect of

PNP by CuFe2O4 nano-particles occurred in CuFe2O4 alone system. In particular, the

7 / 43
adsorption amounts onto CuFe2O4 reached to 16%. Meanwhile, it is noted that the

increase of initial PS dosage to 8 mM improved the degradation efficiency of PNP to

89%, the result could be explained that active sites on CuFe2O4 surface were still not

totally occupied by PS and the increasing PS could reach the surface of CuFe2O4

particles. Consequently, more radicals (i.e., SO4•- and HO•) were produced with the

increasing of PS dosage to decompose PNP. The similar result was also obtained by

our previous studies[29-31]. In addition, the increasing of PS dosage can be activated

by the deposited copper and iron (hydr)oxides (i.e., CuO, FeO, Fe2O3 and FeOOH)

(see Fig. 6) deposited on the surface of CuFe2O4 to generate more radicals[27, 28].

However, the degradation efficiency of PNP remained invariable and even declined

slightly with the PS dosage further increasing to 10 mM, which was attributed to the

quenching of sulfate radicals by radical-scavenging or residual PS (Eqs. (1) and

(2))[32]. Ding et al.[33] also observed that excessive PS could enhance the radical

scavenging ability. Therefore, the optimal PS dosage of 8 mM was selected in the

following experiments.

SO4•- + SO4•- → S2O82- (1)

SO4•- + S2O82- →SO42- + S2O8•- (2)

3.1.3 Effect of initial pH

It is known to all that the performance of homogeneous AOPs strongly depends on

solution pH[14]. Effects of different initial pH (3.0, 5.0, 6.0, 7.0, 9.0, 11.0) on the

degradation efficiency of PNP in aqueous solution were explored in Fig. 1(c). Fig. 1(c)

shows that the PNP removal efficiency increased slightly when initial pH grew from

8 / 43
3.0 to 5.0 and then the degradation rate enhanced dramatically with the increasing of

pH before it reached 7.0. In particular, the degradation rate and degradation amount

reached to the maximum at pH 7.0. However, its degradation rate decreased

apparently when pH increased to 9.0 and PNP removal efficiency (65%) was further

dropped with pH rising to 11.0. Meanwhile, Fig. S1 describes the variation of solution

pH under different initial pH conditions. Obviously, the effluent pH was acidic or

alkaline solution during the whole treatment process due to the hydrolysis of PS (Eqs.

(3) and (4)) when the initial pH was 3.0-9.0 and 11.0, respectively.

H2O + S2O82- →2HSO4-+ 1/2O2 (3)

HSO4- →SO42- + H+ (4)

According to the above description, neutral and acidic pH was more favorable for

the rapid oxidation of PNP, while alkaline conditions exerted some negative effects.

The result was also in accordance with the removal of diphenylamine[34] and

flumequine[35] by persulfate oxidation reported in the literatures. The reason can be

explained from the following aspects: (i) metal oxides catalysts show amphoteric

property in water according to Eqs. (5) and (6)[36]. The surface of catalyst presents a

net positive (negative) charge as solution pH lower (higher) than pHPZC of catalyst[23].

Since the pHPZC of CuFe2O4 was about 7.9[37], the electrical interaction between PS

and CuFe2O4 would facilitate the contact of PS and CuFe2O4 by attractive force when

initial pH ranges from 3.0 to 9.0. However, when initial pH was 11.0, removal of PNP

would decline obviously due to the electrostatic repulsive-force which reduces the

interaction chance of CuFe2O4 and PS; (ii) under acidic conditions, SO4•- as the major

9 / 43
active species play a dominant role in the degradation of pollution[34]. Under alkaline

conditions, SO4•- would react with OH- in the solution so that mounts of HO• would

form (Eq. (7)). Although HO• exerts a higher redox potential than SO4•-, the

accompanying generation of plentiful SO42- may restrain the reactivity of HO• and

SO4•-[38]. In addition, the reaction rate of SO4•- recombination (Eq. (1)) in alkaline

condition is approximate 1 or 3 order of magnitude higher than the rates of HO•

formation reaction (Eq. (7))[39]. Therefore, the initial pH of 7.0 was selected in the

following experiments.

≡ MeOH2+ ⇌ ≡ MeOH + H+ (5)

≡ MeOH ⇌ ≡ MeO- + H+ (6)

SO4•- + OH- →SO42- + HO• (7)

3.1.4 Effect of co-existing inorganic ions

Details pertaining to effects of co-existing inorganic ions in this study are

provided in the Supporting Information.

3.2. Control experiments

Two control experiments (i.e., CuFe2O4 alone and PS alone systems) were setup

to evaluate the catalytic degradation ability for PNP removal by CuFe2O4/PS system

thoroughly under the same condition (i.e., CuFe2O4 dosage of 30 g/L, PS dosage of 8

mM and initial pH of 7.0). The performance of control experiments and CuFe2O4/PS

system were investigated comparatively through analyzing the PNP removal, TOC

removal, variation of pH and UV-vis spectra of the effluent.

3.2.1 PNP and TOC removal analysis

10 / 43
 Fig. 2(a) and (b) show the PNP and TOC removal of CuFe2O4 alone, PS alone and

CuFe2O4/PS systems, respectively. In particular, the combination of CuFe2O4 and PS

enhanced the PNP removal significantly, achieving a PNP removal of 89% and TOC

removal of 81% after 60 min treatment, whereas the only addition of CuFe2O4

nano-particles resulted in the PNP removal of 16% and TOC removal of 9%, and the

PS alone system obtained the PNP removal of 15% and TOC removal of 8% during

the same reaction time, respectively. From the results, the adsorption effect of

CuFe2O4 nano-particles and the oxidation by sole PS for PNP removal were weak.

However, CuFe2O4/PS system could not only provide higher PNP degradation

efficiency, but also improve the capacity of mineralization. That is to say, CuFe2O4

nano-particles could be used as catalyst to activate PS to produce radicals (i.e., SO4•-

and HO•) for the degradation of pollutants, which was mainly owed to the synergistic

effects of active sites of Cu and Fe on the surface of CuFe2O4 particles.

3.2.2 Changes of pH during the treatment process

Variation of solution pH during the 60 min treatment process with CuFe2O4 alone,

PS alone and CuFe2O4/PS systems were depicted in Fig. 2(c). We note that the pH of

CuFe2O4 alone system was almost unchanged during the whole treatment process.

