Environmental Research 201 (2021) 111569

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Environmental Research
journal homepage: www.elsevier.com/locate/envres

Degradation of carbamazepine by UVA/WO3/hypochlorite process: Kinetic

modelling, water matrix effects, and density functional theory calculations
Han Ding, Jiangyong Hu *
Department of Civil & Environmental Engineering, National University of Singapore, 1 Engineering Drive 2, 117576, Singapore

A R T I C L E I N F O A B S T R A C T

Keywords: The rapid recombination of electron/hole pairs is a major setback in the application of WO3-based photocatalysis
Tungsten trioxide in water treatment. In this study, hypochlorite (ClO− ) was used as an electron acceptor to enhance the photo­
Photocatalysis catalytic degradation of carbamazepine (CBZ) using UVA-excited WO3. The results showed that CBZ degradation
Hypochlorite
in the UVA/WO3/ClO− system followed a pseudo-first order reaction kinetic model. The addition of 0.1 ​ mM
Steady-state kinetic model
Density functional theory
ClO− to the UVA/WO3 system at pH values of 8.2 and 6.2 increased the rate constant (kobs) of the degradation
process 5.3- and 11.5-fold, respectively. Further, increasing the WO3 dosage or decreasing the initial CBZ con­
centration resulted in an increase in kobs. However, at high concentrations, ClO− inhibited CBZ degradation.
Based on the kinetic model, it could be suggested that ClO• played a dominant role in the degradation process.
Furthermore, the water matrix effects were as follows: the optimal pH was 6.2; humic acid, chloride, bicarbonate,
and ammonium exhibited inhibitory effects on CBZ degradation; and sulfate ion significantly enhanced the
degradation. Density functional theory (DFT) calculations indicated a strong affinity between ClO− and the WO3
surface. Specifically, the electrical energy per order that was associated with the use of ClO− varied in the range
of 0.100–1.617 ​ kWh/m3. In summary, this study shows that ClO− is an excellent electron acceptor for excited
WO3, while clarifying the CBZ degradation-enhancing effect of ClO− as well as the kinetic model and DFT cal­
culations. These findings can be employed in the degradation of recalcitrant contaminants in a cost-effective
manner, while being significant for the development of more effective catalysts of UV-assisted advanced
oxidation processes.

1. Introduction Recently, WO3 has attracted increasing interest as a visible-light-

active photocatalyst owing to its excellent properties, such as high sta­
The photocatalytic degradation of contaminants, which is considered bility, nontoxicity, and low cost (Quan et al., 2020). Its narrow band gap
a promising advanced oxidation process (AOP) for water purification, (2.4–2.8 ​ eV) renders its excitation by light with wavelengths shorter
has attracted increasing attention in recent years (Long et al., 2020; than 500 ​ nm possible (Kim et al., 2010). In some studies, WO3 was used
Teodosiu et al., 2018). Under the irradiation of photons with sufficient to degrade contaminants under the illumination of visible or UV light,
energy, photocatalysts are capable of generating the hydroxyl radical and the results obtained showed that a high dosage of WO3 or long re­
(HO•, E0 ​ = ​ +2.73 ​ V), which is a powerful oxidizing agent capable of action time is necessary to achieve a satisfactory removal rate (Chu and
decomposing recalcitrant pollutants (Li et al., 2018). TiO2 has been one Rao, 2012; Mohagheghian et al., 2016). Unlike TiO2, with a conduction
of the most extensively studied photocatalysts for application in envi­ band (CB) edge of − 0.5 ​ V, the CB edge of WO3 is approximately in the
ronment and energy fields ever since Fujishima and Honda reported range of +0.3 to +0.5 ​ V (Bessekhouad et al., 2004; Kim et al., 2010),
water splitting via TiO2 photocatalysis (Fujishima and Honda, 1972; and given that the reduction potential of the O2 /O⋅−2 couple is − 0.33 ​ V,
Nakata and Fujishima, 2012). However, its wide band gap (3.0–3.2 ​ eV) the dissolved oxygen cannot strip away the excited electrons in the CB of
makes it responsive only to UV light, which constitutes less than 5% of WO3 (e−CB ) (Ilan et al., 1976). Therefore, the rapid recombination of e−CB
the solar irradiation. Thus, its application in solar energy-assisted water and holes in the valence band (h+ VB ) limits the generation of HO by hVB
• +

treatment is limited (Chen et al., 2020a; Herron et al., 2015; Landmann (Rao et al., 2013). It has also been reported that the capability of WO3 to
et al., 2012). generate HO• is much lower than that of TiO2 (Nagarajan et al., 2017;

* Corresponding author.
E-mail address: [email protected] (J. Hu).

https://doi.org/10.1016/j.envres.2021.111569
Received 16 February 2021; Received in revised form 15 June 2021; Accepted 18 June 2021
Available online 26 June 2021
0013-9351/© 2021 Elsevier Inc. All rights reserved.
H. Ding and J. Hu Environmental Research 201 (2021) 111569

