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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 diseases. More than 15,000 tons of IBP are produced worldwide
each year, but a significant percentage is excreted by patients in its
Ibuprofen (IBP) is a non-prescription, non-steroidal anti- original form or as metabolites (Ghauch et al., 2012; Markovic et al.,
inflammatory drug which has been widely used in the treatment 2015). IBP has been detected in surface water and wastewater at the
of fever, migraine, musculature pain and inflammatory rheumatic 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
* Corresponding author.
impact on the reproduction of aquatic organisms and human
E-mail address: junfengn@bnu.edu.cn (J. Niu).

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 585

endocrine system even at low concentrations (Han et al., 2010; technology. The intermediate products of IBP formed during the
Kang et al., 2015). Hence it is of great importance to develop electrochemical degradation were identified to reveal the electro-
effective technology to eliminate IBP from aquatic environment. chemical mineralization mechanism of IBP.
Various techniques have been studied to prevent the accumu-
lation of IBP in the aquatic environment. Some physical methods, 2. Materials and methods
such as adsorption (Guedidi et al., 2013; Iovino et al., 2015) or
membrane nanofiltration (Narbaitz et al., 2013), did not lead to 2.1. Chemicals
degradation either, which just involved phase transfer of IBP and
thus induced another pollution problem. The drawbacks of bio- Analytical grade IBP, Salicylic Acid (SA), 2,3-dihidroxybenzoic
logical processes were generally inefficient and the subsequent Acid (2,3-DHBA) and 2,5-dihydroxibenzoic Acid (2,5-DHBA) were
disposal of sludge (Kosjek et al., 2007; London ~ o and Pen~ uela, 2015; purchased from Sigma Aldrich. All other chemicals were analytical
Quintana et al., 2005). Chemical methods such as ozonation grade and were purchased from Sinopharm, China. All aqueous
(Quero-Pastor et al., 2014) and ionizing radiation (Illes et al., 2013), solutions used in our experiments were prepared with Milli-Q
as well as some advanced oxidation processes (AOPs) such as deionized water (18.2 MU cm). The pH values of the solution
photocatalytic systems and Fenton reaction based processes, could were adjusted by H2SO4 (5%, v v1) and NaOH (5%, m m1).
provide effective degradation of IBP (Ambuludi et al., 2013b; Li
et al., 2015; Molinari et al., 2006; Xiang et al., 2016). Neverthe- 2.2. Electrode fabrication and characterization
less, strict operational conditions (e.g., oxygen supply and pH) were
required, or more toxic intermediates, like 1,3-dihydroxyl Titanium sheets (purity 99.9%, 50 mm  50 mm  1 mm) were
ibuprofen and 1-(4-isobutylphenyl)ethanone, formed in some previously polished with different grades papers to a mirror-like
methods (Ille s et al., 2013; Quero-Pastor et al., 2014). The devel- surface, then immersed in NaOH solution (10%, m m1) and
opment of cost-effective technologies to eliminate IBP with high etched with boiling oxalic acid solution (10%, m m1). Ti/SnO2-Sb
mineralization rate is thus of great challenge. electrode and the middle layer of the Ti/SnO2-Sb/Ce-PbO2 were
The electrochemical advanced oxidation process (EAOP) has prepared using the sol-gel technique with a coating solution con-
recently demonstrated its great ability to efficiently abate envi- taining ethylene glycol, citric acid, SnCl4$4H2O and SbCl3 with a
ronmental recalcitrant pollutants (García-Go mez et al., 2014; Lin molar ratio of 140:30:9:1. The sol-gel solution was used to coat on
et al., 2013a, 2013b; Niu et al., 2012; Shmychkova et al., 2015). In- the Ti sheets by the dip-coating method. Then, the Ti sheets were
formations about the removal of chemical oxygen demand (COD) dried at 145  C for 10 min and sintered at 500  C for 10 min in a
and total organic carbon (TOC) for IBP solutions were provided muffle furnace. This procedure was repeated 20 times, and the last
using Pt, Ti/Pt/PbO2 and boron-doped diamond (BDD) electrodes baking was annealed for 2 h at 500  C to obtain Ti/SnO2-Sb elec-
(Ambuludi et al., 2013a; Ciríaco et al., 2009; Lima et al., 2013). The trode (Lin et al., 2013a).