And the pH of PS alone system immediately decreased to about 3.9 at the initial phase

and remained constant in the following treatment time, which could be explained that

the hydrolysis of PS could release plenty of H+ to decrease the solution pH (Eqs. (3)

and (4))[40]. In particular, the solution pH of CuFe2O4/PS system declined slightly

from the initial pH of 7.0 to 6.3 after 60 min treatment, which could be explained as

11 / 43
follows: (i) although the hydrolysis of PS would release plenty of H+ ions, the PS

added in the system were consumed and activated rapidly by CuFe2O4 nano-particles

to generate radicals (e.g, SO4•- and HO•) for PNP removal during the whole treatment

process; (ii) the formed HSO5- in the reaction solution through the reaction between

PS and H2O (Eq. (8)) could also be depleted and activated by different valent copper

and iron (i.e., ≡Cu3+, ≡Cu2+, ≡Cu+, ≡Fe3+ and ≡Fe2+) to generate radicals, resulting in

the consumption of H+[25]; (iii) the generated small molecule acid (e.g., fumaric acid

and maleic acid) (see Fig.3) from the decomposition of PNP contributes the H+.

H2O + S2O82- →HSO5- + HSO4- (8)

3.2.3 UV-Vis spectral analysis

Details pertaining to UV-Vis spectral analysis in this study are provided in the

Supporting Information.

3.3. Proposed reaction pathway for the degradation of PNP in CuFe2O4/PS

system

It has been reported that the benzene ring structure of p-benzoquinone would be

opened by oxidation process and generated the small molecular organics (e.g.,

fumaric acid, maleic acid and acrylic acid), which would be further degraded into CO2

and H2O[41, 42]. However, the studies about CuFe2O4/PS heterogeneous catalytic

oxidation process for the degradation of PNP are still rare. Therefore, it is necessary

to determine the intermediates in our system and ascertain the reaction pathways. The

reaction intermediates detected in the study were p-aminophenol, p-benzoquinone,

fumaric acid and maleic acid. The concentration variation of each identified

12 / 43
intermediate and the residual PNP during the reaction process was shown in Fig. 3.

We can note that the concentration of PNP decreased sharply in the initial 20 min

treatment process, resulting in a PNP removal of 86%. In the following 40 min,

degradation of PNP only enhanced slightly to 89%. Meanwhile, the rapid

accumulation of p-aminophenol led that its concentration increased to the maximum

(2.1 mg/L) at the initial 5 min, and then it decreased sharply in the following reaction

process. It might be because that PNP was first reduced to p-nitrosophenol[43] and

further rapidly reduced to p-aminophenol during the initial stage of reaction process

by the ≡Fe2+ on the surface of CuFe2O4 nano-particles (see Fig. 6) and Fe2+ dissolved

in the solution[44]. What’s more, p-aminophenol would be further oxidized by

amounts of radicals (i.e., SO4•- and HO•) predominanted in the catalytic oxidation

system. In addition, hydroquinone was not detected by HPLC in this study, which

might be ascribed that hydroquinone was not formed in this system or was oxidized to

p-benzoquinone instantly in the catalytic oxidation process[43]. Finally, the maximum

concentration of fumaric acid (1.4 mg/L) and maleic acid (1.3 mg/L) was achieved in

the initial stage, and then gradually decreased to 0.7 mg/L and 0.5 mg/L during the

following treatment process, respectively. The results could be explained that

p-benzoquinone and hydroquinone were further oxidized to small molecule acid (e.g.,

fumaric acid and maleic acid) under radicals attack. The influent concentration was 50

mg/L, however, the concentrations of detected intermediates were much lower (< 5

mg/L），which was attributed that the above intermediates would not accumulate

largely and could be further mineralized into CO2 and H2O during the treatment

13 / 43
process. Meanwhile, the high TOC removal (81%) was in accordance with the

excellent performance and vertified the degradation deduction .

Meanwhile, the reasonable transformation pathways of PNP were proposed based

on the intermediates as shown as in Fig. 4. In particular, two degradation pathways

were proposed as follows: (i) combined reduction and oxidation: in pathway I, PNP

is first reduced to p-nitrosophenol and further reduced to p-aminophenol by reduction

≡Fe2+ on the surface of CuFe2O4 nano-particles (see Fig. 6) and Fe2+ dissolved in the

solution. And then p-aminophenol is oxidized to hydroquinone or p-benzoquinone by

radicals (e.g., SO4•- and HO•). Moreover, their benzene rings are opened and further

oxidized to ring cleavage compounds (e.g., fumaric acid and maleic acid). Finally,

most of them are mineralized into CO2 and H2O. (ii) direct oxidation: in pathway II,

since oxidation effect was dominant during the reaction process in the CuFe2O4/PS

heterogeneous catalytic oxidation system, PNP could be converted easily to

p-benzoquinone and hydroquinone by radicals oxidation, which can be further

oxidized to the ring opening products (e.g., fumaric acid and maleic acid) and

mineralized into CO2 and H2O.

3.4. Characterization of CuFe2O4 nano-particles

3.4.1 TEM, BET, VSM and XRD analysis of the CuFe2O4

TEM image of synthetic CuFe2O4 nano-particles is shown in Fig. S3. We can see

from the Fig. S3 that the prepared CuFe2O4 were nanoscale particles with diameters

ranging from 5 nm to 35 nm. Textural properties of fresh catalyst were investigated

by nitrogen sorption analysis. Fig. S4 shows the nitrogen adsorption-desorption

14 / 43
isotherms of CuFe2O4 nano-particles. As observed, the isotherm shows CuFe2O4 type

IV isotherm and type H 3 hysteresis loop, with the hysteretic loop in the range of

0.6-1.0 P/P0, indicating the existence of mesopore in the structure of CuFe2O4

particles. And the specific surface area of CuFe2O4 was 27 m2/g. Meanwhile, the M–H

curve of the fresh CuFe2O4 (Fig. S5) demonstrates that the saturation moment was

about 24 emu/g. And then, the magnetic characterization of CuFe2O4 nano-particles

was verified through an external magnetic field. As shown as in Fig. S6, the CuFe2O4

particles gathered together on the beaker wall by the magnet, which provided a

separation method in the following recycle experiments.

In addition, XRD patterns of the fresh and reacted CuFe2O4 nano-particles in

CuFe2O4/PS system were illustrated in Fig. 5. From Fig. 5, the three intense

diffraction peaks showed in the XRD pattern at 2θ of 29.9◦, 35.9◦, 43.8◦, 57.8◦ and

62.2◦ could be indexed to (1 1 2), (2 1 1), (2 2 0), (3 2 1) and (2 2 4), respectively,

which was in accordance with the literature[45]. The diffraction patterns were well

indexed to the published XRD pattern of the CuFe2O4 particles (JCPDS File No.