Xiang et al., 2011). Therefore, before WO3 can be used in water treat­ purchased from Sigma-Aldrich (St. Louis, MO, USA). Ultrapure water
ment applications, it is imperative to resolve the issue of rapid e−CB -h+ VB
(Milli-Q, 18.2 ​ MΩ ​ cm; Millipore Co., Bedford, MA, USA) was used to
recombination. prepare solutions.
Strategies to inhibit e−CB -h+
VB recombination in WO3 can be divided
into two categories. The first focuses on the material modification of 2.2. Experimental procedures
WO3, including element doping (Chen et al., 2020b), phase and
morphology control (Aslam et al., 2014; Zhang et al., 2015), noble metal Six UVA-LEDs (365 ​ nm, LG3535, South Korea), which were placed
loading (Widiyandari et al., 2012), and coupling with other photo­ above a 325-mL Pyrex crystallizing dish (diameter ​ = ​ 10 ​ cm and
catalysts to form heterojunctions (Shi et al., 2020; Wang et al., 2021). height ​ = ​ 5 ​ cm) and filled with 250 ​ mL of CBZ solution, have been
However, the disadvantage of material modification methods is that used as the light source. The light intensity above the water surface was
changing the method by which WO3 is synthesized may affect its sta­ measured using a radiometer (LT1400, International Light Technolo­
bility and increase cost. The second strategy by which e−CB -h+ gies, Peabody, MA, USA) and adjusted to 2 ​ mW/cm2. The default
VB recom­
bination can be prevented is to use oxidants with reduction potentials concentrations of the solutes WO3, CBZ, and ClO− were 40 ​ mg/L,
higher than the CB edge of WO3 as electron acceptors. In this regard, 7.5 ​ μM, and 0.1 ​ mM, respectively. The initial pH was maintained at 8.2,
unless stated otherwise. To investigate the effect of each operational
H2O2, Ag+, and S2 O2− 8 have shown efficiency in improving the ability of
parameter on CBZ degradation via the UVA/WO3/ClO− process, the
WO3 to degrade pollutants via e−CB scavenging (Chu and Rao, 2012; Rao
concentrations of WO3, ClO− , and CBZ were varied in the ranges of
and Chu, 2010; Rao et al., 2013). Additionally, hypochlorite (ClO− ,
20–50 ​ mg/L, 0.1–0.7 ​ mM, and 3.7–14.0 ​ μM, respectively. When one
E0 ​ = ​ +0.89 ​ V), which has been extensively used for water disinfection
concentration type varied, the other two were kept constant. Further,
owing to its low cost and high efficacy, also meets the requirement for
the effects of the water matrix characteristics were investigated by
e−CB scavenging (Collivignarelli et al., 2018; Cotton and Wilkinson, 1980;
varying the pH in the range of 4.2–10.2 and altering the concentrations
Rosińska and Rakocz, 2021). Specifically, the advantage of applying
of humic acid (HA), the anions Cl− , SO2− 4 , and HCO3 , and NH4 in the
− +
ClO− over other oxidants as an e−CB scavenger is that the residual chlorine
ranges 1–7 ​ mg/L, 1–7 ​ mM, and 0.03–0.1 ​ mM, respectively. Samples
after the disinfection stage can be utilized directly, thus saving costs
withdrawn from the reactor were immediately quenched using excessive
related to additional chemicals. However, based on the existing litera­
thiosulfate (Ding and Hu, 2021b) and then filtered through 0.2-μm PTFE
ture, there are no reports on the utilization of ClO− to enhance the
syringe filters (Whatman, UK) before measuring the CBZ concentrations.
photocatalytic activity of WO3.
In this study, the degradation of carbamazepine (CBZ) via the UVA/
2.3. Analytical methods
WO3/ClO− process was systematically investigated. CBZ, a widely used
anticonvulsant drug, was selected as the model pollutant given that it is
The CBZ concentration was analyzed using a high-performance
highly recalcitrant to conventional wastewater treatment processes and
liquid chromatography (HPLC) apparatus that was coupled with a
its removal rates are typically below 10% (Zhang et al., 2008). Addi­
diode array detector for performing UV absorbance measurements
tionally, it is frequently detected in secondary effluents, with its highest
(Shimadzu LC2010, Japan). The peak wavelength of CBZ used for UV
concentrations reaching 6300 ​ ng/L (Clara et al., 2004; Heberer, 2002;
absorbance measurement was 285 ​ nm. The mobile phase constituted a
Zhang et al., 2008). CBZ may pose potential risks to the aquatic envi­
mixture of 70% methanol and 30% water. For the analysis, 15 ​ μL
ronment as its predicted no-effect concentration (PNEC) is only
samples and the mobile phase were injected into a C18 column
0.42 ​ μg/L (Ferrari et al., 2003). Further, in this study, the role of ClO− in
(2.1 ​ × ​ 150 ​ mm, particle size 3.5 ​ μm, Zorbax, Agilent Technologies,
facilitating CBZ degradation was confirmed by comparing the
Santa Clara, CA, USA) for separation at a flow rate of 0.2 ​ mL/min and a
CBZ-degradation performances of the UVA/ClO− , WO3/ClO− ,
temperature of 40◦ C. The point of zero charge (pHPZC) associated with
UVA/WO3, and UVA/WO3/ClO− processes. The effects of operational
WO3 (4.0) was measured using a modified pH drift method (Ding and
parameters (WO3 dosage, ClO− concentration, and CBZ concentration)
Hu, 2021a). Additionally, using the indophenol method, a DR/890
as well as those of water matrix characteristics (pH, and humic acid,
Portable Colorimeter (Hach, USA) was used to measure the concentra­
chloride, sulfate, bicarbonate, and ammonium concentrations) on CBZ
tion of ClO. The total organic carbon (TOC) content of the water samples
degradation via the UVA/WO3/ClO− process were comprehensively
was measured using a TOC-VCSH analyzer (Shimadzu, Japan).
studied. The concentrations and contributions of different reactive ox­
ygen species (ROS) to CBZ degradation were estimated using a
2.4. Steady-state kinetic model
steady-state kinetic model, and the interactions between ClO− and the
WO3 surface were analyzed by performing density functional theory
The major reactions in the UVA/WO3/ClO− system are listed in
(DFT) calculations. These allowed the clarification of the CBZ degra­
Table 1. These reactions were selected because they involve at least one
dation mechanism at a molecular level. The results of this study could
reactant that exists in large amounts (i.e., CBZ, H2O, ClO− , or O2). Other
provide valuable insights into the ability of ClO− to inhibit rapid e−CB - h+VB typical reactions in the UV/ClO− system were ignored, owing to their
recombination in excited WO3 and inspire the coupling of ClO− with
very low reaction rates or the very low concentration of both reactants
other photocatalysts.
(Nikravesh et al., 2020). The selected reactions allowed the simplifica­
tion of the model, while maintaining the representativeness of the sys­
2. Materials and methods
tem. The changes in the concentrations of ROS in the UVA/WO3/ClO−
system were expressed according to Eqs. (1)–(8). Given that the decay of
2.1. Materials
ClO− was less than 10% during the reaction (Fig. S1), it could be
assumed that its concentration remained constant. Detailed explana­
Tungsten trioxide (WO3) nanopowder (diameter ​ < ​ 100 ​ nm, spe­
tions and assumptions regarding the equations are listed in Table S1 and
cific surface area <8 ​ m2/g) was purchased from Sigma-Aldrich (St.
Text S1, respectively.
Louis, MO, USA). Sodium hypochlorite (NaClO, available chlorine,
10–15%), sodium chloride (NaCl, ≥99.5%), sodium sulfate (Na2SO4, d[h+
VB ]ss
= φobs I − kH2 O,h+VB [H2 O][h+
VB ]ss (1)
>99%), sodium bicarbonate (NaHCO3, >99%), ammonium chloride dt
(NH4Cl, ≥99%), humic acid salt (technical grade), sodium hydroxide
(NaOH, ≥98%), sulfuric acid (H2SO4, >99%), sodium thiosulfate d[e−CB ]ss
= φobs I − kClO− ,e−CB [ClO
−
]0 [e−CB ]ss (2)
(Na2S2O3, >99%), and methanol (CH3OH, >99.9%) were also dt

