Chemosphere 163 (2016) 584e591

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Insights of ibuprofen electro-oxidation on metal-oxide-coated Ti

anodes: Kinetics, energy consumption and reaction mechanisms
Chong Wang, Yanxin Yu, Lifeng Yin, Junfeng Niu*, Li-An Hou
State Key Laboratory of Water Environment Simulation, Beijing Normal University, Beijing 100875, 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

Electrochemical degradation of
ibuprofen (IBP) was investigated.

The degradation efficiency was gov-
erned by applied current and plate
distance.

The economic feasibility was evalu-
ated by energy consumption per or-
der (EEO).

The electrochemical mineralization
mechanism of IBP was proposed.

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

Article history: Electrochemical degradation of ibuprofen (IBP) was performed on three types of Ti-based metal oxide
Received 27 June 2016 electrodes. The degradation of IBP followed pseudo-first-order kinetics and the electrochemical degra-
Received in revised form dation rate constant (k) over Ti/SnO2-Sb/Ce-PbO2 (9.4  102 min1) was 2.0 and 1.7 times of the values
11 August 2016
over Ti/Ce-PbO2 (4.7  102 min1) and Ti/SnO2-Sb (5.6  102 min1), respectively. The removal of total
Accepted 12 August 2016
Available online 25 August 2016
organic carbon and the energy consumption per order for IBP degradation were 93.2% and 13.1 Wh L1,
respectively, under the optimal conditions using Ti/SnO2-Sb/Ce-PbO2 anode. Six aromatic intermediate
Handling Editor: E. Brillas products of IBP were identified by ultra-high-performance liquid chromatography coupled with a
quadrupole time-of-flight mass spectrometer. The electrochemical mineralization mechanism of IBP was
Keywords: proposed. It was supposed that
OH radicals produced on the surface of anode attacked IBP to form
Ibuprofen hydroxylated IBP derivatives that were then followed by a series of hydroxylation, loss of isopropanol and
Electrochemical oxidation isopropyl, decarboxylation and benzene ring cleavage processes to form simple linear carboxylic acids. By
Electrodes successive hydroxylation, these carboxylic acids were then oxidized to CO2 and H2O, achieving the
Energy cost
complete mineralization of IBP.
Mineralization
© 2016 Elsevier Ltd. All rights reserved.
Mechanisms

1. Introduction
Ibuprofen (IBP) is a non-prescription, non-steroidal anti-
inflammatory drug which has been widely used in the treatment
of fever, migraine, musculature pain and inflammatory rheumatic
* Corresponding author.
E-mail address: junfengn@bnu.edu.cn (J. Niu).
diseases. More than 15,000 tons of IBP are produced worldwide
each year, but a significant percentage is excreted by patients in its
original form or as metabolites (Ghauch et al., 2012; Markovic et al.,
2015). IBP has been detected in surface water and wastewater at the
range from nanogram to low microgram amounts per litter, and is
continuously being discharged into the environment (Eslami et al.,
2015; Khan et al., 2014; Nebot et al., 2015; Wang et al., 2011). The
ubiquity of IBP is particularly alarming due to the potential adverse
impact on the reproduction of aquatic organisms and human