34-0425), suggesting the formation of CuFe2O4 with a considerable degree of

crystallization. According to the full width at the half-maximum of the diffraction

peak, the average crystallite size of CuFe2O4 nano-particles can be calculated to be

13.9 nm, respectively, using the Scherrer equation:

Kλ
Dhkl =
βhkl cos
hkl
where Dhkl is the crystallite size perpendicular to the normal line of the (hkl) plane, K

a constant (0.89), βhkl the full width at half maximum (fwhm) of the (hkl) diffraction

15 / 43
peak, θhkl the Bragg angle of the (hkl) peak, and λ the X-ray wavelength.

According to the XRD result, compared with the fresh particles, the reacted

CuFe2O4 exhibited little change and no additional peaks were observed, which

suggests that the structure and component of CuFe2O4 particles were not destroyed

after the reaction process. The XRD pattern of CuFe2O4 after reaction also proved that

the structure of CuFe2O4 as the catalyst was stable, providing the potential of CuFe2O4

to be recycled in the following recycling processes.

3.4.2 XPS analysis of the fresh and reacted CuFe2O4

X-ray photoelectron spectroscopy is an efficient surface characterization

technique that provides qualitative and quantitative information from the outermost

few atomic layers[46]. In order to better understand the surface composition and

chemical states of the fresh and reacted CuFe2O4 and the roles of Cu and Fe species,

the chemical states of Cu, Fe and O of the fresh and reacted CuFe2O4 nano-particles in

CuFe2O4/PS catalytic oxidation system for the degradation of PNP were measured by

XPS, and the fitting results are shown in Fig. 6. The survey scan of the CuFe2O4

nano-particles revealed the presence of Cu (2p), Fe (2p) and O (1s), as seen in Fig.

6(a). Binding energies were corrected relative to the carbon 1 s signal at 284.8 eV to

calibrate the acquired spectra. More detailed scan have performed for Cu 2p, Fe 2p

and O 1s core level spectra to determine charge state of elements present in CuFe2O4

magnetic nano-particles. All XPS core level spectra were fitted using Shirley

background.

To better understand the roles of Cu in CuFe2O4/PS catalytic process, the detail

16 / 43
XPS survey scan of Cu of the fresh and reacted CuFe2O4 nano-particles is displayed

in Fig. 6(b). We can observe that binding energy positions of fresh CuFe2O4

nano-particles are 934.1 eV (Cu 2p3/2), 941.3 eV (Cu 2p1/2) and 943.7 eV (Cu 2p1/2).

The main peak at binding energies of 934.1 eV for the Cu 2p3/2 line was attributed to

Cu(II)[47, 48], and the peaks at 941.3 eV and 943.7 eV are primarily similar to that of

dominated Cu(II) oxide species[14]. Compared with the fresh particles, two peaks at

933.2 eV and 936.8 eV formed in the reacted CuFe2O4 nano-particles. The binding

energy at 936.8 eV was assigned to Cu(II) according to the literature[48]. And the

lower binding energy at 933.2 eV suggested that the valence of Cu has changed and

Cu(II) was transferred to Cu(I) partially[49]. In other words, a few of copper oxides

(e.g., Cu2O and CuO) might be generated on the surface of CuFe2O4.

In order to characterize the valance state of the Fe in CuFe2O4 particles before and

after CuFe2O4/PS heterogeneous catalytic oxidation process, the XPS survey curves

of CuFe2O4 for the Fe 2p regions are presented in Fig. 6(c). The XPS spectra of the

fresh CuFe2O4 in Fig. 6(c) shows the presence of three peaks at binding energy of

710.9 eV, 713.1eV for Fe 2p3/2 and 724.4 eV for Fe 2p1/2, which indicated the

presence of Fe(III) according to the literatures[29, 50, 51]. For the XPS spectra of

reacted CuFe2O4, the peak of Fe 2p 3/2 slightly shifted to lower binding energy value at

912.5 eV, suggesting that the valences of the Fe species had changed and formed a

mixture of species. Ji and his collaborator also found the similar phenomenon of

negative shift of binding energy value[47]. Meanwhile, a new peak appeared at the

binding energy of 717.3 eV belongs to Fe(II), which manifests that a certain

17 / 43
proportion of Fe(II) was formed, transferring from Fe(III). According to the above

discussion, a few of iron (hydr)oxides (i.e., FeO, Fe2O3 and FeOOH) might be formed

on the surface of CuFe2O4 particles, which have an effect on the PS activation.

XPS spectra of the O 1s core level is depicted in Fig. 6(d). The main peak about

530.1 eV is attributed to the lattice oxygen O of all surface oxygen in fresh CuFe2O4

and the peak located at binding energy around 531.6 eV is attributed to the (OH)

adsorbed at the sample surface as reported in the literature[49]. For the reacted

CuFe2O4 particles, the peak at 530.1 eV has slightly shifted to 529.8 eV and the O in

adsorbed H2O at 533.0 eV increased greatly with the decline of the lattice oxygen O at

the peak of 530.1 eV, indicating that the CuFe2O4 surface was strongly hydroxylated

after the degradation process[49]. It would be attributed that the generation of a few

of FeOOH on the surface of CuFe2O4, which are the active sites for catalytic

decomposition and reactive radical generation and also could activate PS to generate

radicals[52, 53]. The formed peak located at binding energy around 531.2 eV is

attributed to the (OH) adsorbed at the sample surface, as reported in the literature[54].

3.5. Stability and recyclability of the CuFe2O4 nano-particles

The leaching total copper and iron ions were measured after the CuFe2O4/PS

treatment process for PNP removal. It found that the total copper and iron ions

leaching after the 60 min reaction process were 0.796 mg/L and 0.238 mg/L (not

shown, effluent pH of 6.3), respectively. In addition, the total copper ions

concentration decreased to 0.26 mg/L through adjusting the effluent pH to 7.0.

According to the Discharge standard of Pollutants for Municipal Wastewater

18 / 43
Treatment Plant of China (GB 18918 - 2002), the maximum permissible limit of

copper ions in effluent was 0.5 mg/L.