BDD anode had better characteristics for the TOC removal of IBP Ti/Ce-PbO2 and the top layer of Ti/SnO2-Sb/Ce-PbO2 electrode
solution, which could achieve more than 92% with the current were prepared by electro-deposition. The Ce-doped PbO2 layer was
density of 20e30 mA cm2 after 360e480 min of electrolysis in generated coating on the Ti and Ti/SnO2-Sb, respectively, with an
200 mL IBP solution (Ambuludi et al., 2013a; Ciríaco et al., 2009). acidic electrolyte (68  C) consisting of 0.1 M HNO3, 200 g L1
Unfortunately, intermediate products were not followed, or just a Pb(NO3)2, 0.4 g L1 Ce(NO3)3, and 0.5 g L1 NaF at a constant current
few small molecular carboxylic acids were identified in these density of 20 mA cm2 for 60 min (Lin et al., 2013b).
studies, while explicit mineralization pathway of IBP by electro- The microstructure and morphology of the prepared electrodes
chemical treatment has not been fully understood yet. Besides, the were observed by scanning electron microscopy (SEM; S4800,
high production cost makes BDD not feasible for large-scale Hitachi, Japan) with an accelerating voltage of 10 kV and X-ray
application (Lin et al., 2013a; Panizza and Cerisola, 2009). Con- diffraction (XRD; Thermo ARL SCINTAG XTRA, Netherlands) using
cerning over the commercial application of electrochemical Cu Ka radiation, respectively. The oxygen evolution potential (OEP)
degradation of IBP, it is essential to search anodes with high of the electrodes were measured with the linear sweep voltam-
mineralization rate, mild condition and low cost. metry (LSV) technique conducted in conventional three-electrode
The explored Ti-based metal oxide electrodes (e.g., Ti/RuO2, Ti/ electrochemical cells on an electrochemical workstation (CHI
SnO2 and Ti/PbO2) have proven to be efficient electrode materials 660D, Chenhua, Shanghai, China). The prepared electrodes served
for the treatment of recalcitrant pollutants in aqueous solution as the work electrode (1 cm  2 cm), a platinum foil and a saturated
(García-Go mez et al., 2014; Shmychkova et al., 2015; Santos et al., calomel electrode (SCE) as the counter electrode and the reference
2013; Xu et al., 2015; Yang et al., 2015; Zhao et al., 2014; Zhou electrode, respectively. The characterized results are shown in
et al., 2005). In previous researches, we found that Ti/SnO2-Sb Figs. SM-1e3 of the Supplementary Material (SM).
and Ti/SnO2-Sb/Ce-PbO2 electrodes can rapidly and almost
completely remove various organic contaminants, such as penta- 2.3. Electrochemical experiments
chlorophenol, perfluorocarboxylic acids (PFCAs) and sulfamethox-
azole from aqueous solution (Lin et al., 2013a, 2013b; Niu et al., The electrochemical oxidation experiments were conducted in
2013). Even the performance of Ti/SnO2-Sb/Ce-PbO2 electrode undivided electrolytic cells made of organic glass. The Ti/SnO2-Sb/
was comparable with that of BDD electrode for the degradation of Ce-PbO2, Ti/Ce-PbO2 and Ti/SnO2-Sb electrodes were used as an-
PFCAs (Lin et al., 2013b). Thus Ti-based metal oxide electrodes may odes, and Ti sheets as the cathodes. Before electrolysis experiments,
have great potentiality to completely mineralize IBP to harmless controlled trials with no power supply were conducted. No obvious
byproducts. losses of IBP were detected after 240 min, indicating that degra-
The aim of this study was to investigate the performance of the dation by sorption or hydrolysis was negligible. For most experi-
electrochemical oxidation process for the degradation of IBP using ments, a relative high initial concentration of IBP (20.0 mg L1) was
three Ti-based metal oxide anodes. The mineralization of IBP was used to investigate the effects of main operating factors on the