http://dx.doi.org/10.1016/j.chemosphere.2016.08.057
0045-6535/© 2016 Elsevier Ltd. All rights reserved.
 C. Wang et al. / Chemosphere 163 (2016) 584e591
endocrine system even at low concentrations (Han et al., 2010;
Kang et al., 2015). Hence it is of great importance to develop
effective technology to eliminate IBP from aquatic environment.
Various techniques have been studied to prevent the accumu-
lation of IBP in the aquatic environment. Some physical methods,
such as adsorption (Guedidi et al., 2013; Iovino et al., 2015) or
membrane nanofiltration (Narbaitz et al., 2013), did not lead to
degradation either, which just involved phase transfer of IBP and
thus induced another pollution problem. The drawbacks of bio-
logical processes were generally inefficient and the subsequent
disposal of sludge (Kosjek et al., 2007; London ~ o and Pen~ uela, 2015;
Quintana et al., 2005). Chemical methods such as ozonation
(Quero-Pastor et al., 2014) and ionizing radiation (Illes et al., 2013),
as well as some advanced oxidation processes (AOPs) such as
photocatalytic systems and Fenton reaction based processes, could
provide effective degradation of IBP (Ambuludi et al., 2013b; Li
et al., 2015; Molinari et al., 2006; Xiang et al., 2016). Neverthe-
less, strict operational conditions (e.g., oxygen supply and pH) were
required, or more toxic intermediates, like 1,3-dihydroxyl
ibuprofen and 1-(4-isobutylphenyl)ethanone, formed in some
methods (Ille s et al., 2013; Quero-Pastor et al., 2014). The devel-
opment of cost-effective technologies to eliminate IBP with high
mineralization rate is thus of great challenge.
The electrochemical advanced oxidation process (EAOP) has
recently demonstrated its great ability to efficiently abate envi-
ronmental recalcitrant pollutants (García-Go mez et al., 2014; Lin
et al., 2013a, 2013b; Niu et al., 2012; Shmychkova et al., 2015). In-
formations about the removal of chemical oxygen demand (COD)
and total organic carbon (TOC) for IBP solutions were provided
using Pt, Ti/Pt/PbO2 and boron-doped diamond (BDD) electrodes
(Ambuludi et al., 2013a; Ciríaco et al., 2009; Lima et al., 2013). The
BDD anode had better characteristics for the TOC removal of IBP
solution, which could achieve more than 92% with the current
density of 20e30 mA cm2 after 360e480 min of electrolysis in
200 mL IBP solution (Ambuludi et al., 2013a; Ciríaco et al., 2009).
Unfortunately, intermediate products were not followed, or just a
few small molecular carboxylic acids were identified in these
studies, while explicit mineralization pathway of IBP by electro-
chemical treatment has not been fully understood yet. Besides, the
high production cost makes BDD not feasible for large-scale
application (Lin et al., 2013a; Panizza and Cerisola, 2009). Con-
cerning over the commercial application of electrochemical
degradation of IBP, it is essential to search anodes with high
mineralization rate, mild condition and low cost.
The explored Ti-based metal oxide electrodes (e.g., Ti/RuO2, Ti/
SnO2 and Ti/PbO2) have proven to be efficient electrode materials
for the treatment of recalcitrant pollutants in aqueous solution
(García-Go mez et al., 2014; Shmychkova et al., 2015; Santos et al.,
2013; Xu et al., 2015; Yang et al., 2015; Zhao et al., 2014; Zhou
et al., 2005). In previous researches, we found that Ti/SnO2-Sb
and Ti/SnO2-Sb/Ce-PbO2 electrodes can rapidly and almost
completely remove various organic contaminants, such as penta-
chlorophenol, perfluorocarboxylic acids (PFCAs) and sulfamethox-
azole from aqueous solution (Lin et al., 2013a, 2013b; Niu et al.,
2013). Even the performance of Ti/SnO2-Sb/Ce-PbO2 electrode
was comparable with that of BDD electrode for the degradation of
PFCAs (Lin et al., 2013b). Thus Ti-based metal oxide electrodes may
have great potentiality to completely mineralize IBP to harmless
byproducts.
The aim of this study was to investigate the performance of the
electrochemical oxidation process for the degradation of IBP using
three Ti-based metal oxide anodes. The mineralization of IBP was
elucidated by assessing the removal of the TOC. The energy con-
sumption per order (EEO) of IBP degradation was evaluated to assess
the application potential of the electrochemical oxidation
585
technology. The intermediate products of IBP formed during the
electrochemical degradation were identified to reveal the electro-
chemical mineralization mechanism of IBP.
2. Materials and methods
2.1. Chemicals
Analytical grade IBP, Salicylic Acid (SA), 2,3-dihidroxybenzoic
Acid (2,3-DHBA) and 2,5-dihydroxibenzoic Acid (2,5-DHBA) were
purchased from Sigma Aldrich. All other chemicals were analytical
grade and were purchased from Sinopharm, China. All aqueous
solutions used in our experiments were prepared with Milli-Q
deionized water (18.2 MU cm). The pH values of the solution
were adjusted by H2SO4 (5%, v v1) and NaOH (5%, m m1).
2.2. Electrode fabrication and characterization
Titanium sheets (purity 99.9%, 50 mm  50 mm  1 mm) were
previously polished with different grades papers to a mirror-like
surface, then immersed in NaOH solution (10%, m m1) and
etched with boiling oxalic acid solution (10%, m m1). Ti/SnO2-Sb
electrode and the middle layer of the Ti/SnO2-Sb/Ce-PbO2 were
prepared using the sol-gel technique with a coating solution con-
taining ethylene glycol, citric acid, SnCl4$4H2O and SbCl3 with a
molar ratio of 140:30:9:1. The sol-gel solution was used to coat on
the Ti sheets by the dip-coating method. Then, the Ti sheets were
dried at 145  C for 10 min and sintered at 500  C for 10 min in a
muffle furnace. This procedure was repeated 20 times, and the last
baking was annealed for 2 h at 500  C to obtain Ti/SnO2-Sb elec-
trode (Lin et al., 2013a).
Ti/Ce-PbO2 and the top layer of Ti/SnO2-Sb/Ce-PbO2 electrode
were prepared by electro-deposition. The Ce-doped PbO2 layer was
generated coating on the Ti and Ti/SnO2-Sb, respectively, with an
acidic electrolyte (68  C) consisting of 0.1 M HNO3, 200 g L1
Pb(NO3)2, 0.4 g L1 Ce(NO3)3, and 0.5 g L1 NaF at a constant current
density of 20 mA cm2 for 60 min (Lin et al., 2013b).
The microstructure and morphology of the prepared electrodes
were observed by scanning electron microscopy (SEM; S4800,
Hitachi, Japan) with an accelerating voltage of 10 kV and X-ray
diffraction (XRD; Thermo ARL SCINTAG XTRA, Netherlands) using
Cu Ka radiation, respectively. The oxygen evolution potential (OEP)
of the electrodes were measured with the linear sweep voltam-
metry (LSV) technique conducted in conventional three-electrode
electrochemical cells on an electrochemical workstation (CHI
660D, Chenhua, Shanghai, China). The prepared electrodes served
as the work electrode (1 cm  2 cm), a platinum foil and a saturated
calomel electrode (SCE) as the counter electrode and the reference
electrode, respectively. The characterized results are shown in
Figs. SM-1e3 of the Supplementary Material (SM).
2.3. Electrochemical experiments
The electrochemical oxidation experiments were conducted in
undivided electrolytic cells made of organic glass. The Ti/SnO2-Sb/
Ce-PbO2, Ti/Ce-PbO2 and Ti/SnO2-Sb electrodes were used as an-
odes, and Ti sheets as the cathodes. Before electrolysis experiments,
controlled trials with no power supply were conducted. No obvious
losses of IBP were detected after 240 min, indicating that degra-
dation by sorption or hydrolysis was negligible. For most experi-
ments, a relative high initial concentration of IBP (20.0 mg L1) was
used to investigate the effects of main operating factors on the
degradation efficiency and the monitoring of major degradation
intermediates during the treatment. When investigating the effect
of operating parameters on IBP electrochemical degradation, 30 mL
586 C. Wang et al. / Chemosphere 163 (2016) 584e591
of IBP solution was used to conduct the experiments with different
current density (2e40 mA cm2), initial pH value (4.0e12.0) with
10 mM Na2SO4 as supporting electrolyte. 30e100 mL of IBP solution
was used to investigate the effect of electrode distance (5e20 mm).
Besides, relative low initial IBP concentrations (1.0e10.0 mg L1)
were also used to better simulate the degradation efficiency of the
real wastewater. The solution was not stirred due to the short
electrodes distance. The electrolysis was conducted with a power
supply (DH1715A, Beijing Dahua Electronic Co., China) at constant
current. The solution pH was detected by a microprocessor pH
meter (pH211, EUTECH Co., USA). All the electrochemical experi-
ments were conducted at least in triplicate and operated at
(25 ± 1)  C.
2.4. Instrumental analysis
The concentrations of IBP were determined by a high-
performance liquid chromatography (HPLC, Dionex U3000, USA)
equipped with a fluorescence detector and an Athena C18-WP
column (4.6 mm  250 mm, 5 mm particle size). The production
of hydroxyl radical (
OH) was determined with SA trapping and
analyzed by HPLC-UV (Peralta et al., 2014). The details are provided
in Text SM-1 and SM-2 of the SM. TOC was measured using a TOC-L-
CPN analyzer (Shimadzu Co, Japan) to evaluate the mineralization
of IBP.
The intermediate products formed during the electrochemical
process of IBP were identified using an ultra-high-performance
liquid chromatography coupled with a quadrupole time-of-flight
mass spectrometer (UPLC-Q-TOF-MS, Xevo G2, Waters Corp, USA)
equipped with an ACQUITY UPLC BEH C18 column (2.1
mm  100 mm; 1.7 mm particle size; Waters, USA). The column
oven was kept at 35  C. The mobile phase A was Milli-Q water with
0.1% formic acid (v v1), and the mobile phase B was acetonitrile.
The flow rate and gradient condition are shown in Text SM-3 of the
SM. Before analysis, solution sample was prepared by an enrich-
ment and clean-up step with a solid phase extraction (SPE) system
with HLB cartridges (6 mL, 500 mg, Waters, Watford, UK).
2.5. Energy consumption
EEO is a powerful scale-up parameter of merit for comparing the
efficiency and electric cost of the treatment system with other
AOPs. The EEO for operating system can be calculated in Eq. (1) (Xia
et al., 2015):
SjUt
EEO ¼ (1)
V logðC0 =CÞ
where EEO is the electric energy consumed to degrade the con-
centration of IBP by one order of magnitude in 1 L solution
(Wh L1), S is the anode surface area (cm2), j is the applied current
density (mA cm2), U is the recorded average voltage (V) during
electrolysis in each experimental condition, and V is the volume of
the reaction solution (mL), C0 is the initial concentration of IBP
(mg L1), and C is the final concentration of IBP (mg L1), t is the
time (min) needed to degrade IBP from the initial concentration to
the final concentration.
3. Results and discussion
3.1. Electrochemical degradation kinetics of IBP
3.1.1. Effect of anode materials
Since
OH played a significant role in electrochemical degrada-
tion of recalcitrant pollutants over “non-active” anodes (Carter and
Farrell, 2008; Lin et al., 2013a; Liao and James, 2009; Zhao et al.,
2010), the generation capacity of
OH on the anodes under a cur-
rent density of 5 mA cm2 was determined based on their reaction
with SA to form hydroxylated products. In our study, only 2,5-DHBA
was detected during the electrolysis process, so the
OH concen-
tration was equal to the 2,5-DHBA concentration according to the
reaction stoichiometry. Fig. 1 shows that the concentration of
OH
generated on the Ti/SnO2-Sb/Ce-PbO2 anode was higher than that
on Ti/Ce-PbO2 and Ti/SnO2-Sb anodes. The production of
OH fol-
lowed pseudo-zero-order kinetics (R2 > 0.99) before 15 min on all
anodes due to the excess of SA. The production rate constants (k) of