In order to investigate the sustaining catalytic ability of CuFe2O4, the PNP

degradation by CuFe2O4/PS heterogeneous oxidation process was conducted for five

cycles. And the recycled catalysts were tested for the following reaction under the

same experimental conditions (i.e., CuFe2O4 dosage of 30 g/L, PS dosage of 8 mM,

initial pH of 7.0, and treatment time of 60 min), as exhibited in Fig. 7. To be specific,

PNP degradation efficiencies in five cycles after 60 min treatment were 89%, 88%,

87%, 86% and 84%, respectively. Though the PNP removal efficiency decreased

slightly after the first run, the degradation efficiency was still very high in the

following four cycles. The above results suggested that CuFe2O4 particles still

maintained a satisfying activity after five catalytic cycles. The similar results about

the stability and recyclability of CuFe2O4 have also been reported previously in

CuFe2O4-based catalytic systems in the literatures[14, 23, 48]. The result of recycling

experiments was also consistent with the analysis of the XRD pattern (Fig. 5) that the

CuFe2O4 nano-particles did not show any obvious changes, suggesting that the

structure of the CuFe2O4 nano-particles is stable.

3.6. Reaction mechanism of the CuFe2O4/PS process

Radical scavenging experiments were carried out to identify the dominant radical

species responsible for PNP degradation generated in the CuFe2O4/PS heterogeneous

catalytic system through adding excessive radical scavengers. Sulfate and hydroxyl

radicals might be generated in the reaction process and hydroxyl radicals were formed

19 / 43
by the reaction of sulfate radical with H2O through Eq. (9). It is widely reported in the

literature that ethanol (EtOH, with an α hydrogen) readily reacts with both HO• and

SO4•−, and the rate constants for the reactions with HO• and SO4•− are (1.2–2.8) ×109

mol L−1 s−1 and (1.6–7.7) ×107 mol L−1 s−1, respectively[55]. By contrast, tert-butyl

alcohol (TBA, without α hydrogen) has different reaction rate constants with HO• and

SO4•−, and the rate constant for HO• ((3.8–7.6) ×10 8 mol L−1 s−1) is 418-1900 times

greater than that for SO4•− ((4–9.1) ×105 mol L−1 s−1)[49]. Therefore, EtOH and TBA

were employed as two radical scavengers.

SO4•- +H2O →SO42- + HO•+ H+ (9)

Fig. 8 shows the quenching tests performed with either EtOH or TBA. From Fig.

8, about 89% PNP was degraded after 60 min treatment when no quenching agents

were added. Obviously, the PNP removal rate and removal efficiency was much

higher than those with radical inhibitors. In the presence of 500 mM TBA, the PNP

degradation efficiency declined to 84% during the same treatment process, the result

indicated that HO• was formed in the CuFe2O4/PS system. Furthermore, the addition

of 500 mM EtOH in the CuFe2O4/PS system directly led to PNP removal decreasing

from 89% to 72%. The phenomena suggested that the main radical species formed

during the CuFe2O4/PS heterogeneous oxidation process were SO4•−, while HO• was

also involved in this process. Similar consequences were also obtained by Zhang et

al.[25], who proposed that SO4•− were the main radicals in the activation of persulfate

by CuFe2O4/MWCNTs for the removal of diethyl phthalate. In addition, Fan et al.[56],

who proved that SO4•− was the predominant reactive species under acid condition for

20 / 43
the removal of sulfamethazine by heat-activated persulfate oxidation process.

It has been reported that the mechanism of sulfate radical based oxidation is

similar to what occurs in the heterogeneous Fenton reaction[57]. Sulfate radicals are

formed though the activation of PS by electron transfer between redox pairs on the

surface of the catalysts. In particular, XPS study is an effective method to investigate

electron transfer on the surface of MFe2O4 (M = Mn, Co, Cu, Zn)[17]. Thus,

according to the XPS analysis and the above discussion, a proposed mechanism

depended on electron transfer and radical generation in CuFe2O4/PS heterogeneous

catalytic oxidation process for the PNP degradation was put forwarded as seen in Fig.

9.

3.6.1 Heterogeneous catalytic oxidation

≡Cu2+ is the main catalytic center for PS activation according to the literature[25].

On the surface of the CuFe2O4 nano-particles, ≡Cu 2+ was first oxidized to ≡Cu 3+ by

the adsorbed PS in the catalytic oxidation process (Eq. (10)). Meanwhile, part of PS

would react with H2O in PNP aqueous solution to form HSO5- according to Eq. (8).

Consequently, bivalent and trivalent copper ions (i.e., ≡Cu2+ and ≡Cu3+) would

activate S2O82- and HSO5- to form sulfate radicals (Eqs. (11)-(12)). Furthermore, the

monovalent copper ions (i.e., ≡Cu+) reduced from ≡Cu 2+ would further react with

both PS and HSO5- to generate sulfate radicals (Eqs. (13)-(14)). What’s more, ≡Fe2+

would firstly reduce PNP to p-nitrosophenol and p-aminophenol further. In addition,

iron ions (e.g., ≡Fe2+, ≡Fe3+) could also react with S2O82- and HSO5- to generate

radicals (Eqs. (15)-(17)). Also, Cu + and Fe2+ shown by XPS analysis (see Fig. 6(b)

21 / 43
and (c)) in the reacted CuFe2O4 nano-particles confirmed the above deduction.

Moreover, although oxidizing of HSO5- by ≡Cu2+ or ≡Fe3+ (Eqs. (12) and (15)) is

thermodynamically unfavorable, the reactions were still likely to occur at highly

reactive metal center in defects or oxygen vacancies since CuFe2O4 particles were

nanoscaled[25]. In particular, the reactions (Eqs. (13)-(14) and (16)-(17)) could not

only make HSO5- and S2O82- to generate sulfate radicals, which were the main radicals

in the CuFe2O4/PS process for PNP degradation confirmed by the quenching

experiment (see Fig. 8), but also make the metal centers return to the initial oxidation

state. Significantly, recovery of ≡Cu2+ center was achieved by the reduction of ≡Cu 3+

(Eq. (18)). In addition, PNP and its intermediates would be absorbed on the surface of

CuFe2O4 nano-particles. Therefore, the SO4•- and HO• generated on the surface of

CuFe2O4 would oxidize the adsorbed pollutants in situ. Meanwhile, slight of

surface-bound radicals (i.e., SO4•- and HO•) might also diffuse from the surface of the

CuFe2O4 catalyst into the solution to oxidize the non-adsorbed pollutants. What’s

more, most of the formed copper and iron (hydr)oxides (i.e., CuO, FeO, Fe2O3 and

FeOOH) (see Fig. 6) could activate PS for the generation of sulfate radicals[27, 53].