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H. Ding and J. Hu Environmental Research 201 (2021) 111569

Table 1
Reactions in the UVA/WO3/ClO− system during CBZ degradation.
1 − 1
No. Reaction Second-order rate constant k (M− s ) Reference

1 WO3 + hv→e−CB + h+
VB
– –
2 – –

3 5.3 × 1010 Buxton and Subhani (1972a)

4 108 ​ s− 1 Buxton et al. (1988)
5 1.85 × 109 Chuang et al. (2017)
6 OCl− + hv →Cl− + O(3 P) φa = 0.28 Buxton and Subhani (1972b)
7 φb = 0.08 Buxton and Subhani (1972b)
8 O(3 P) + O2 →O3 4 × 109 Bulman et al. (2019)
9 O(3 P) + OCl− →ClO−2 9.4 × 109 Bulman et al. (2019)
10 8.25 × 109 Bulman et al. (2019)
11 O3 + OCl− →2O2 + Cl− 110 Haag and Hoigné (1983)
12 O3 + OCl− →O2 + ClO−2 30 Haag and Hoigné (1983)
13 8.8 × 109 Huber et al. (2003)
14 9.2 × 107 Guo et al. (2017)
15 5.6 × 1010 Wang et al. (2016)
16 CBZ + O3 →Products 3 × 105 McDowell et al. (2005)

(3)

(4)

(5)

(6)

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H. Ding and J. Hu Environmental Research 201 (2021) 111569

Fig. 1. (a) Degradation of CBZ by different processes; (b) Effect of WO3 dosage on CBZ degradation by the UVA/WO3/ClO− process; (c) Effect of ClO− concentration
on CBZ degradation by the UVA/WO3/ClO− process; (d) Effect of initial CBZ concentration on CBZ degradation by the UVA/WO3/ClO− process.

(10)
d[O(3 P)]ss
= 2.303φa I ε[ClO− ]0 − kO(3 P),O2 [O(3 P)]ss [O2 ]0
dt
(11)
− kO(3 P),ClO− [O(3 P)]ss [ClO− ]0 (7)

d[O3 ]ss (12)

= kO(3 P),O2 [O(3 P)]ss [O2 ]0 − kO3 ,CBZ ​ [O3 ]ss [CBZ]0
dt
− kO3 ,ClO− [O3 ]ss [ClO− ]0 (8) kO3 ,CBZ [O3 ]ss
R O3 = (13)
CBZ could be oxidized using HO , ClO , Cl , and O3. The observed
• • • kobs ​
pseudo-first-order rate constant (kobs) of CBZ degradation could be
where φobs represents the net quantum yields of e−CB and h+
VB that escaped
expressed according to Eq. (9):
recombination; I represents the light intensity on the water surface
(2 ​ mW/cm2); ε represents the molar absorptivity of ClO− at 365 ​ nm
(M− 1cm− 1); φa and φb represent the quantum yields of O(3P) and Cl•
Further, the relative contributions of HO•, ClO•, Cl•, and O3 to CBZ
owing to the photolysis of ClO− by UV light (365 ​ nm), respectively; and
degradation were calculated according to Eqs. (10)–(13):

(9)

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H. Ding and J. Hu Environmental Research 201 (2021) 111569

2.303φa Iε[ClO− ]0 and 2.303φb Iε[ClO− ]0 represent the generation of O followed a pseudo-first order kinetic model and an increase in the WO3
(3P) and Cl• owing to the photolysis of ClO− , respectively (Chuang et al., dosage monotonically resulted in an increase in kobs. With more WO3
2017). added into the solution, the generation of e−CB and h+ VB was enhanced,
and more reaction sites on the WO3 surface were available to ClO− .
2.5. Density functional theory calculations Thus, the generation of HO• was stimulated, resulting in an enhance­
ment of CBZ degradation. However, the relationship between kobs and
The models corresponding to the adsorption of ClO− on the surface of WO3 dosage was not linear and tended to remain stable after the WO3
WO3 were constructed using Materials Studio 2018. The DFT-based dosage exceeded 40 ​ mg/L. Rao and Chu (2010) also observed that the
calculations of adsorption energy, density of states (DOS), and charge rate of linuron degradation via the visible light/TiO2/H2O2 process
density differences were performed using Cambridge Serial Total Energy gradually slowed down when the TiO2 dosage exceeded 0.4 ​ g/L. They
Package (CASTEP) (Clark et al., 2005). Detailed parameter settings of suggested that an increase in the TiO2 particle content of the solution
the software program can be found in our previous study (Ding and Hu, attenuated the penetration of photons. This possibly resulted in a
2021a). decrease in the generation of e−CB and h+ VB (Rao and Chu, 2010).
Considering the low concentration of WO3 used in this study, it was
3. Results and discussion unlikely that the turbidity of the solution had a significant effect on the
absorption of light by WO3. Therefore, the kobs might have been limited
3.1. Enhancement of WO3 photocatalytic activity by ClO− by the concentration of ClO− , which was fixed at 0.1 ​ mM.