OH were 17.2, 12.3, and 14.5 mM (min m2)1 on Ti/SnO -Sb/Ce-
2
PbO2, Ti/Ce-PbO2 and Ti/SnO2-Sb anodes, respectively, at the cur-
rent density of 5 mA cm2. (It is noted that these calculated values
might be lower than actual generation rate due to the short life
time of
OH (Peralta et al., 2014) and their incompletely reaction
with SA.) This suggested that Ti/SnO2-Sb/Ce-PbO2 might have the
best electrochemical oxidation performance.
To verify above speculation, the degradation of IBP on these
three metal-oxide-coated Ti based electrodes was carried out at
5 mA cm2 with the initial IBP concentration of 20.0 mg L1 (Fig. 2).
The degradation ratios of IBP on Ti/SnO2-Sb/Ce-PbO2, Ti/Ce-PbO2
and Ti/SnO2-Sb anodes were 92.4%, 65.2% and 78.6%, respectively,
after 30 min of electrolysis. The degradation of IBP followed
pseudo-first-order kinetics on all anodes. The electrochemical
degradation rate constant (k) over Ti/SnO2-Sb/Ce-PbO2
(9.4  102 min1) was 2.0 and 1.7 times of the values over Ti/Ce-
PbO2 (4.7  102 min1) and Ti/SnO2-Sb (5.6  102 min1),
respectively. Besides, the degradation of IBP were significantly
Fig. 1. Concentrations of hydroxyl radicals produced on Ti/Ce-PbO2, Ti/SnO2-Sb and Ti/
SnO2-Sb/Ce-PbO2 electrodes at the applied current density of 5 mA cm2. Initial
trapping agent SA: 7 mM, Na2SO4: 10 mM, electrode distance: 5 mm, pH: without
adjusted, T: (25 ± 1)  C.
Fig. 2. Electrochemical degradation of 20.0 mg L1 IBP without (solid lines) and with
(dotted lines) isopropanol (IPA) (5%, v v1) on IBP removal by electrochemical degra-
dation by Ti/Ce-PbO2, Ti/SnO2-Sb and Ti/SnO2-Sb/Ce-PbO2 electrodes at the applied
current density of 5 mA cm2. Na2SO4:10 mM, electrode distance: 5 mm, pH: without
adjusted, T: (25 ± 1)  C.
 C. Wang et al. / Chemosphere 163 (2016) 584e591 587

inhibited on all anodes (see Fig. 2) by adding 5% (v v1) isopropanol
(IPA), one scavenger of
OH (Li et al., 2009), to the solution. This
proved indirectly that the
OH generation ability of the electrode
material dominated the electrochemical degradation of IBP. Thus
Ti/SnO2-Sb/Ce-PbO2, which had the highest generation capacity of

OH, was used to conduct the following experiments.
3.1.2. Effect of applied current density
The effect of current density on the degradation efficiency of IBP
(20.0 mg L1) with Ti/SnO2-Sb/Ce-PbO2 electrode was determined
and the result is shown in Fig. 3a. The results showed that the
increasing current density could significantly accelerate the
degradation rate of IBP. The k values increased from 5.8  102 to
2.1  101 min1 as the current density increased from 2 to
40 mA cm2 (see Table 1). A much quicker degradation rate was
observed at a higher applied current density (20 mA cm2), with
almost complete degradation of IBP after 30 min, which was
probably due to the higher
OH production with higher current
densities (Lin et al., 2012). As shown in Table 1, the t1/2 values of IBP
were 11.9, 7.3, 5.4, 4.4, 3.7 and 3.4 min for the current density values
of 2, 5, 10, 20, 30, and 40 mA cm2, respectively. The results indi-
cated that the t1/2 values decreased with limited as the applied
current density was higher than 20 mA cm2, implying that further
increase current density (20 mA cm2) was not as efficient. The