≡Cu2++ S2O82- → ≡Cu3+ + SO4•- + SO42- (10)

≡Cu3+ + HSO5-→≡Cu2++ SO4•-+ H+ (11)

≡Cu2++ HSO5-→≡Cu++ SO4•-+ H+ (12)

≡Cu++ S2O82- → ≡Cu2+ + SO4•- + SO42- (13)

≡Cu++ HSO5- → ≡Cu2+ + SO4•- + HO- (14)

≡Fe3++ HSO5-→≡Fe2++ SO4•-+ H+ (15)

22 / 43
≡Fe2++ S2O82- → ≡Fe3+ + SO4•- + SO42- (16)

≡Fe2++ HSO5- → ≡Fe3+ + SO4•- + HO- (17)

≡Cu3+ + ≡Fe2+→≡Cu2++ ≡Fe3+ (18)

3.6.2 Homogeneous catalytic oxidation, adsorption and direct oxidation

A small amount of dissolved metal ions (e.g., Fe3+, Fe2+, Cu 3+, Cu2+ and Cu+) in

the reaction solution would also react with HSO5- or S2O82- to generate sulfate radicals.

Furthermore, it is well-known that the generated SO4•- can react with H2O to generate

HO• under all pH values that can partially contribute to the degradation process (Eq.

(9)), even though the rate constant of this reaction is low (k = 2.0×10-3 s-1)[58].

What’s more, the adsorption of PNP by 30 g/L CuFe2O4 nano-particles reached 16%,

which was attributed that CuFe2O4 nano-particles possess high specific surface area

(see Fig. 2(a)). In addition, the removal of PNP by the direction oxidation of 8 mM PS

(without catalyst added) was 15% (see Fig. 2(a)). Wang and his co-workers have also

reported that meso-CuFe2O4 adsorption and H2O2 oxidation could contribute to the

imidacloprid removal in the similar meso-CuFe2O4/H2O2 system[48]. In other words,

the above combinative effects (i.e., (a) heterogeneous catalytic oxidation, (b)

homogeneous catalytic oxidation, (c) adsorption of CuFe2O4 nano-particles and (d) PS

oxidation) work together in the CuFe2O4/PS system and performed synergistic effect

for the PNP degradation.

4. Conclusions

A CuFe2O4/PS heterogeneous catalytic oxidation system was developed to

disintegrate the PNP (50 mg/L) in aqueous solution at ambient temperature. CuFe2O4

23 / 43
magnetic nano-particles were synthesized with a sol-gel combustion method. First,

key parameters (i.e., CuFe2O4 dosage, PS dosage, initial pH and co-existing inorganic

ions) were investigated to obtain the optimal conditions (i.e., CuFe2O4 dosage of 30

g/L, PS of 8.0 mM and initial pH of 7.0). Compared with CuFe2O4 alone and PS alone

systems, it was noted that CuFe2O4/PS process received high PNP removal (i.e., 89 %)

and TOC removal (i.e., 81 %) after 60 min treatment, revealing the high catalytic

performance of the CuFe2O4 particles. Besides, the contradistinctive analysis of

UV-vis spectra and TOC removal of the effluent in 3 systems further confirmed that

CuFe2O4 particles had a strong effect on PS activation. Furthermore, CuFe2O4

particles kept stable in the catalytic process, exhibiting favorable catalytic

performance and reusability after five runs. In addition, quenching experiments

proved that SO4•- were the major radical species for the degradation of PNP. Based on

the intermediates measured by HPLC, the PNP degradation pathway was proposed.

And the results suggested that PNP was decomposed by two pathways (i.e., (i)

combination of reduction and oxidation and (ii) direct oxidation). According to the

analysis results of catalyst characterization, it further confirmed that CuFe2O4

nano-particles process benign stability and reusability. Moreover, the catalytic

mechanism in CuFe2O4/PS was proposed according to the above discussions. All the

results indicated that the CuFe2O4/PS catalytic oxidation was an efficient and cleaning

technology for the toxic and refractory industrial wastewater.

Acknowledgment

The authors would like to acknowledge the financial support from National

24 / 43
Natural Science Foundation of China (No. 21207094), and Fundamental Research

Funds for the Central Universities (No. 2015SCU04A09).

25 / 43
Reference

[1] X. Chen, M. Murugananthan, Y. Zhang, Degradation of p-Nitrophenol by

thermally activated persulfate in soil system, Chem Eng J 283 (2016) 1357-1365.

[2] S.Q. Yu, J. Hu, J.L. Wang, Gamma radiation-induced degradation of p-nitrophenol

(PNP) in the presence of hydrogen peroxide (H2O2) in aqueous solution, J Hazard

Mater 177 (2010) 1061-1067.

[3] H. Feng, T. Tran. T, L. Chen, L. Yuan, Q. Cai, Visible light-induced efficiently

oxidative decomposition of p-Nitrophenol by CdTe/TiO2 nanotube arrays, Chem Eng

J 215–216 (2013) 591-599.

[4] C. Martínez, M. Canle L, M.I. Fernández, J.A. Santaballa, J. Faria, Kinetics and

mechanism of aqueous degradation of carbamazepine by heterogeneous

photocatalysis using nanocrystalline TiO2, ZnO and multi-walled carbon

nanotubes–anatase composites, Applied Catalysis B: Environmental 102 (2011)

563-571.

[5] Y. Segura, F. Martínez, J.A. Melero, Effective pharmaceutical wastewater

degradation by Fenton oxidation with zero-valent iron, Appl Catal B-environ 136-137

(2013) 64-69.

[6] R. Cheng, C. Cheng, G.H. Liu, X. Zheng, G. Li, J. Li, Removing

pentachlorophenol from water using a nanoscale zero-valent iron/H2O2 system,

Chemosphere 141 (2015) 138-143.

[7] H.Y. Shu, M.C. Chang, C.C. Chang, Integration of nanosized zero-valent iron

particles addition with UV/H2O2 process for purification of azo dye Acid Black 24

26 / 43
solution, J Hazard Mater 167 (2009) 1178-1184.

[8] M. Kuosa, A. Laari, A. Solonen, H. Haario, J. Kallas, Multicomponent reaction

kinetics for the ozonation of -nitrophenol and its decomposition products under acidic

conditions at constant pH, Chem Eng Sci 64 (2009) 2332-2342.

[9] L. Zhao, Y. Ji, D. Kong, J. Lu, Q. Zhou, X. Yin, Simultaneous removal of

bisphenol A and phosphate in zero-valent iron activated persulfate oxidation process,

Chem Eng J 303 (2016) 458-466.

[10] Y. Ji, Y. Shi, W. Dong, X. Wen, M. Jiang, J. Lu, Thermo-activated persulfate

oxidation system for tetracycline antibiotics degradation in aqueous solution, Chem

Eng J 298 (2016) 225-233.