elucidated by assessing the removal of the TOC. The energy con- degradation efficiency and the monitoring of major degradation
sumption per order (EEO) of IBP degradation was evaluated to assess intermediates during the treatment. When investigating the effect
the application potential of the electrochemical oxidation 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 Farrell, 2008; Lin et al., 2013a; Liao and James, 2009; Zhao et al.,
current density (2e40 mA cm2), initial pH value (4.0e12.0) with 2010), the generation capacity of OH on the anodes under a cur-
10 mM Na2SO4 as supporting electrolyte. 30e100 mL of IBP solution rent density of 5 mA cm2 was determined based on their reaction
was used to investigate the effect of electrode distance (5e20 mm). with SA to form hydroxylated products. In our study, only 2,5-DHBA
Besides, relative low initial IBP concentrations (1.0e10.0 mg L1) was detected during the electrolysis process, so the OH concen-
were also used to better simulate the degradation efficiency of the tration was equal to the 2,5-DHBA concentration according to the
real wastewater. The solution was not stirred due to the short reaction stoichiometry. Fig. 1 shows that the concentration of OH
electrodes distance. The electrolysis was conducted with a power generated on the Ti/SnO2-Sb/Ce-PbO2 anode was higher than that
supply (DH1715A, Beijing Dahua Electronic Co., China) at constant on Ti/Ce-PbO2 and Ti/SnO2-Sb anodes. The production of OH fol-
current. The solution pH was detected by a microprocessor pH lowed pseudo-zero-order kinetics (R2 > 0.99) before 15 min on all
meter (pH211, EUTECH Co., USA). All the electrochemical experi- anodes due to the excess of SA. The production rate constants (k) of
ments were conducted at least in triplicate and operated at OH were 17.2, 12.3, and 14.5 mM (min m2)1 on Ti/SnO -Sb/Ce-
2
(25 ± 1)  C. 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
2.4. Instrumental analysis might be lower than actual generation rate due to the short life
time of OH (Peralta et al., 2014) and their incompletely reaction
The concentrations of IBP were determined by a high- with SA.) This suggested that Ti/SnO2-Sb/Ce-PbO2 might have the
performance liquid chromatography (HPLC, Dionex U3000, USA) best electrochemical oxidation performance.
equipped with a fluorescence detector and an Athena C18-WP To verify above speculation, the degradation of IBP on these
column (4.6 mm  250 mm, 5 mm particle size). The production three metal-oxide-coated Ti based electrodes was carried out at
of hydroxyl radical (OH) was determined with SA trapping and 5 mA cm2 with the initial IBP concentration of 20.0 mg L1 (Fig. 2).
analyzed by HPLC-UV (Peralta et al., 2014). The details are provided The degradation ratios of IBP on Ti/SnO2-Sb/Ce-PbO2, Ti/Ce-PbO2
in Text SM-1 and SM-2 of the SM. TOC was measured using a TOC-L- and Ti/SnO2-Sb anodes were 92.4%, 65.2% and 78.6%, respectively,
CPN analyzer (Shimadzu Co, Japan) to evaluate the mineralization after 30 min of electrolysis. The degradation of IBP followed
of IBP. pseudo-first-order kinetics on all anodes. The electrochemical
The intermediate products formed during the electrochemical degradation rate constant (k) over Ti/SnO2-Sb/Ce-PbO2
process of IBP were identified using an ultra-high-performance (9.4  102 min1) was 2.0 and 1.7 times of the values over Ti/Ce-
liquid chromatography coupled with a quadrupole time-of-flight PbO2 (4.7  102 min1) and Ti/SnO2-Sb (5.6  102 min1),
mass spectrometer (UPLC-Q-TOF-MS, Xevo G2, Waters Corp, USA) respectively. Besides, the degradation of IBP were significantly
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): 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
SjUt trapping agent SA: 7 mM, Na2SO4: 10 mM, electrode distance: 5 mm, pH: without
EEO ¼ (1) adjusted, T: (25 ± 1)  C.