Fig. 3. The degradation of IBP in 10 mM Na2SO4 at (25 ± 1)  C. (a) Effect of the applied current density on degradation of 20 mg L1 IBP at electrode distance 5 mm, pH: without
adjusted. (b) Effect of the electrode distance on degradation of 20 mg L1 IBP at applied current density 10 mA cm2, pH: without adjusted. (c) Effect of the initial pH on degradation
of 20 mg L1 IBP at electrode distance 5 mm at applied current density 10 mA cm2. (d) Effect of the initial concentration on degradation of IBP at electrode distance 5 mm at applied
current density 10 mA cm2, pH: without adjusted.

Table 1
The kinetics and energy cost for the IBP degradation by Ti/SnO2-Sb/Ce-PbO2 electrode.

Parameters Average voltage (V) Rate constants (k, min1)a Half-lives (t1/2, min) R2 EEOb (Wh L1)
2 2
Current density (mA cm ) 2 3.9 5.8  10 11.9 0.995 4.3
5 4.2 9.4  102 7.3 0.993 7.1
10 5.2 1.3  101 5.4 0.991 13.1
20 5.8 1.6  101 4.4 0.986 23.3
30 6.5 1.8  101 3.7 0.989 33.6
40 6.8 2.1  101 3.4 0.995 42.1
Plate distance (mm) 5 5.2 1.3  101 5.4 0.991 13.1
10 5.5 7.6  102 9.1 0.994 16.6
15 6.1 4.3  102 15.9 0.993 26.9
20 6.8 3.1  102 22.7 0.987 30.6
pH 4 4.5 1.3  101 5.2 0.989 10.8
6 4.8 1.2  101 5.3 0.990 13.0
8 4.6 1.2  101 5.9 0.997 12.4
10 4.7 9.1  102 7.5 0.994 16.0
12 4.8 7.7  102 9.0 0.996 20.1
Initial concentration (C0, mg L1) 1 6.8 2.1  101 3.2 0.990 4.7
2 5.9 1.8  101 3.8 0.987 6.8
5 4.9 1.6  101 4.3 0.991 8.5
10 5.2 1.4  101 5.0 0.986 11.6
20 5.2 1.3  101 5.4 0.991 13.1

Other operating conditions are given in Fig. 3.