CBZ degradation via the different processes employed in this study is 3.2.2. Effect of ClO− concentration
shown in Fig. 1(a). From this figure, it is evident that all degradation The effect of ClO− concentration on CBZ degradation via the UVA/
processes followed a pseudo-first order reaction kinetic model given that WO3/ClO− process is shown in Fig. 1(c), based on which it is evident
the R2 values corresponding to a linear regression were well above 0.9. that CBZ degradation improved slightly. Furthermore, kobs increased by
CBZ oxidation by ClO− in the dark was negligible; this is consistent with 11% when ClO− concentration was increased from 0.1 to 0.5 ​ mM.
the results of previous reports (Wang et al., 2016, 2018). The slight However, kobs decreased by 27% when the concentration of ClO− was
degradation of CBZ via the UVA/ClO− process indicated weak ClO− further increased from 0.5 to 0.7 ​ mM. These observations suggest that
decomposition under irradiation with light at a wavelength of 365 ​ nm. ClO− plays a dual role in CBZ degradation. On the one hand, it accepts
This could be primarily attributed to the low molar absorptivity of ClO− e−CB to prolong the existence of h+
VB , thereby facilitating the generation of
at 365 ​ nm (Remucal and Manley, 2016). Further, due to the rapid HO•. On the other hand, it possibly reacted with HO• rapidly to form
recombination of e−CB and h+ VB , the rate of CBZ degradation via the ClO•, which is a less powerful radical whose second-order rate constant
UVA/WO3 process was also very low and the corresponding kobs was with CBZ was found to be two orders of magnitude lower than that of
0.021 min− 1. Conversely, the kobs corresponding to the UVA/WO3/ClO− HO• with CBZ (Table 1). This observation suggests that the inhibitory
process was 0.111 min− 1; i.e., it was 5.3-fold higher than that corre­ effect of ClO− could overwhelm its CBZ degradation enhancing effect
sponding to the UVA/WO3 process. Furthermore, given that the con­ when it is applied at high concentrations. Further, this quenching effect
tributions of the ClO− and UVA/ClO− processes to CBZ degradation of ClO− has also been observed in the UV/chlorine process in a previous
were insignificant, it could be concluded that the enhancement of the study, which showed that atrazine degradation did not improve and was
degradation rate was mainly achieved via the inhibition of e−CB -h+ VB inhibited when the concentration of ClO− increased (Kong et al., 2016).
recombination by ClO− . Moreover, the reaction of ClO− with e−CB yields Therefore, the optimization of the ClO− dosage is necessary.
O•− , which reacts with H2O to form HO• (Reactions 3 and 4 in Table 1).
This further accelerated CBZ removal. The rates of CBZ mineralization 3.2.3. Effect of CBZ concentration
under the different processes also confirmed the enhancing effect As shown in Fig. 1(d), increasing the initial concentration of CBZ
resulting from ClO− addition. As shown in Fig. S2, the TOC removal rate from 3.7 to 14.0 ​ μM resulted in a dramatic decrease in the steepness of
of the UVA/WO3/ClO− process was much higher than the sum of the the kinetic curve. Furthermore, there was good linearity (R2 ​ = ​ 0.97)
removal rates corresponding to the UVA/ClO− and UVA/WO3 processes. between 1/kobs and the initial concentration of CBZ (C0), as shown in
Fig. S3. Chu and Rao (2012) observed that the relationship between the
3.2. Effects of operational parameters initial concentration of monuron and kobs could be well described using
the Langmuir-Hinshelwood model (Eq. (14)) by considering CBZ
3.2.1. Effect of WO3 dosage degradation via the UV–vis/WO3 process.
As shown in Fig. 1(b), CBZ degradation at different WO3 dosages

Fig. 2. Absolute and relative contributions of ROS to CBZ degradation in the UVA/WO3/ClO− system under different (a) WO3 dosage; (b) ClO− concentration; (c)
CBZ concentration.

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H. Ding and J. Hu Environmental Research 201 (2021) 111569

Table 2
Concentrations of e−CB and ROS in the UVA/WO3/ClO− system.
15 14 11 16 10
Parameter Concentration (mg/L for WO3, mM for ClO− , μM for e−CB ( ​ × ​ 10− ​ M) HO• ( ​ × ​ 10− ​ M) ClO• ( ​ × ​ 10− ​ M) Cl• ( ​ × ​ 10− ​ M) O3 ( ​ × ​ 10− ​ M)
CBZ)

WO3 20 0.69 3.15 0.90 4.63 4.61

30 0.90 4.04 1.14 4.63 4.61
40 1.10 4.88 1.36 4.63 4.61
50 1.15 5.09 1.42 4.63 4.61
ClO− 0.1 1.10 4.88 1.36 4.63 4.61
0.3 0.29 1.75 1.62 5.97 6.95
0.5 0.15 1.07 1.81 6.35 7.69
0.7 0.02 0.39 1.27 6.52 8.02
CBZ 3.7 1.07 5.48 3.12 5.59 9.29
7.5 1.10 4.88 1.36 4.63 4.61
10.5 1.29 5.14 1.02 4.08 3.29
14.0 1.12 4.03 0.60 3.59 2.47