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


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-
3.1.1. Effect of anode materials dation by Ti/Ce-PbO2, Ti/SnO2-Sb and Ti/SnO2-Sb/Ce-PbO2 electrodes at the applied
Since OH played a significant role in electrochemical degrada- current density of 5 mA cm2. Na2SO4:10 mM, electrode distance: 5 mm, pH: without
tion of recalcitrant pollutants over “non-active” anodes (Carter and 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 degradation rate of IBP. The k values increased from 5.8  102 to
(IPA), one scavenger of OH (Li et al., 2009), to the solution. This 2.1  101 min1 as the current density increased from 2 to
proved indirectly that the OH generation ability of the electrode 40 mA cm2 (see Table 1). A much quicker degradation rate was
material dominated the electrochemical degradation of IBP. Thus observed at a higher applied current density (20 mA cm2), with
Ti/SnO2-Sb/Ce-PbO2, which had the highest generation capacity of almost complete degradation of IBP after 30 min, which was
OH, was used to conduct the following experiments. 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
3.1.2. Effect of applied current density were 11.9, 7.3, 5.4, 4.4, 3.7 and 3.4 min for the current density values
The effect of current density on the degradation efficiency of IBP of 2, 5, 10, 20, 30, and 40 mA cm2, respectively. The results indi-
(20.0 mg L1) with Ti/SnO2-Sb/Ce-PbO2 electrode was determined cated that the t1/2 values decreased with limited as the applied
and the result is shown in Fig. 3a. The results showed that the current density was higher than 20 mA cm2, implying that further
increasing current density could significantly accelerate the 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 some other AOPs, but some organic byproducts (i.e., 1,3-dihydroxyl
anode surface with the increasing applied current density might ibuprofen and 1-(4-isobutylphenyl)ethanone) with greater toxicity
account for this phenomenon (Ambuludi et al., 2013a; Li et al., were formed during the degradation process (Ille s et al., 2013;
2014; Lin et al., 2013a; Skoumal et al., 2009). It could be deduced Quero-Pastor et al., 2014). Thus high degree of mineralization of
that a current oversupply led to energy waste and this opinion IBP is still desirable. To determine whether IBP could be completely
would be proven in later part. mineralized by the Ti/SnO2-Sb/Ce-PbO2 anode during the electro-
chemical oxidation process, the removal of TOC were investigated
3.1.3. Effect of electrode distance at initial concentration of 20.0 mg L1 under the optimum condi-
Fig. 3b shows a rapid degradation of IBP at the electrode dis- tions. As shown in Fig. 4, the removal of TOC was quick at the first
tance of 5 mm with complete disappearance after 40 min applying 30 min and the mineralization rate achieved to 72.0%. The results
the current density of 10 mA cm2. At the plate distance of were due to the fact that large quantities of OH generated on the
15e20 mm, the complete degradation of IBP needed more than surface of Ti/SnO2-Sb/Ce-PbO2 anode under the applied condition,
60 min. As shown in Table 1, the k value at the electrode distance of making IBP and its byproducts being simultaneously mineralized
5 mm was 1.3  101 min1, which was approximately 1.7, 3.0, and (Li et al., 2014; Lin et al., 2013b; Yuan et al., 2013). At the later stage,
4.2 times of those at the electrode distance of 10, 15 and 20 mm, the decay of TOC tended to be slow and the removal rate was 93.2%
respectively. It meant that more electrolysis time was required at a after 60 min electrolysis. It indicated that the Ti/SnO2-Sb/Ce-PbO2
larger electrode distance due to the longer diffusion distance of IBP. anode could rapidly mineralize IBP at a relative low applied current
The results indicated that a shorter plate distance resulted in a density of 10 mA cm2. Previous studies found that the removal of
higher degradation efficiency of IBP. TOC could achieve 92% (current density: 30 mA cm2, initial con-
centrations of IBP: 1.75 mM, 360 min) and 96% (current density:
3.1.4. Effect of initial pH value 20 mA cm2, initial concentrations of IBP: 0.2 mM, 480 min) using
The initial pH is of crucial importance in the electrochemical BDD electrodes (Ambuludi et al., 2013a; Ciríaco et al., 2009).
oxidation process (Chen et al., 2015). The initial pH of the solution Therefore, it can be indicative of effective mineralization of IBP in
without adjusted was about 5.2. The effect of the initial pH on the aqueous solution by electrochemical technique using Ti/SnO2-Sb/
degradation efficiency of IBP was examined by adjustment of the Ce-PbO2 electrode.