a
Pseudo-first-order rate constants of electrochemical degradation.
b
Electrical energy cost per order of magnitude in 1 L.
588 C. Wang et al. / Chemosphere 163 (2016) 584e591
excess production of
OH which was oxidized to oxygen on the
anode surface with the increasing applied current density might
account for this phenomenon (Ambuludi et al., 2013a; Li et al.,
2014; Lin et al., 2013a; Skoumal et al., 2009). It could be deduced
that a current oversupply led to energy waste and this opinion
would be proven in later part.
3.1.3. Effect of electrode distance
Fig. 3b shows a rapid degradation of IBP at the electrode dis-
tance of 5 mm with complete disappearance after 40 min applying
the current density of 10 mA cm2. At the plate distance of
15e20 mm, the complete degradation of IBP needed more than
60 min. As shown in Table 1, the k value at the electrode distance of
5 mm was 1.3  101 min1, which was approximately 1.7, 3.0, and
4.2 times of those at the electrode distance of 10, 15 and 20 mm,
respectively. It meant that more electrolysis time was required at a
larger electrode distance due to the longer diffusion distance of IBP.
The results indicated that a shorter plate distance resulted in a
higher degradation efficiency of IBP.
3.1.4. Effect of initial pH value
The initial pH is of crucial importance in the electrochemical
oxidation process (Chen et al., 2015). The initial pH of the solution
without adjusted was about 5.2. The effect of the initial pH on the
degradation efficiency of IBP was examined by adjustment of the
medium pH to 4.0, 6.0, 8.0 10.0 and 12.0 before electrolysis, since in
strong acidic solution the solubility of IBP decreases sharply, lead-
ing to the precipitation of IBP (Ciríaco et al., 2009). As shown in
Fig. 3c, the initial pH had no significant effect on the degradation
kinetics of IBP in acid and weak alkaline conditions, and the k
values were 1.3  101, 1.2  101 and 1.2  101 min1, respec-
tively, at the pH values of 4.0, 6.0 and 8.0. The k values decreased
slightly to 9.1  102 and 7.7  102 min1 when the initial pH
increased to 10.0 and 12.0. One mechanism was proposed to
explain the degradation trend: the oxidation potential of
OH was
lower in alkaline condition (þ2.02 V) than in acid condition
(þ2.85 V) (Zhao et al., 2014), thus high pH enhanced the oxygen
evolution at the anode surface and caused the decrease of IBP
degradation efficiency (Wang et al., 2010; Zhou et al., 2005). In
general, initial pH have little effect on the degradation kinetics of
IBP at tested level, thus the pH of the solution was not adjusted in
the following experiments.
3.1.5. Effect of initial IBP concentration
Fig. 3d shows the degradation of IBP as a function of its initial
concentration. For all cases, the almost complete elimination of IBP
was reached after 40 min at the applied current density of
10 mA cm2. The k values of IBP electrolysis with initial concen-
trations of 1.0, 2.0, 5.0, 10.0, and 20.0 mg L1 were 2.1  101,
1.8  101, 1.6  101, 1.4  101, and 1.3  101 min1, respectively.
This indicated that the lower the initial concentration of IBP, the
faster its oxidation rate. One reason causing this phenomenon was
that the
OH generated on the surface of the anode was almost
identical at a given current density (Zhao et al., 2014). Thus at lower
initial IBP concentrations, the higher ratio of
OH to IBP led to the
greater probability for IBP molecules being attacked by
OH,
allowing rapid degradation of IBP. Another reason was that more
intermediates produced with the increase of initial concentration
of IBP and these intermediates may compete for the oxidation re-
action with IBP for
OH on the surface of the electrode, restraining
the degradation efficiency of IBP.
3.2. The mineralization of IBP under the optimum conditions
Although high degradation rate of IBP could be achieved by
some other AOPs, but some organic byproducts (i.e., 1,3-dihydroxyl
ibuprofen and 1-(4-isobutylphenyl)ethanone) with greater toxicity
were formed during the degradation process (Ille s et al., 2013;
Quero-Pastor et al., 2014). Thus high degree of mineralization of
IBP is still desirable. To determine whether IBP could be completely
mineralized by the Ti/SnO2-Sb/Ce-PbO2 anode during the electro-
chemical oxidation process, the removal of TOC were investigated
at initial concentration of 20.0 mg L1 under the optimum condi-
tions. As shown in Fig. 4, the removal of TOC was quick at the first
30 min and the mineralization rate achieved to 72.0%. The results
were due to the fact that large quantities of
OH generated on the
surface of Ti/SnO2-Sb/Ce-PbO2 anode under the applied condition,
making IBP and its byproducts being simultaneously mineralized
(Li et al., 2014; Lin et al., 2013b; Yuan et al., 2013). At the later stage,
the decay of TOC tended to be slow and the removal rate was 93.2%
after 60 min electrolysis. It indicated that the Ti/SnO2-Sb/Ce-PbO2
anode could rapidly mineralize IBP at a relative low applied current
density of 10 mA cm2. Previous studies found that the removal of
TOC could achieve 92% (current density: 30 mA cm2, initial con-
centrations of IBP: 1.75 mM, 360 min) and 96% (current density:
20 mA cm2, initial concentrations of IBP: 0.2 mM, 480 min) using
BDD electrodes (Ambuludi et al., 2013a; Ciríaco et al., 2009).
Therefore, it can be indicative of effective mineralization of IBP in
aqueous solution by electrochemical technique using Ti/SnO2-Sb/
Ce-PbO2 electrode.
3.3. Energy cost upon electrochemical oxidation of IBP solutions
The economic feasibility of IBP mineralization by the Ti/SnO2-
Sb/Ce-PbO2 anode was evaluated by calculating the EEO (Eq. (1)).
Table 1 shows the EEO required for degrading IBP by Ti/SnO2-Sb/Ce-
PbO2 under different conditions. It can be seen that the EEO for IBP
degradation would increase from 4.3 to 42.1 Wh L1, as the applied
current density increased from 2 to 40 mA cm2. Therefore the EEO
at 40 mA cm2 was 9.7 times of the value at 2 mA cm2, while the k
value only increased 3.6 times, indicating that a higher applied
current density leads to large amounts of energy waste. On the
contrary, though a lower applied current density costs lower en-
ergy, it requires more residence time, thus decreases the space