1 1 1 3.3. Contribution and concentrations of ROS

= C0 + (14)
kobs k kK
Radical probes are frequently used to determine the contributions of
where kobs represents the apparent pseudo-first-order rate constant various radicals to the degradation of contaminants. However, in a
(min− 1), k is the reaction rate corresponding to maximum coverage (M heterogeneous system, the adsorption of radical quenchers on the sur­
min− 1), and K is the adsorption constant of adsorbate on the photo­ face of a photocatalyst may lead to the direct quenching of h+ VB , rather
catalyst surface at equilibrium status (M− 1). The Langmuir-Hinshelwood than the selective scavenging of the radicals. Rao et al. (2013) reported
model assumes a preadsorption of adsorbate on the photocatalyst as well that both methanol and ethanol can enhance CBZ degradation via the
as heterogeneous reactions (Fox and Dulay, 1993). However, a linear UV–vis/WO3/persulfate process. In our previous study, the quenching
relationship between 1/kobs and C0 has also been observed in a homo­ effect of tert-butanol on CBZ degradation via the UVA/WO3/persulfate
geneous system (Deng et al., 2013). Therefore, whether the oxidation of process was weakened when its concentration was increased (Ding and
CBZ occurred on the surface of WO3 or in the liquid solution cannot be Hu, 2021a). These results suggest that the measurement of radical
determined purely based on the relationship between 1/kobs and C0. concentrations in WO3-based photocatalytic systems using probes might
Further, considering the fact that the WO3 surface is hydrophilic (water be inaccurate. To overcome this setback, electron paramagnetic reso­
tangle ​ < ​ 90◦ ) and that CBZ is highly hydrophobic (logKow ​ = ​ 2.45) nance (EPR) could be employed to qualitatively identify the existence of
(Azimirad et al., 2007; Huang et al., 2019), the adsorption of CBZ onto HO•; however, this method does not offer the possibility to distinguish
the WO3 surface would be weak. This was also confirmed by the negli­ ClO• and Cl• (Li et al., 2016). Considering these facts, it was difficult to
gible adsorption of CBZ onto the WO3 surface in this study. Given that experimentally measure the concentrations of radicals in the
the absorption of UVA light (365 ​ nm) by CBZ is negligible (BIZI, 2019), UVA/WO3/ClO− system.
it was unlikely that the decrease in kobs resulted from the attenuated In this study, the contributions and concentrations of four ROS (HO•,
light intensity. Here, we proposed that CBZ was primarily oxidized by ClO•, Cl•, and O3) were estimated using a steady-state kinetic model. O3
radicals close to the WO3 surface rather than by h+ VB on the WO3 surface. was included in the model because Bulman et al. (2019) observed the
An increase in the concentration of CBZ resulted in a decrease in the formation of O3 during the photolysis of ClO− under 365 ​ nm UV light
concentration of ROS, owing to the quenching effect of CBZ. Moreover, irradiation; its accumulation was the highest at a pH of 8, representing a
given that kobs was determined using the concentrations of ROS (Eq. condition similar to that observed in this study. As shown in Fig. 2(a),
(9)), it decreased as the initial CBZ concentration increased. the relative contributions of the ROS to CBZ degradation were slightly
affected by the concentration of WO3. Further, ClO• was identified as the
dominant radical; its contribution to CBZ degradation was over 65%,

Fig. 3. (a) Effect of pH on CBZ degradation by the UVA/WO3/ClO− process; (b) Effect of HA concentration on CBZ degradation by the UVA/WO3/ClO− process.

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H. Ding and J. Hu Environmental Research 201 (2021) 111569

which was followed by that of HO• and O3 (approximately 20% and This can be attributed to the stronger photolysis of ClO− at higher
10%, respectively). Even though the second-order rate constant corre­ concentrations, which led to the generation of more O(3P). Conversely,
sponding to the reaction between HO• and CBZ was two orders of the contribution of Cl• remained negligible even at a ClO− dosage of
magnitude higher than that corresponding to the reaction between ClO• 0.7 ​ mM. The scavenging of Cl• by ClO− possibly suppressed its con­
and CBZ, the concentration of ClO• in the system was three orders of centration and reaction with CBZ, even though the photolysis of ClO−
magnitude higher than that of HO• (Table 2); thus, ClO• contributed the produced more Cl•. Further, the increase in ClO− concentration from 0.1
most to CBZ degradation. The negligible contribution of Cl• could be to 0.7 ​ mM also led to a 98% decline in e−CB concentration, indicating that
primarily attributed to its low concentration owing to the weak its scavenging effect on e−CB was quite significant.
photolysis of ClO− . Further, the concentrations of O3 and Cl• were in­ The relative contributions of the ROS at different initial CBZ con­
dependent of WO3 concentration as they were generated via the centrations are shown in Fig. 2(c). The relative contribution of ClO•
photolysis of ClO− . It was also observed that the concentration of declined sharply from 78 to 55%, while that of HO• rose monotonically
increased monotonically with the WO3 dosage, as more photons were from 13 to 35%. Further, given that CBZ and ClO− competed for HO•, the
absorbed by the photocatalyst. increase in CBZ concentration made it possible for more HO• to take part
Furthermore, the effect of ClO− concentration on the relative con­ in the CBZ degradation; hence, less ClO• was generated. The contribu­
tributions of the four ROS is shown in Fig. 2(b). The relative contribution tion of O3 to CBZ degradation remained relatively stable, while that of
of ClO• increased from 68 to 82% and then decreased slightly to 78% Cl• was still insignificant. Additionally, an increase in CBZ concentration
when the concentration of ClO− was increased from 0.1 to 0.7 ​ mM. resulted in a decrease in the concentration of the four ROS, suggesting
Conversely, the relative contribution of HO• decreased dramatically and the self-inhibitory effect of CBZ that was evidenced by the limited kobs.
continuously from 23 to 2% as the concentration of ClO− increased,
indicating that the quenching of HO• by ClO− significantly reduced its
contribution to CBZ degradation. Additionally, the contribution and 3.4. Effects of water matrix
concentration of O3 increased steadily as the concentration of ClO−
increased. Thus, O3 was identified as the second most important oxidant 3.4.1. Effect of pH
with respect to CBZ degradation at ClO− concentrations above 0.3 ​ mM. The highest degradation rate was observed at a pH of 6.2, and the
corresponding kobs was 0.241 min− 1. Lowering the pH to 4.2 or elevating

Fig. 4. Effects of ions concentration on CBZ degradation by the UVA/WO3/ClO− process: (a) Cl− ; (b) SO2−
4 ; (c) HCO3 ; (d) NH4 .
− +