[11] Q. Wang, Y. Shao, N. Gao, W. Chu, X. Shen, X. Lu, J. Chen, Y. Zhu, Degradation

kinetics and mechanism of 2,4-Di-tert-butylphenol with UV/persulfate, Chem Eng J

304 (2016) 201-208.

[12] M. Nie, C. Yan, M. Li, X. Wang, W. Bi, W. Dong, Degradation of

chloramphenicol by persulfate activated by Fe2+ and zerovalent iron, Chem Eng J 279

(2015) 507-515.

[13] O.S. Furman, A.L. Teel, R.J. Watts, Mechanism of Base Activation of Persulfate,

Environ Sci Technol 44 (2010) 6423-6428.

[14] Y. Lei, C.-S. Chen, Y.-J. Tu, Y.-H. Huang, H. Zhang, Heterogeneous Degradation

of Organic Pollutants by Persulfate Activated by CuO-Fe3O4: Mechanism, Stability,

and Effects of pH and Bicarbonate Ions, Environ Sci Technol 49 (2015) 6838-6845.

[15] R. Li, X. Jin, M. Megharaj, R. Naidu, Z. Chen, Heterogeneous Fenton oxidation

27 / 43
of 2,4-dichlorophenol using iron-based nanoparticles and persulfate system, Chem

Eng J 264 (2015) 587-594.

[16] A. Özcan, A. Atılır Özcan, Y. Demirci, E. Şener, Preparation of Fe2O3 modified

kaolin and application in heterogeneous electro-catalytic oxidation of enoxacin,

Applied Catalysis B: Environmental 200 (2017) 361-371.

[17] Y. Ren, L. Lin, J. Ma, J. Yang, J. Feng, Z. Fan, Sulfate radicals induced from

peroxymonosulfate by magnetic ferrospinel MFe2O4 (M = Co, Cu, Mn, and Zn) as

heterogeneous catalysts in the water, Applied Catalysis B: Environmental 165 (2015)

572-578.

[18] Y. Du, W. Ma, P. Liu, B. Zou, J. Ma, Magnetic CoFe2O4 nanoparticles supported

on titanate nanotubes (CoFe2O4/TNTs) as a novel heterogeneous catalyst for

peroxymonosulfate activation and degradation of organic pollutants, J Hazard Mater

308 (2016) 58-66.

[19] K. Faungnawakij, Y. Tanaka, N. Shimoda, T. Fukunaga, R. Kikuchi, K. Eguchi,

Hydrogen production from dimethyl ether steam reforming over composite catalysts

of copper ferrite spinel and alumina, Applied Catalysis B: Environmental 74 (2007)

144-151.

[20] Y. Feng, C. Liao, K. Shih, Copper-promoted circumneutral activation of H2O2 by

magnetic CuFe2O4 spinel nanoparticles: Mechanism, stoichiometric efficiency, and

pathway of degrading sulfanilamide, Chemosphere 154 (2016) 573-582.

[21] F. Qi, W. Chu, B. Xu, Ozonation of phenacetin in associated with a magnetic

catalyst CuFe2O4: The reaction and transformation, Chem Eng J 262 (2015) 552-562.

28 / 43
[22] K. Shih, T. White, J.O. Leckie, Nickel stabilization efficiency of aluminate and

ferrite spinels and their leaching behavior, Environ Sci Technol 40 (2006) 5520-5526.

[23] Y.-H. Guan, J. Ma, Y.-M. Ren, Y.-L. Liu, J.-Y. Xiao, L.-q. Lin, C. Zhang,

Efficient degradation of atrazine by magnetic porous copper ferrite catalyzed

peroxymonosulfate oxidation via the formation of hydroxyl and sulfate radicals,

Water Res 47 (2013) 5431-5438.

[24] X. Zhang, M. Feng, L. Wang, R. Qu, Z. Wang, Catalytic degradation of

2-phenylbenzimidazole-5-sulfonic acid by peroxymonosulfate activated with nitrogen

and sulfur co-doped CNTs-COOH loaded CuFe2O4, Chem Eng J 307 (2017) 95-104.

[25] X. Zhang, M. Feng, R. Qu, H. Liu, L. Wang, Z. Wang, Catalytic degradation of

diethyl phthalate in aqueous solution by persulfate activated with nano-scaled

magnetic CuFe2O4/MWCNTs, Chem Eng J 301 (2016) 1-11.

[26] J.E. Tasca, C.E. Quincoces, A. Lavat, A.M. Alvarez, M.G. González, Preparation

and characterization of CuFe2O4 bulk catalysts, Ceram Int 37 (2011) 803-812.

[27] H.-y. Liang, Y.-q. Zhang, S.-b. Huang, I. Hussain, Oxidative degradation of

p-chloroaniline by copper oxidate activated persulfate, Chem Eng J 218 (2013)

384-391.

[28] A. Babuponnusami, K. Muthukumar, A review on Fenton and improvements to

the Fenton process for wastewater treatment, Journal of Environmental Chemical

Engineering 2 (2014) 557-572.

[29] J. Li, Q. Liu, Q.q. Ji, B. Lai, Degradation of p-nitrophenol (PNP) in aqueous

solution by Fe0-PM-PS system through response surface methodology (RSM),

29 / 43
Applied Catalysis B: Environmental 200 (2017) 633-646.

[30] D. Sannino, V. Vaiano, L.A. Isupova, P. Ciambelli, Heterogeneous Photo-Fenton

Oxidation of Organic Pollutants on Structured Catalysts, Journal of Advanced

Oxidation Technologies 15 (2012) 294-300.

[31] D. Sannino, V. Vaiano, P. Ciambelli, L.A. Isupova, Mathematical modelling of

the heterogeneous photo-Fenton oxidation of acetic acid on structured catalysts, Chem

Eng J 224 (2013) 53-58.

[32] J.M. Monteagudo, A. Durán, R. González, A.J. Expósito, In situ chemical

oxidation of carbamazepine solutions using persulfate simultaneously activated by

heat energy, UV light, Fe2+ ions, and H2O2, Applied Catalysis B: Environmental

176–177 (2015) 120-129.

[33] Y. Ding, L. Zhu, N. Wang, H. Tang, Sulfate radicals induced degradation of

tetrabromobisphenol A with nanoscaled magnetic CuFe2O4 as a heterogeneous

catalyst of peroxymonosulfate, Applied Catalysis B: Environmental 129 (2013)

153-162.

[34] S.-X. Li, D. Wei, N.-K. Mak, Z. Cai, X.-R. Xu, H.-B. Li, Y. Jiang, Degradation of

diphenylamine by persulfate: Performance optimization, kinetics and mechanism, J

Hazard Mater 164 (2009) 26-31.