utilization in the practice application. So the applied current den-
sity of 10 mA cm2 is appropriate due to relative low EEO
(13.1 Wh L1) and the relative short half-life time (5.4 min).
As shown in Table 1, the electrode distance also has a significant
effect on energy cost. The EEO is 13.1 Wh L1 at the electrode dis-
tance of 5 mm, much lower than the values of 16.6, 26.9, and
30.6 Wh L1 at the electrode distance of 10, 15, and 20 mm,
respectively. Higher EEO required at larger electrode distance can be
attributed to the increase of the electrolysis resistance and
Fig. 4. TOC removal as a function of electrolysis time under the optimal conditions.
Applied current density: 10 mA cm2, Na2SO4:10 mM, electrode distance: 5 mm, pH:
without adjusted, T ¼ (25 ± 1)  C.
 C. Wang et al. / Chemosphere 163 (2016) 584e591
substrate diffusion distance (Lin et al., 2013a). Thus short plate
distance is beneficial to rapid mineralize IBP with low energy cost.
3.4. Intermediate analysis of IBP and possible mineralization
mechanisms
The structural assignments of intermediates were identified by
means of UPLC-Q-TOF-MS in the positive and negative mode to
elucidate the mineralization mechanism of IBP by electrochemical
oxidation. In virtue of the accurate mass measurements of TOF-MS,
the elemental composition and their fragment ions of the in-
termediates can be obtained reliably (Bueno et al., 2007). A total of
six aromatic intermediates of IBP were identified. Detailed infor-
mation is shown in Table SM-1 and Fig. SM-4 of the SM. Most of
these aromatic intermediates of IBP have also been observed in
other
OH-initiated AOPs (Ille s et al., 2013; Li et al., 2014; Zheng
et al., 2011). The results suggested that
OH produced by Ti/SnO2-
Sb/Ce-PbO2 anode played a significant role on IBP mineralization
during the electrochemical process. Only one mono-hydroxylated
IBP (2-(4-isobutylphenyl)-2-hydroxypropionic acids, p1) was
detected in this study, whereas other studies reported that both
positions of propanoic acid and isobutyl substituents of IBP could
be attacked by
OH to form different hydroxylated IBP (Ille s et al.,
2013; Li et al., 2014). Previous studies also reported that the hy-
droxylation process could be the initial reaction stage of the
mineralization of IBP by electro-peroxone (Li et al., 2014) and
photoelectron-Fenton (Skoumal et al., 2009) processes. Two de-
rivatives of decarboxylated IBPs, 1-(4-(1-hydroxyethyl) phenyl)-2-
methylpropan-1-one (p2) and 4-isobutylacetophenone (p3), were
detected and the formation of these intermediates was associated
with the oxidation of hydroxyl to yield carbonyl. 2-(4-
methylphenyl) propanoic acid (p5) with the structure of carboxyl
group was detected. Besides, smaller aromatic intermediates,
including 4-(1-hydroxyethyl) benzaldehyde (p4) and 4-
acetyltoluene (p6), with the property of benzene ring readily be-
ing cleaved, were identified. Interestingly, p6 (MW ¼ 134) was not
identified in other
OH-initiated AOPs, but another isomers of p6
(4-ethylbenzaldehyde) was detected (Ille s et al., 2013; Li et al.,
2014; Zheng et al., 2011), implying that a difference mineraliza-
tion mechanism of IBP might exist compared with other
OH-
Fig. 5. Proposed reaction pathways for the mineralization of IBP by electrochemical oxidation.
589
initiated AOPs.
Based on the detected intermediates, a possible degradation
scheme of IBP with two main pathways (A and B) was proposed
(see Fig. 5), including the products detected and hypothetical in-
termediates within bracket. As the utilized Ti/SnO2-Sb/Ce-PbO2
anode is a typical non-active electrode, it can persistently produce a
large amount of
OH during electrochemical process (Lin et al.,
2013a; Zhu et al., 2008). The produced
OH attacked IBP at the
C(2) position of its isobutyl substituent or the C(2) position of its
propionic acid group, resulting in the formation of hydroxylated IBP
isomers the hypothetical 2-hydroxy-ibuprofen or identified p1,
respectively. The first hydroxylated IBP then underwent through
hydroxylation, decarboxylation and loss of isopropanol to form p6
along route A. Pathway B was undertaken by the formation of 1-(1-
hydroxyethyl)-4-isobutylbenzene via the decarboxylation of p1.
This intermediate subsequently evolved to p2 or p3 through
OH
attacking at the C(1) position of its isobutyl substituent or the C(1)
position of its ethanol group, respectively. These two compounds
were then oxidized to p4 and p6, along with the loss of isopropyl
reactions. Further oxidation of these smaller aromatics (p4 and p6)
by
OH resulted in cleavages of the benzene ring, which produced a
variety of linear carboxylic acids. These acids could be finally
mineralized to CO2 and H2O via successive hydroxylation reactions.
Note that, the solution pH decreased slowly from 5.2 (initial pH of
the IBP solution) to about 4.3 at ~30 min and increased to 5.7 at
~60 min during electrolysis, indicating that the slow accumulation
of carboxylic acids and then oxidized by
OH in the mineralization
process of IBP.
The degradation mechanisms of IBP proposed in this study was
different from that using non-thermal plasma (NTP), in which 1-(4-
acetylphenyl)-2-methyl-1-propanone was detected and still
remained after 120 min treatment (Zeng et al., 2015). The difference
of degradation mechanisms led directly to different mineralization
efficiency of IBP, i.e. the removal rate of TOC achieved to 93.2% after
60 min in this study, while only 66.0% of TOC was removed even
after 180 min by NTP. Besides, the proposed degradation mecha-
nism was also different from that proposed by Skoumal et al.
(2009), who used photoelectron-Fenton with BDD combination
technique to eliminate IBP. By comparison, the end aromatic
byproducts (p4 and p6) listed in Fig. 5 possessed more simple
590 C. Wang et al. / Chemosphere 163 (2016) 584e591
structure. It makes the cleavages of the benzene ring of these
byproducts easier, thus favor the absolutely mineralization of IBP.
The great ability of high mineralization efficiency of the electro-
chemical oxidation process makes it an interesting alternative for
the remediation of IBP in aqueous solution.
4. Conclusions
The electrochemical degradation of IBP followed pseudo-first-