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 3.3. Energy cost upon electrochemical oxidation of IBP solutions
Fig. 3c, the initial pH had no significant effect on the degradation
kinetics of IBP in acid and weak alkaline conditions, and the k The economic feasibility of IBP mineralization by the Ti/SnO2-
values were 1.3  101, 1.2  101 and 1.2  101 min1, respec- Sb/Ce-PbO2 anode was evaluated by calculating the EEO (Eq. (1)).
tively, at the pH values of 4.0, 6.0 and 8.0. The k values decreased Table 1 shows the EEO required for degrading IBP by Ti/SnO2-Sb/Ce-
slightly to 9.1  102 and 7.7  102 min1 when the initial pH PbO2 under different conditions. It can be seen that the EEO for IBP
increased to 10.0 and 12.0. One mechanism was proposed to degradation would increase from 4.3 to 42.1 Wh L1, as the applied
explain the degradation trend: the oxidation potential of OH was current density increased from 2 to 40 mA cm2. Therefore the EEO
lower in alkaline condition (þ2.02 V) than in acid condition at 40 mA cm2 was 9.7 times of the value at 2 mA cm2, while the k
(þ2.85 V) (Zhao et al., 2014), thus high pH enhanced the oxygen value only increased 3.6 times, indicating that a higher applied
evolution at the anode surface and caused the decrease of IBP current density leads to large amounts of energy waste. On the
degradation efficiency (Wang et al., 2010; Zhou et al., 2005). In contrary, though a lower applied current density costs lower en-
general, initial pH have little effect on the degradation kinetics of ergy, it requires more residence time, thus decreases the space
IBP at tested level, thus the pH of the solution was not adjusted in utilization in the practice application. So the applied current den-
the following experiments. 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).
3.1.5. Effect of initial IBP concentration As shown in Table 1, the electrode distance also has a significant
Fig. 3d shows the degradation of IBP as a function of its initial effect on energy cost. The EEO is 13.1 Wh L1 at the electrode dis-
concentration. For all cases, the almost complete elimination of IBP tance of 5 mm, much lower than the values of 16.6, 26.9, and
was reached after 40 min at the applied current density of 30.6 Wh L1 at the electrode distance of 10, 15, and 20 mm,
10 mA cm2. The k values of IBP electrolysis with initial concen- respectively. Higher EEO required at larger electrode distance can be
trations of 1.0, 2.0, 5.0, 10.0, and 20.0 mg L1 were 2.1  101, attributed to the increase of the electrolysis resistance and
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 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:
Although high degradation rate of IBP could be achieved by without adjusted, T ¼ (25 ± 1)  C.
C. Wang et al. / Chemosphere 163 (2016) 584e591 589

substrate diffusion distance (Lin et al., 2013a). Thus short plate initiated AOPs.
distance is beneficial to rapid mineralize IBP with low energy cost. Based on the detected intermediates, a possible degradation
scheme of IBP with two main pathways (A and B) was proposed
3.4. Intermediate analysis of IBP and possible mineralization (see Fig. 5), including the products detected and hypothetical in-
mechanisms termediates within bracket. As the utilized Ti/SnO2-Sb/Ce-PbO2
anode is a typical non-active electrode, it can persistently produce a
The structural assignments of intermediates were identified by large amount of OH during electrochemical process (Lin et al.,
means of UPLC-Q-TOF-MS in the positive and negative mode to 2013a; Zhu et al., 2008). The produced OH attacked IBP at the
elucidate the mineralization mechanism of IBP by electrochemical C(2) position of its isobutyl substituent or the C(2) position of its
oxidation. In virtue of the accurate mass measurements of TOF-MS, propionic acid group, resulting in the formation of hydroxylated IBP
the elemental composition and their fragment ions of the in- isomers the hypothetical 2-hydroxy-ibuprofen or identified p1,
termediates can be obtained reliably (Bueno et al., 2007). A total of respectively. The first hydroxylated IBP then underwent through
six aromatic intermediates of IBP were identified. Detailed infor- hydroxylation, decarboxylation and loss of isopropanol to form p6
mation is shown in Table SM-1 and Fig. SM-4 of the SM. Most of along route A. Pathway B was undertaken by the formation of 1-(1-
these aromatic intermediates of IBP have also been observed in hydroxyethyl)-4-isobutylbenzene via the decarboxylation of p1.