[35] M. Feng, R. Qu, X. Zhang, P. Sun, Y. Sui, L. Wang, Z. Wang, Degradation of

flumequine in aqueous solution by persulfate activated with common methods and

polyhydroquinone-coated magnetite/multi-walled carbon nanotubes catalysts, Water

Res 85 (2015) 1-10.

30 / 43
[36] J. Ma, M. Sui, T. Zhang, C. Guan, Effect of pH on MnOx/GAC catalyzed

ozonation for degradation of nitrobenzene, Water Res 39 (2005) 779-786.

[37] T. Zhang, H. Zhu, J.-P. Croué, Production of Sulfate Radical from

Peroxymonosulfate Induced by a Magnetically Separable CuFe2O4 Spinel in Water:

Efficiency, Stability, and Mechanism, Environ Sci Technol 47 (2013) 2784-2791.

[38] J. Deng, Y. Shao, N. Gao, Y. Deng, S. Zhou, X. Hu, Thermally activated

persulfate (TAP) oxidation of antiepileptic drug carbamazepine in water, Chem Eng J

228 (2013) 765-771.

[39] X. Zou, T. Zhou, J. Mao, X. Wu, Synergistic degradation of antibiotic

sulfadiazine in a heterogeneous ultrasound-enhanced Fe0/persulfate Fenton-like

system, Chem Eng J 257 (2014) 36-44.

[40] C. Liang, I.L. Lee, I.Y. Hsu, C.-P. Liang, Y.-L. Lin, Persulfate oxidation of

trichloroethylene with and without iron activation in porous media, Chemosphere 70

(2008) 426-435.

[41] M. Martín-Hernández, J. Carrera, M.E. Suárez-Ojeda, M. Besson, C. Descorme,

Catalytic wet air oxidation of a high strength p-nitrophenol wastewater over Ru and Pt

catalysts: Influence of the reaction conditions on biodegradability enhancement, Appl

Catal B-environ 123–124 (2012) 141-150.

[42] B. Lai, Y.H. Zhang, Z.Y. Chen, P. Yang, Y.X. Zhou, J.L. Wang, Removal of

p-nitrophenol (PNP) in aqueous solution by the micron-scale iron-copper (Fe/Cu)

bimetallic particles, Appl Catal B-environ 144 (2014) 816-830.

[43] S. Yuan, M. Tian, Y. Cui, L. Lin, X. Lu, Treatment of nitrophenols by cathode

31 / 43
reduction and electro-Fenton methods, J Hazard Mater 137 (2006) 573-580.

[44] Y. Ren, B. Lai, Comparative study on the characteristics, operational life and

reactivity of Fe/Cu bimetallic particles prepared by electroless and displacement

plating process, RSC Adv. 6 (2016) 58302-58314.

[45] P. Laokul, V. Amornkitbamrung, S. Seraphin, S. Maensiri, Characterization and

magnetic properties of nanocrystalline CuFe2O4, NiFe2O4, ZnFe2O4 powders prepared

by the Aloe vera extract solution, Current Applied Physics 11 (2011) 101-108.

[46] J.A. Mielczarski, G.M. Atenas, E. Mielczarski, Role of iron surface oxidation

layers in decomposition of azo-dye water pollutants in weak acidic solutions, Applied

Catalysis B: Environmental 56 (2005) 289-303.

[47] F. Ji, C. Li, L. Deng, Performance of CuO/Oxone system: Heterogeneous

catalytic oxidation of phenol at ambient conditions, Chem Eng J 178 (2011) 239-243.

[48] Y. Wang, H. Zhao, M. Li, J. Fan, G. Zhao, Magnetic ordered mesoporous copper

ferrite as a heterogeneous Fenton catalyst for the degradation of imidacloprid, Applied

Catalysis B: Environmental 147 (2014) 534-545.

[49] Y. Xu, J. Ai, H. Zhang, The mechanism of degradation of bisphenol A using the

magnetically separable CuFe2O4/peroxymonosulfate heterogeneous oxidation

process, J Hazard Mater 309 (2016) 87-96.

[50] H. Li, J. Wan, Y. Ma, M. Huang, Y. Wang, Y. Chen, New insights into the role of

zero-valent iron surface oxidation layers in persulfate oxidation of dibutyl phthalate

solutions, Chem Eng J 250 (2014) 137-147.

[51] L. Xu, J. Wang, Magnetic Nanoscaled Fe3O4/CeO2 Composite as an Efficient

32 / 43
Fenton-Like Heterogeneous Catalyst for Degradation of 4-Chlorophenol, Environ Sci

Technol 46 (2012) 10145-10153.

[52] M. Sui, L. Sheng, K. Lu, F. Tian, FeOOH catalytic ozonation of oxalic acid and

the effect of phosphate binding on its catalytic activity, Applied Catalysis B:

Environmental 96 (2010) 94-100.

[53] L.W. Matzek, K.E. Carter, Activated persulfate for organic chemical degradation:

A review, Chemosphere 151 (2016) 178-188.

[54] F. Mercier, C. Alliot, L. Bion, N. Thromat, P. Toulhoat, XPS study of Eu(III)

coordination compounds: Core levels binding energies in solid mixed-oxo-compounds

EumXxOy, J Electron Spectrosc 150 (2006) 21-26.

[55] C. Liang, H.-W. Su, Identification of Sulfate and Hydroxyl Radicals in Thermally

Activated Persulfate, Ind Eng Chem Res 48 (2009) 5558-5562.

[56] Y. Fan, Y. Ji, D. Kong, J. Lu, Q. Zhou, Kinetic and mechanistic investigations of

the degradation of sulfamethazine in heat-activated persulfate oxidation process,

Journal of hazardous materials 300 (2015) 39-47.

[57] Y. Pang, H. Lei, Degradation of p-nitrophenol through microwave-assisted

heterogeneous activation of peroxymonosulfate by manganese ferrite, Chem Eng J

287 (2016) 585-592.

[58] O.P. Chawla, R.W. Fessenden, Electron spin resonance and pulse radiolysis

studies of some reactions of peroxysulfate (SO4•1,2-), Journal of Physical Chemistry 79

(2002) 2693-2700.