order kinetics and the k value of the Ti/SnO2-Sb/Ce-PbO2
(9.4  102 min1) was 2.0 and 1.7 times of the values over Ti/Ce-
PbO2 (4.7  102 min1) and Ti/SnO2-Sb (5.6  102 min1),
respectively. Kinetic investigations demonstrated that the degra-
dation rate constant increased with the increasing applied current
density and the decreasing electrode distance. The degradation of
IBP was favored in acid and weak alkaline conditions
(pH ¼ 4.0e8.0). The k values were 2.1  101 to 1.3  101 min1 at
the initial IBP concentrations range from 1.0 to 20.0 mg L1, indi-
cating higher degradation rate of IBP achieved at relative lower
initial concentrations. Under the optimum condition, the removal
of TOC and the EEO for IBP degradation were 93.2% and 13.1 Wh L1,
with short half-life time (5.4 min). Six aromatic intermediates of
IBP were identified by UPLC-Q-TOF-MS and a possible electro-
chemical mineralization pathway was proposed. The mineraliza-
tion process of IBP mainly includes hydroxylation, decarboxylation,
loss of isopropanol and isopropyl reactions.
Acknowledgements
This study was financially supported by the National Natural
Science Foundation of China (Nos. 51238006 and 51378065) and
the Fund for Innovative Research Group of the National Natural
Science Foundation of China (No. 51421065).
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.chemosphere.2016.08.057.
References
€
Ambuludi, S.L., Panizza, M., Oturan, N., Ozcan, A., Oturan, M.A., 2013a. Kinetic
behavior of anti-inflammatory drug ibuprofen in aqueous medium during its
degradation by electrochemical advanced oxidation. Environ. Sci. Pollut. Res.
20, 2381e2389.
€
Ambuludi, S.L., Panizza, M., Oturan, N., Ozcan, A., Oturan, M.A., 2013b. Electro-
Fenton degradation of anti-inflammatory drug ibuprofen in hydroorganic me-
dium. J. Electroanal. Chem. 702, 31e36.
Bueno, M.J.M., Aguera, A., Gomez, M.J., Hernando, M.D., Garcia-Reyes, J.F., Fernan-
dez-Alba, A.R., 2007. Application of liquid chromatography/quadrupole-linear
ion trap mass spectrometry and time-of-flight mass spectrometry to the
determination of pharmaceuticals and related contaminants in wastewater.
Anal. Chem. 79, 9372e9384.
Carter, K.E., Farrell, J., 2008. Oxidative destruction of perfluorooctane sulfonate
using boron-doped diamond film electrodes. Environ. Sci. Technol. 42,
6111e6115.
Chen, J.M., Xia, Y.J., Dai, Q.Z., 2015. Electrochemical degradation of chloramphenicol
with a novel Al doped PbO2 electrode: performance, kinetics and degradation
mechanism. Electrochim. Acta 165, 277e287.
Ciríaco, L., Anjo, C., Correia, J., Pacheco, M.J., Lopes, A., 2009. Electrochemical
degradation of ibuprofen on Ti/Pt/PbO2 and Si/BDD electrodes. Electrochim.
Acta 54, 1464e1472.
Eslami, A., Amini, M.M., Yazdanbakhsh, A.R., Rastkari, N., Mohseni-Bandpei, A.,
Nasseri, S., Piroti, E., Asadi, A., 2015. Occurrence of non-steroidal anti-inflam-
matory drugs in Tehran source water, municipal and hospital wastewaters, and
their ecotoxicological risk assessment. Environ. Monit. Assess. 187, 1e15.
García-Gomez, C., Drogui, P., Zaviska, F., Seyhi, B., Gort
ares-Moroyoqui, P., Buelna, G.,
Neira-Sa enz, C., Estrada-Alvarado, M., Ulloa-Mercado, R.G., 2014. Experimental
design methodology applied to electrochemical oxidation of carbamazepine
using Ti/PbO2 and Ti/BDD electrodes. J. Electroanal. Chem. 732, 1e10.
Ghauch, A., Tuqan, A.M., Kibbi, N., 2012. Ibuprofen removal by heated persulfate in
aqueous solution: a kinetics study. Chem. Eng. J. 197, 483e492.
Guedidi, H., Reinert, L., Le v e
^que, J.M., Soneda, Y., Bellakhal, N., Duclaux, L., 2013. The
effects of the surface oxidation of activated carbon, the solution pH and the
temperature on adsorption of ibuprofen. Carbon 54, 432e443.
Han, S., Choi, K., Kim, J., Ji, K., Kim, S., Ahn, B., Yun, J., Choi, K., Khim, J.S., Zhang, X.,
Giesy, J.P., 2010. Endocrine disruption and consequences of chronic exposure to
ibuprofen in Japanese medaka (Oryzias latipes) and freshwater cladocerans
Daphnia magna and Moina macrocopa. Aquat. Toxicol. 98, 256e264.
s, E., Taka
Ille cs, E., Dombi, A., Gajda-Schrantz, K., R acz, G., Gonter, K., Wojn arovits, L.,
2013. Hydroxyl radical induced degradation of ibuprofen. Sci. Total Environ.
447, 286e292.
Iovino, P., Canzano, S., Capasso, S., Erto, A., Musmarra, D., 2015. A modeling analysis
for the assessment of ibuprofen adsorption mechanism onto activated carbons.
Chem. Eng. J. 277, 360e367.
Kang, K., Jang, M., Cui, M.C., Qiu, P., Na, S., Son, Y., Khim, J., 2015. Enhanced sono-
catalytic treatment of ibuprofen by mechanical mixing and reusable magnetic
core titanium dioxide. Chem. Eng. J. 264, 522e530.
Khan, S.J., Wang, L.L., Hashim, N.H., Mcdonald, J.A., 2014. Distinct enantiomeric
signals of ibuprofen and naproxen in treated wastewater and sewer overflow.
Chirality 26, 739e746.
Kosjek, T., Heath, E., Kompare, B., 2007. Removal of pharmaceutical residues in a
pilot wastewater treatment plant. Anal. Bioanal. Chem. 387, 1379e1387.
Li, F.H., Yao, K., Lv, W.Y., Liu, G.G., Chen, P., Huang, H.P., Kang, Y.P., 2015. Photo-
degradation of ibuprofen under UVeVis irradiation: mechanism and toxicity of
photolysis products. Bull. Environ. Contam. Toxicol. 94, 479e483.
Li, G., Wong, K.H., Zhang, X., Hu, C., Yu, J.C., Chan, R.C.Y., Wong, P.K., 2009. Degra-
dation of Acid orange 7 using magnetic AgBr under visible light: the roles of
oxidizing species. Chemosphere 76, 1185e1191.
Li, X., Wang, Y.J., Yuan, S., Li, Z.X., Wang, B., Huang, J., Deng, S.B., Yu, G., 2014.
Degradation of the anti-inflammatory drug ibuprofen by electro-peroxone
process. Water Res. 63, 81e93.
Liao, Z.H., James, F., 2009. Electrochemical oxidation of perfluorooctane sulfonate
using boron-doped diamond film electrodes. J. Appl. Electrochem. 39,
1993e1999.
Lima, A.B., Faria, E.O., Montes, R.H.O., Cunha, R.R., Richter, E.M., Munoz, R.A.A., Dos
Santos, W.T.P., 2013. Electrochemical oxidation of ibuprofen and its voltam-
metric determination at a boron-doped diamond electrode. Electroanalysis 25,
1585e1588.
Lin, H., Niu, J.F., Ding, S.Y., Zhang, L.Y., 2012. Electrochemical degradation of per-
fluorooctanoic acid (PFOA) by Ti/SnO2-Sb, Ti/SnO2-Sb/PbO2 and Ti/SnO2-Sb/
MnO2 anodes. Water Res. 46, 2281e2289.