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H. Ding and J. Hu Environmental Research 201 (2021) 111569

it to values above 8.2 decreased the kobs by more than 50% (Fig. 3(a)). negative, owing to the dissociation of its carboxylic groups (Simelane
Given that the pKa of hypochlorous acid (HClO) is 7.6 (Folkes et al., et al., 2017). The occupation of reaction sites on the WO3 surface and the
1995), HClO would exist as the dominant species at a pH of 6.2 or 4.2, enhanced repulsive electrostatic force between the WO3 surface and
while HClO deprotonation would result in the existence of ClO− as the ClO− could inhibit e−CB from being accepted by ClO− . Moreover, the
dominant species at a pH of 8.2 or 10.2. Further, the surfaces of WO3 rapid reactions of HA with HO• (2.5 ​ × ​ 104 ​ L ​ mg C− 1 s− 1) (Fang et al.,
particles are negatively charged given that its pHpzc is 4.0, which is 2014), ClO• (4.5 ​ × ​ 104 ​ L ​ mg C− 1 s− 1) (Guo et al., 2017), O3 (Miao and
below the pH range of the experiment. Thus, the repulsive electrostatic Tao, 2008), and Cl• (1.3 ​ × ​ 104 ​ L ​ mg C− 1 s− 1) (Fang et al., 2014) could
interaction between ClO− and the WO3 surface would hinder the quench the reactive species available to CBZ. The absorbance of UV light
acceptance of e−CB by ClO− , thereby weakening CBZ degradation under by HA could also reduce the number of photons absorbed by WO3,
alkaline conditions. Additionally, the second-order rate constant of the hindering the generation of e−CB and h+ VB . However, given that the molar
reaction between HO• and ClO− was more than three-fold higher than absorptivity of HA at 365 ​ nm was only 0.009 ​ L ​ mg− 1 cm− 1, it is
that corresponding to the reaction between HO• and HClO (Guo et al., possible that photon absorption by HA was negligible when its con­
2017). Thus, the quenching of HO• was stronger under alkaline condi­ centration was 1 ​ mg/L in this study. Therefore, the adsorption of HA on
tions than under acidic conditions, leading to lower kobs values at pH WO3 and reactive species quenching by HA were the primary reasons for
values of 8.2 and 10.2. However, the kobs at a pH of 4.2 was also much the dramatic drop in the CBZ degradation rate in the presence of HA.
lower than that at a pH of 6.2, suggesting that H+ possibly inhibited CBZ Even though HA could stabilize WO3 nanoparticles in a solution
degradation. One possible explanation for this observation is that H+ (Simelane et al., 2017), the results indicated that its inhibitory effect
occupied some of the reaction sites on the negatively charged WO3 overwhelmed the benefits it generated.
surface as a result of electrostatic interactions, rendering them inac­
cessible to HClO. Furthermore, given that the concentration of H+ at a 3.4.3. Effects of ions
pH of 4.2 was close to that of HClO (approximately 0.1 ​ mM), the Four ubiquitous ions in wastewater (Cl− , SO2− 4 , HCO3 , and NH4 )
− +

adsorption of H+ on WO3 possibly surpassed that of HClO. were selected, and their effects on CBZ degradation via the UVA/WO3/
ClO− process were investigated. As shown in Fig. 4(a) 1 mM of Cl−
3.4.2. Effect of humic acid brought about a slight decrease (9%) in the rate of CBZ degradation.
HA had a significant inhibitory effect on CBZ degradation, with However, a further increase in Cl− concentration only led to a negligible
1 ​ mg/L of HA led to a 63% decline in kobs (Fig. 3(b)). This inhibitory decrease in kobs. In a previous study, Cl− was identified as an inhibitor of
effect of HA on contaminant degradation via WO3-based heterogeneous the TiO2-based photocatalytic degradation process (Abdullah et al.,
photocatalysis has also been reported in some previous studies (Moha­ 1990; Dugandžić et al., 2017), and ROS scavenging by Cl− might be
gheghian et al., 2016; Yazdanbakhsh et al., 2020). HA interferes with the primarily responsible for retarding the oxidation of organic pollutants
photocatalytic degradation process primarily through reaction site (Farner Budarz et al., 2017). Further, in the presence of Cl− , HO• can be
blockage, reactive species scavenging, and photon absorbance (Brame
converted to the less reactive radical ( ) under alkaline conditions
et al., 2015; Doll and Frimmel, 2005). Additionally, increasing the
concentration of HA could render the zeta potential of WO3 more (Eqs. (15) and (16)) (Guo et al., 2017). Even though could be

Fig. 5. Configurations of ClO− on the WO3 (001) surface: (a) Geometry 1 of ClO− on the WO3 surface before adsorption; (b) Geometry 1 of ClO− on the WO3 surface
after adsorption; (c) Geometry 2 of ClO− on the WO3 surface before adsorption; (d) Geometry 2 of ClO− on the WO3 surface after adsorption. Red, aqua and green
balls represent O, W and Cl atoms, respectively. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of
this article.)

8
H. Ding and J. Hu Environmental Research 201 (2021) 111569

decomposed to Cl• (Eq. (17)), the presence of Cl− could result in a shift in
the equilibrium to the left, thereby maintaining a much higher con­
centration of than (Wang et al., 2016). Further, given that the
second-order rate constant of the reaction between CBZ and Contrary to the inhibitory effect of Cl− , SO2−
4 significantly enhanced

(4.3 ​ × ​ 107 ​ M− 1s− 1) was two orders of magnitude lower than that CBZ degradation (Fig. 4(b)). The enhancing effect of SO2− 4 peaked at
between CBZ and HO• (8.8 ​ × ​ 109 ​ M− 1s− 1) (Huber et al., 2003; Lei 3 ​ mM, with the corresponding kobs showing a 33% increase. However,
et al., 2019), the scavenging of HO• by Cl− could slow down the rate of this enhancing effect declined when the concentration of SO2−
4 surpassed
CBZ degradation. However, the low relative contribution of HO• to CBZ 3 ​ mM. As the second-order rate constant corresponding to the reaction
6 − 1 − 1
degradation possibly limited the inhibitory effect of Cl− , as reflected by between HO• and SO2− 4 (1.5 ​ × ​ 10 ​ M s ) is three orders of magni­
the slight decrease in kobs in the presence of Cl− . tude lower than corresponding to the reaction between HO• and ClO−
(1.85 ​ × ​ 109 ​ M− 1s− 1) (Chuang et al., 2017; Dorfman and Adams,

(15)

(16)

(17)

Table 3
EEO values for CBZ degradation by the UVA/WO3/ClO− process under different conditions.
Initial condition kobs (min− 1) EEO (kWh/m3)

CBZ (μM) WO3 (mg/L) ClO (mM)