other OH-initiated AOPs (Ille s et al., 2013; Li et al., 2014; Zheng This intermediate subsequently evolved to p2 or p3 through OH
et al., 2011). The results suggested that OH produced by Ti/SnO2- attacking at the C(1) position of its isobutyl substituent or the C(1)
Sb/Ce-PbO2 anode played a significant role on IBP mineralization position of its ethanol group, respectively. These two compounds
during the electrochemical process. Only one mono-hydroxylated were then oxidized to p4 and p6, along with the loss of isopropyl
IBP (2-(4-isobutylphenyl)-2-hydroxypropionic acids, p1) was reactions. Further oxidation of these smaller aromatics (p4 and p6)
detected in this study, whereas other studies reported that both by OH resulted in cleavages of the benzene ring, which produced a
positions of propanoic acid and isobutyl substituents of IBP could variety of linear carboxylic acids. These acids could be finally
be attacked by OH to form different hydroxylated IBP (Ille s et al., mineralized to CO2 and H2O via successive hydroxylation reactions.
2013; Li et al., 2014). Previous studies also reported that the hy- Note that, the solution pH decreased slowly from 5.2 (initial pH of
droxylation process could be the initial reaction stage of the the IBP solution) to about 4.3 at ~30 min and increased to 5.7 at
mineralization of IBP by electro-peroxone (Li et al., 2014) and ~60 min during electrolysis, indicating that the slow accumulation
photoelectron-Fenton (Skoumal et al., 2009) processes. Two de- of carboxylic acids and then oxidized by OH in the mineralization
rivatives of decarboxylated IBPs, 1-(4-(1-hydroxyethyl) phenyl)-2- process of IBP.
methylpropan-1-one (p2) and 4-isobutylacetophenone (p3), were The degradation mechanisms of IBP proposed in this study was
detected and the formation of these intermediates was associated different from that using non-thermal plasma (NTP), in which 1-(4-
with the oxidation of hydroxyl to yield carbonyl. 2-(4- acetylphenyl)-2-methyl-1-propanone was detected and still
methylphenyl) propanoic acid (p5) with the structure of carboxyl remained after 120 min treatment (Zeng et al., 2015). The difference
group was detected. Besides, smaller aromatic intermediates, of degradation mechanisms led directly to different mineralization
including 4-(1-hydroxyethyl) benzaldehyde (p4) and 4- efficiency of IBP, i.e. the removal rate of TOC achieved to 93.2% after
acetyltoluene (p6), with the property of benzene ring readily be- 60 min in this study, while only 66.0% of TOC was removed even
ing cleaved, were identified. Interestingly, p6 (MW ¼ 134) was not after 180 min by NTP. Besides, the proposed degradation mecha-
identified in other OH-initiated AOPs, but another isomers of p6 nism was also different from that proposed by Skoumal et al.
(4-ethylbenzaldehyde) was detected (Ille s et al., 2013; Li et al., (2009), who used photoelectron-Fenton with BDD combination
2014; Zheng et al., 2011), implying that a difference mineraliza- technique to eliminate IBP. By comparison, the end aromatic
tion mechanism of IBP might exist compared with other OH- byproducts (p4 and p6) listed in Fig. 5 possessed more simple

Fig. 5. Proposed reaction pathways for the mineralization of IBP by electrochemical oxidation.
590 C. Wang et al. / Chemosphere 163 (2016) 584e591

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This study was financially supported by the National Natural
MnO2 anodes. Water Res. 46, 2281e2289.
Science Foundation of China (Nos. 51238006 and 51378065) and Lin, H., Niu, J.F., Xu, J.L., Li, Y., Pan, Y.H., 2013a. Electrochemical mineralization of
the Fund for Innovative Research Group of the National Natural sulfamethoxazole by Ti/SnO2-Sb/Ce-PbO2 anode: kinetics, reaction pathways,
and energy cost evolution. Electrochim. Acta 97, 167e174.
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Appendix A. Supplementary data fluorocarboxylic acids (C9-C10) by Ti/SnO2-Sb/Ce-PbO2. Environ. Sci. Technol.
47, 13039e13046.
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