Lin, H., Niu, J.F., Xu, J.L., Li, Y., Pan, Y.H., 2013a. Electrochemical mineralization of
sulfamethoxazole by Ti/SnO2-Sb/Ce-PbO2 anode: kinetics, reaction pathways,
and energy cost evolution. Electrochim. Acta 97, 167e174.
Lin, H., Niu, J.F., Xu, J.L., Huang, H.O., Li, D., Yue, Z.H., Feng, C.H., 2013b. Highly
efficient and mild electrochemical mineralization of long-chain per-
fluorocarboxylic acids (C9-C10) by Ti/SnO2-Sb/Ce-PbO2. Environ. Sci. Technol.
47, 13039e13046.
London ~ o, Y.A., Pen~ uela, G.A., 2015. Biological removal of different concentrations of
ibuprofen and methylparaben in a sequencing batch reactor (SBR). Water Air
Soil Pollut. 226 http://dx.doi.org/10.1007/s11270-015-2654-5.
Markovic, M., Jovic, M., Stankovic, D., Kovacevic, V., Roglic, G., Gojgic-Cvijovic, G.,
Manojlovic, D., 2015. Application of non-thermal plasma reactor and Fenton
reaction for degradation of ibuprofen. Sci. Total Environ. 505, 1148e1155.
Molinari, R., Pirillo, F., Loddo, V., Palmisano, L., 2006. Heterogeneous photocatalytic
degradation of pharmaceuticals in water by using polycrystalline TiO2 and a
nanofiltration membrane reactor. Catal. Today 118, 205e213.
Narbaitz, R.M., Rana, D., Dang, H.T., Morrissette, J., Matsuura, T., Jasim, S.Y., Tabe, S.,
Yang, P., 2013. Pharmaceutical and personal care products removal from
drinking water by modified cellulose acetate membrane: field testing. Chem.
Eng. J. 225, 848e856.
Nebot, C., Falcon, R., Boyd, K.G., Gibb, S.W., 2015. Introduction of human pharma-
ceuticals from wastewater treatment plants into the aquatic environment: a
rural perspective. Environ. Sci. Pollut. Res. 22, 10559e10568.
Niu, J.F., Lin, H., Xu, J.L., Wu, H., Li, Y.Y., 2012. Electrochemical mineralization of
perfluorocarboxylic acids (PFCAs) by Ce-doped modified porous nanocrystalline
PbO2 film electrode. Environ. Sci. Technol. 46, 10191e10198.
Niu, J.F., Bao, Y.P., Li, Y., Chai, Z., 2013. Electrochemical mineralization of penta-
chlorophenol (PCP) by Ti/SnO2eSb electrodes. Chemosphere 92, 1571e1577.
Panizza, M., Cerisola, G., 2009. Direct and mediated anodic oxidation of organic
pollutants. Chem. Rev. 109, 6541e6569.
Peralta, E., Roa, G., Hernandez-Servin, J.A., Romero, R., Balderas, P., Natividad, R.,
2014. Hydroxyl radicals quantification by UV spectrophotometry. Electrochim.
Acta 129, 137e141.
Quero-Pastor, M.J., Garrido-Perez, M.C., Acevedo, A., Quiroga, J.M., 2014. Ozonation
of ibuprofen: a degradation and toxicity study. Sci. Total Environ. 466e467,
957e964.
Quintana, J.B., Weiss, S., Reemtsma, T., 2005. Pathways and metabolites of microbial
degradation of selected acidic pharmaceutical and their occurrence in munic-
ipal wastewater treated by a membrane bioreactor. Water Res. 39, 2654e2664.
Santos, I.D., Dezotti, M., Dutra, A.J.B., 2013. Electrochemical treatment of effluents
from petroleum industry using a Ti/RuO2 anode. Chem. Eng. J. 226, 293e299.
Shmychkova, O., Luk’Yanenko, T., Yakubenko, A., Amadelli, R., Velichenko, A., 2015.
Electrooxidation of some phenolic compounds at Bi-doped PbO2. Appl. Catal. B
Environ. 162, 346e351.
Skoumal, M., Rodríguez, R.M., Cabot, P.L., Centellas, F., Garrido, J.A., Arias, C.,
 C. Wang et al. / Chemosphere 163 (2016) 584e591
Brillas, E., 2009. Electro-Fenton, UVA photoelectro-Fenton and solar
photoelectro-Fenton degradation of the drug ibuprofen in acid aqueous me-
dium using platinum and boron-doped diamond anodes. Electrochim. Acta 54,
2077e2085.
Wang, Y., Shen, Z.Y., Chen, X.C., 2010. Effects of experimental parameters on 2,4-
dichlorphenol degradation over Er-chitosan-PbO2 electrode. J. Hazard. Mater.
178, 867e874.
Wang, C.A., Shi, H.L., Adams, C.D., Gamagedara, S., Stayton, I., Timmons, T., Ma, Y.F.,
2011. Investigation of pharmaceuticals in Missouri natural and drinking water
using high performance liquid chromatography-tandem mass spectrometry.
Water Res. 45, 1818e1828.
Xia, Y.J., Dai, Q.Z., Weng, M.L., Peng, Y., Luo, J.M., Meng, X.Y., Luo, X.B., Chen, J.M.,
Crittenden, J., 2015. Fabrication and electrochemical treatment application of
Al-doped PbO2 electrode with high oxidation capability, oxygen evolution po-
tential and reusability. J. Electrochem. Soc. 162, E258eE262.
Xiang, Y.Y., Fang, J.Y., Shang, C., 2016. Kinetics and pathways of ibuprofen degra-
dation by the UV/chlorine advanced oxidation process. Water Res. 90, 301e308.
Xu, L., Li, M., Xu, W., 2015. Preparation and characterization of Ti/SnO2-Sb electrode
with copper nanorods for AR 73 removal. Electrochim. Acta 166, 64e72.
Yang, B., Jiang, C.J., Yu, G., Zhuo, Q.F., Deng, S.B., Wu, J.H., Zhang, H., 2015. Highly
efficient electrochemical degradation of perfluorooctanoic acid (PFOA) by F-
doped Ti/SnO2 electrode. J. Hazard. Mater. 299, 417e424.
591
Yuan, S.H., Gou, N., Alshawabkeh, A.N., Gu, A.Z., 2013. Efficient degradation of
contaminants of emerging concerns by a new electro-Fenton process with Ti/
MMO cathode. Chemosphere 93, 2796e2804.
Zeng, J.H., Yang, B., Wang, X.P., Li, Z.J., Zhang, X.W., Lei, L.C., 2015. Degradation of
pharmaceutical contaminant ibuprofen in aqueous solution by cylindrical
wetted-wall corona discharge. Chem. Eng. J. 267, 282e288.
Zhao, G.H., Zhang, Y.G., Lei, Y.Z., Lv, B.Y., Gao, J.X., Zhang, Y.N., Li, D.M., 2010.
Fabrication and electrochemical treatment application of a novel lead dioxide
anode with superhydrophobic surfaces, high oxygen evolution potential, and
oxidation capability. Environ. Sci. Technol. 44, 1754e1759.
Zhao, J., Zhu, C.Z., Lu, J., Hu, C.J., Peng, S.C., Chen, T.H., 2014. Electro-catalytic
degradation of bisphenol A with modified Co3O4/b-PbO2/Ti electrode. Electro-
chim. Acta 118, 169e175.
Zheng, B.G., Zheng, Z., Zhang, J.B., Luo, X.Z., Wang, J.Q., Liu, Q., Wang, L.H., 2011.
Degradation of the emerging contaminant ibuprofen in aqueous solution by
gamma irradiation. Desalination 276, 379e385.
Zhou, M.H., Dai, Q.Z., Lei, L.C., Ma, C., Wang, D.H., 2005. Long life modified lead
dioxide anode for organic wastewater treatment electrochemical characteristics
and degradation mechanism. Environ. Sci. Technol. 39, 363e370.
Zhu, X.P., Tong, M.P., Shi, S.Y., Zhao, H.Z., Ni, J.R., 2008. Essential explanation of the
strong mineralization performance of boron-doped diamond electrodes. Envi-
ron. Sci. Technol. 42, 4914e4920.