−
pH HA (mg/L) Cl (mM)
−
SO2−
4 (mM)
HCO−3 (mM) NH+
4 (mM)

7.5 0 0.1 8.2 0 0 0 0 0 0.009 2.802

7.5 40 0 8.2 0 0 0 0 0 0.021 1.153
7.5 40 0.1 8.2 0 0 0 0 0 0.111 0.218
7.5 20 0.1 8.2 0 0 0 0 0 0.076 0.317
7.5 30 0.1 8.2 0 0 0 0 0 0.094 0.256
7.5 50 0.1 8.2 0 0 0 0 0 0.115 0.209
7.5 40 0.3 8.2 0 0 0 0 0 0.113 0.213
7.5 40 0.5 8.2 0 0 0 0 0 0.122 0.198
7.5 40 0.7 8.2 0 0 0 0 0 0.089 0.271
3.7 40 0.1 8.2 0 0 0 0 0 0.220 0.110
10.5 40 0.1 8.2 0 0 0 0 0 0.091 0.266
14.0 40 0.1 8.2 0 0 0 0 0 0.060 0.400
7.5 40 0.1 4.2 0 0 0 0 0 0.111 0.218
7.5 40 0.1 6.2 0 0 0 0 0 0.241 0.100
7.5 40 0.1 10.2 0 0 0 0 0 0.108 0.224
7.5 40 0.1 8.2 1 0 0 0 0 0.040 0.603
7.5 40 0.1 8.2 3 0 0 0 0 0.020 1.230
7.5 40 0.1 8.2 5 0 0 0 0 0.018 1.369
7.5 40 0.1 8.2 7 0 0 0 0 0.015 1.617
7.5 40 0.1 8.2 0 1 0 0 0 0.101 0.238
7.5 40 0.1 8.2 0 3 0 0 0 0.099 0.244
7.5 40 0.1 8.2 0 5 0 0 0 0.095 0.253
7.5 40 0.1 8.2 0 7 0 0 0 0.095 0.254
7.5 40 0.1 8.2 0 0 1 0 0 0.119 0.203
7.5 40 0.1 8.2 0 0 3 0 0 0.167 0.145
7.5 40 0.1 8.2 0 0 5 0 0 0.147 0.164
7.5 40 0.1 8.2 0 0 7 0 0 0.133 0.182
7.5 40 0.1 8.2 0 0 0 1 0 0.078 0.308
7.5 40 0.1 8.2 0 0 0 3 0 0.072 0.337
7.5 40 0.1 8.2 0 0 0 5 0 0.077 0.311
7.5 40 0.1 8.2 0 0 0 7 0 0.081 0.298
7.5 40 0.1 8.2 0 0 0 0 0.03 0.040 0.609
7.5 40 0.1 8.2 0 0 0 0 0.05 0.020 1.236
7.5 40 0.1 8.2 0 0 0 0 0.1 0.019 1.296

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H. Ding and J. Hu Environmental Research 201 (2021) 111569

1973), the scavenging of HO• by SO2−4 was more or less negligible and
3.5. Interactions between ClO− and the WO3 surface
could hardly explain the enhancing effect observed. It has been sug­
gested that the enhancement of CBZ degradation was mainly due to the Two geometries of ClO− (G1 in Fig. 5(a) and G2 in Fig. 5(c)) on the
improvement in the stability of the WO3 nanoparticles, owing to the surface of WO3 were set as the initial configurations (the optimized
presence of SO2− geometries of G1 and G2 are shown in Fig. 5(b) and (d), respectively).
4 in solution. Farner Budarz et al. (2017) reported that
The properties of ClO− on the WO3 surface corresponding to G1 and G2
SO2−
4 can enhance the stability of negatively charged TiO2 nanoparticles
before and after adsorption are listed in Table S2, which shows that the
by preventing aggregation. Similarly, SO2− possibly facilitated the
4 adsorption energies of G1 and G2 were − 0.12 and − 2.53 ​ eV, respec­
dispersion of the negatively charged WO3 nanoparticles; this could
tively, indicating that G2 is a more stable configuration than G1. The
enlarge the surface area of the photocatalyst exposed to photons.
high adsorption energy of G2 suggested a high affinity between ClO−
However, the increase in ionic strength may compress the electrical
and WO3. This helped in explaining why ClO− could overcome the
double layer, thereby destabilizing the suspended particles and pro­
electrostatic repulsion between itself and the negatively charged WO3
moting aggregation (Crittenden et al., 2012). This possibly explains why
surface to enable the abstraction of e−CB . Further, it was observed that the
the enhancing effect was hindered when the concentration of SO2− 4 was Cl–O bond was stretched 1.8- and 3.4-fold longer for G1 and G2 after
elevated above 3 ​ mM. optimization, respectively, indicating that a dissociative adsorption
The presence of HCO−3 resulted in a decrease in the rate of CBZ process possibly occurred on the WO3 surface. The Mulliken charge of
degradation, with kobs being decreased by approximately 30%. Further, the Cl atom also changed from negative to positive, indicating that it had
this inhibition effect of HCO−3 seemed to be independent of its concen­ lost electrons. Conversely, the O atom gained electrons from Cl as its
tration in solution (Fig. 4(c)). The scavenging of HO• by HCO−3 generates Mulliken charge became more negative, and ClO− lost electrons to WO3
(Eq. (18)) (Buxton et al., 1988; Neta et al., 1988) and the as the total Mulliken charges of Cl and O became higher than − 1.
second-order rate constant corresponding to the reaction between Additionally, as shown in Fig. S4, there was a decrease in the electron
and CBZ is 2.3 ​ × ​ 106 ​ M− 1s− 1 (Jasper and Sedlak, 2013), which density around Cl, while that around O was enriched. Meanwhile, some
is three orders of magnitude lower than that corresponding to the re­ electrons from ClO− were transferred to WO3 and distributed in the cell.
action between HO• and CBZ. This also explains the more potent The DOS of WO3 shifted slightly to lower energy levels (Fig. S5), indi­
inhibitory effect of HCO−3 than that of Cl− as is less reactive than cating that the positions of the valence and conduction bands of WO3
were lowered after the adsorption of ClO− (Long et al., 2006). Thus,
. Additionally, given that the reactivity of ClO• toward HCO−3 is
some new states that could increase the concentration of h+ VB in the
negligible (Guo et al., 2017), HCO−3 could selectively quench HO• in the valence band were generated between − 50 and − 10 ​ eV, thereby
system. The percentage decline of kobs was close to the relative contri­ elevating the photoactivity of WO3 (Zhang et al., 2019).
bution of HO•, suggesting that HCO−3 completely extinguished CBZ
degradation by HO•. The stable inhibition of CBZ degradation at
3.6. Assessment of electrical energy consumption
different HCO−3 concentrations indicated that the quenching of HO• by
HCO−3 was complete even at a concentration of 1 ​ mM.
The electrical energy per order (EEO, kWh/m3), which is the energy