33 / 43
 1.0
(a)
CuFe2O4= 0 g/L
0.8 CuFe2O4= 5 g/L
CuFe2O4= 10 g/L
CuFe2O4= 15 g/L
0.6
CuFe2O4= 20 g/L

C/C0
CuFe2O4= 25 g/L
0.4 CuFe2O4= 30 g/L
[PNP]0=50 mg/L CuFe2O4= 35 g/L
[PS]0=10 mM CuFe2O4= 40 g/L
0.2
Initial pH=6.0
Stirring speed=300 rpm
0.0
0 10 20 30 40 50 60
Time (min)

1.0 (b) 1.0

[PNP]0=50 ppm (c)
CuFe2O4=30 g/L
[PS]0= 8mM pH=3.0
0.8 pH=5.0
0.8 Stirring speed=300 rpm pH=6.0
[PNP]0 =50 ppm PS=0 mM pH=7.0
[CuFe2O4]0 =30 g/L PS=2 mM pH=9.0
0.6 PS=5 mM 0.6
Initial pH=6.0 pH=11.0
PS=7 mM
C/C0
C/C 0

Stirring speed=300 rpm

PS=8 mM
0.4 PS=9 mM 0.4
PS=10 mM

0.2 0.2

0.0 0.0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)

Fig. 1. Effects of (a) CuFe2O4 dosage, (b) PS dosage and (c) initial pH on the degradation of

PNP.

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 1.0 (a)

0.8

[PNP]0=50 mg/L
0.6 [CuFe2O4]0=30 g/L CuFe2O4

C/C0
[PS]0= 8 mM PS
Initial pH= 7.0 CuFe2O4-PS
0.4 Stirring speed=300 rpm

0.2

0.0
0 10 20 30 40 50 60
Time (min)

(b) 7
(c)
80

70
6 [PNP] 0=50 mg/L
60 [PNP]0=50 ppm [CuFe2O4]0=30 g/L
TOC Removal (%)

CuFe2O4=30 g/L [PS]0= 8mM CuFe2O4

50 5 PS
[PS]0= 8mM Initial pH= 7.0

pH
Stirring speed=300 rpm CuFe2O4-PS
40 Initial pH= 7.0
Stirring speed=300 rpm 4
30

20 3

10
2
0 0 10 20 30 40 50 60
PS CuFe2O4 CuFe2O4-PS Time (min)
3.0
(d) 2.5
(e)
[PNP]0=50 mg/L Influent
2.5 Influent 5min
[CuFe2O4]0=30 g/L PS [PNP]0=50 mg/L 10min
[PS]0= 8mM CuFe2O4 2.0
2.0 [CuFe2O4]0=30 g/L 15min
Absorbance (a.u.)

Absorbance(a.u.)

Initial pH= 7.0 CuFe2O4-PS 20min

[PS]0= 8 mM
Stirring speed=300 rpm 1.5 30min
1.5 Initial pH= 7.0
40min
Stirring speed=300 rpm
50min
1.0 60min
1.0
PS

0.5 0.5
CuFe2O4-PS

0.0 0.0

200 250 300 350 400 450 500 200 250 300 350 400 450 500
Wavelength (nm) Wavelength (nm)

Fig. 2. (a) PNP removal, (b) TOC removal, (c) pH and (d) UV spectra of the effluent of 3

different treatment processes, and (e) time course variations of UV spectra during 60 min

process in CuFe2O4/PS system.

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 p-Aminophenol

Concentration (mg/L)
50
2.4 p-Benzoquinone 40 PNP
Fumaric acid
30
Maleic acid
2.0 20

Concentration (mg/L)
10
1.6 0
0 10 20 30 40 50 60
Time (min)
1.2

0.8

0.4

0.0

0 10 20 30 40 50 60
Time (min)
Fig. 3. PNP and its degradation intermediates detected in CuFe2O4/PS system.

Fig. 4. Proposed reaction pathway for the degradation of PNP by CuFe2O4 /PS system.

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 (211)

Fresh CuFe2O4
(112) (224)
(220) (321)
Intensity (a.u.)

Reacted CuFe2O4

PDF#34-0425-CuFe2O4

10 20 30 40 50 60 70 80 90
2-Theta (Deg.)
Fig. 5. XRD patterns of the fresh and reacted CuFe2 O4 nano-particles in CuFe2O4/PS system.

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 Cu
(a) 934.1 eV (b)
941.3 eV 943.7 eV
Fe
Fresh O

Intensity (a.u)
Fresh
Intensity (a.u.)
Cu
FeCu C

941.3 eV
934.1 eV 943.7 eV
936.8 eV
Used
933.2 eV
Reacted

0 200 400 600 800 1000 1200 925 930 935 940 945
Binding Energy (eV) Binding Energy (eV)

724.4 eV (c) (d)

530.1 eV
713.0 eV
710.9 eV

531.6 eV
Fresh Fresh
Intensity (a.u)

Intensity (a.u)
712.5 eV 724.4 eV 529.8 eV

710.9 eV 717.3 eV
531.2 eV

Reacted Reacted 534.0 eV

705 710 715 720 725 730 735 740 525 530 535 540 545

Binding Energy (eV) Binding Energy (eV)

Fig. 6. XPS spectra of fresh and reacted CuFe2O4 nano-particles in CuFe2O4/PS system, (a)
full-range scan of the samples, (b) Cu 2p core level, (c) Fe 2p core level and (d) O 1 s core
level.

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 1.0
1st 2nd 3rd 4th 5th
0.8

0.6

C/C0
0.4

0.2

0.0
0 30 60 90 120 150 180 210 240 270 300

Time (min)

Fig. 7. Operational life of CuFe2 O4 nano-particles in CuFe2 O4/PS system. Experimental

conditions: [PNP]0= 50 mg/L, [CuFe2O4 ]0= 30 g/L, [PS]0= 8 mM, initial pH= 7.0, stirring
speed= 300 rpm.E

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 1.0
[PNP]0=50 mg/L
No scavengers CuFe2O4=30 g/L
500 mM EtOH
0.8 [PS]0=8 mM
500 mM TBA
Initial pH=7.0
Stirring speed=300 rpm
0.6
C/C0

0.4

0.2

0.0
0 10 20 30 40 50 60
Time (min)
Fig. 8. The effects of scavengers (EtOH and TBA) on the degradation of PNP in the
CuFe2O4/PS system.

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Fig. 9. Reaction mechanism for the degradation of PNP by CuFe2O4/PS system.

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 Highlights

(1) The effects of CuFe2O4 dosages, PS dosages, initial pH and co-existing inorganic

ions were investigated thoroughly.

(2) The materials characterization of CuFe2O4 nano-particles were analyzed by TEM,

BET, VSM, XRD and XPS.

(3) The main radical specie (i.e., SO4•−) and the stability of CuFe2O4 nano-particles

were proved.

(4) Degradation pathway of PNP was proposed according to the detected

intermediates.

(5) Mechanism of CuFe2O4/PS system was investigated comprehensively.

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