(18)

required to degrade a specific contaminant in 1 ​ m3 water by one log

(Wang et al., 2017), was applied to estimate the electrical energy con­
The effect of NH+ 4 on CBZ degradation via the UVA/WO3/ClO
−
sumption associated with the UVA/WO3/ClO− process. The EEO values
process is shown in Fig. 4(d). Compared with the control group, kobs were calculated according to Eq. (21) (Bolton et al., 1996), and the re­
decreased by 64% when the [ClO− ]/[NH+ 4 ] value was 3. However, the
sults obtained are listed in Table 3.
rates of CBZ degradation at [ClO− ]/[NH+ 4 ] values of 2 or 1 were basi­ P×t
cally the same as that corresponding to the UVA/WO3 system, suggest­ EEO = (21)
V × log(CC0t )
ing that the function of ClO− as an electron acceptor was entirely
inhibited by NH+ 4 . This inhibition, resulting from the presence of NH4 ,
+
where P represents the photon energy received by the reactor (kW); t
could be primarily attributed to the consumption of ClO by NH+ −
4 represents the reaction time (h); V represents the volume of the reactor
(Equations (19) and (20)). Further, when [ClO− ]/[NH+ 4 ] was 1, Eq. (19) (m3); and C0 and Ct represent the initial and final concentrations of CBZ,
was identified as the primary reaction and free chlorine in the solution respectively. The EEO values corresponding to CBZ degradation using
was converted to NH2Cl, which failed to prevent e−CB -h+ VB recombination. the UVA/WO3/ClO− process varied in the range of 0.100–1.617 ​ kWh/
When [ClO− ]/[NH+ 4 ] was elevated to 2 and surpassed the breakpoint at m3; thus, they are much lower than those corresponding to other UV/
1.5 (Crittenden et al., 2012), the reaction shown in Eq. (20) occurred; photocatalyst processes, with median values above 200 ​ kWh/m3
subsequently, only a small portion of the free chlorine, which was not (Miklos et al., 2018). Therefore, the introduction of solar light as a light
enough to enhance the UVA/WO3 process, remained in the solution. source may reduce the energy cost since WO3 is a visible-light-active
Furthermore, when [ClO− ]/[NH+ photocatalyst. Additionally, given that the concentration of CBZ in
4 ] was 3, approximately half of the
initial free chlorine remained after the reaction; this enhanced CBZ wastewater was in the order of several μg/L (much lower than those
degradation via the UVA/WO3 process. used in this study), lower EEO values might be needed for real waters
considering the shorter reaction time. However, the constituents of
NH+
4 + HOCl→NH2 Cl + H2 O + H
+
(19) natural waters could be much more complex than those of simulated
water samples. This may hinder the degradation process and prolong the
2NH2 Cl + HOCl→N2 + 3HCl + H2 O (20) needed reaction time. Therefore, future research is needed to investigate
the degradation of CBZ in real waters.

10
H. Ding and J. Hu Environmental Research 201 (2021) 111569

4. Conclusions Brame, J., Long, M., Li, Q., Alvarez, P., 2015. Inhibitory effect of natural organic matter
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presence of 0.1 ​ mM ClO− at pH 8.2, the CBZ degradation rate based on constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals
the UVA/WO3 process increased from 0.021 to 0.111 min− 1, suggesting (⋅OH/⋅O− ) in aqueous solution. J. Phys. Chem. Ref. Data 17, 513–886.
Buxton, G.V., Subhani, M.S., 1972a. Radiation chemistry and photochemistry of
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ClO− increased from 0.1 to 0.5 ​ mM, kobs increased only by 9%. How­ Chen, D., Cheng, Y., Zhou, N., Chen, P., Wang, Y., Li, K., Huo, S., Cheng, P., Peng, P.,
ever, increasing the ClO− concentration from 0.5 to 0.7 ​ mM decreased Zhang, R., Wang, L., Liu, H., Liu, Y., Ruan, R., 2020a. Photocatalytic degradation of
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greatly improved CBZ degradation. DFT calculations suggested the ex­ Clark, S.J., Segall, M.D., Pickard, C.J., Hasnip, P.J., Probert, M.I., Refson, K., Payne, M.C.,
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Declaration of competing interest process with peroxydisulfate: effects of light wavelength and water matrix. J. Hazard
Mater. 404, 124126.
The authors declare that they have no known competing financial Ding, H., Hu, J., 2021b. The optimal method for peroxydisulfate quenching: a
comparison of commonly used reductants. Chemosphere 262, 128000.
interests or personal relationships that could have appeared to influence Doll, T.E., Frimmel, F.H., 2005. Photocatalytic degradation of carbamazepine, clofibric
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Acknowledgement solutions. National Standard Reference Data System.
Dugandžić, A.M., Tomašević, A.V., Radišić, M.M., Šekuljica, N.Ž., Mijin, D.Ž., Petrović, S.
This research was supported by the President’s Graduate Fellowship D., 2017. Effect of inorganic ions, photosensitisers and scavengers on the
photocatalytic degradation of nicosulfuron. J. Photochem. Photobiol. Chem. 336,
(GRSUP0000003 President Grad Fel-PVO(SP)-IS) awarded by the Min­ 146–155.
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degradation in the UV/free chlorine system. Environ. Sci. Technol. 48, 1859–1868.
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