Separation and Purification Technology 255 (2021) 117726

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Separation and Purification Technology

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Enhanced photocatalytic oxidizing ability of Zn1-xIn2x/3S solid solution via

band structure by composition regulation
Yang Zheng a, 1, Xiufen Hu a, 1, Fang Deng a, *, Jian Li a, Dionysios D. Dionysiou b, Xubiao Luo a
a
National-Local Joint Engineering Research Center of Heavy Metal Pollutants Control and Resource Utilization, Nanchang Hangkong University, Nanchang 330063, PR
China
b
Environmental Engineering and Science Program, Department of Chemical and Environmental Engineering (DBCEE), University of Cincinnati, Cincinnati, OH 45221-
0012, USA

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

Keywords: Rational design of solid solutions is an efficacious strategy to enhance their photocatalytic performance. In this
Zn1-xIn2x/3S solid solution study, Zn1-xIn2x/3S solid solution with controllable band structures was obtained by optimizing the feed ratio of
Visible-light photocatalytic activity Zn/In in the synthesis. The feed Zn/In ratio has important influence on the crystalline structure, morphology,
Degradation pathway
light-absorption, band structure, carrier separation, ROS production and photocatalytic performance of Zn1-
Mineralization
xIn2x/3S solid solution for the degradation of multiple pollutants. With increasing indium content in the synthesis,
the band gap energy (Eg) of Zn1-xIn2x/3S solid solution gradually reduced. Zn0.6In0.27S solid solution showed the
highest photocatalytic activity with 97.10% 2-nitrophenol removal due to high ROS generation capacity arose
from the largest specific surface area and oxidizing capacity of h+. Chloramphenicol (CAP), ceftriaxone sodium,
2-nitrophenol (2NP) and 4-nitrophenol (4NP) can be degraded by photocatalysis of Zn1-xIn2x/3S solid solution,
and were decomposed to small molecules, NO–3 and Cl− ions via ring opening reaction, dechloridation and
denitrification, achieving efficient mineralization and toxicity reduction.

1. Introduction their incomparable advantages [12–17]. Some chalcogenide semi­

conductors such as ZnS and In2S3 are attractive photocatalysts in envi­
Chlorinated and nitrogen-containing organic compounds (ClNOCs) ronmental remediation [18–20], but they usually have their inherent
are widely distributed in natural environment owing to the wide use in defects. For example, ZnS is a wide band gap semiconductor, and suffers
chemical industry, agriculture and production of pharmaceuticals [1–3]. from low utilization of visible light and quantum efficiency, and short
ClNOCs have good chemical and thermal stability, and cannot be lifetime of photogenerated charge carriers [21]. In2S3 possesses a band
decomposed or biodegraded easily [4,5]. Most ClNOCs are carcinogenic, gap of 2.0 ~ 2.3 eV with low VB potential, thus shows a weak redox
teratogenic, mutagenic, and are easy to be enriched in organisms capacity. The design of Z-scheme heterojunctions is common strategy to
through food chain, leading to serious threat to natural ecology and remedy these shortcomings, but it still suffers from interface stress and
human health [6–8]. The toxicity of ClNOCs is mainly due to the lattice mismatching [22,23]. The fabrication of solid solution photo­
introduction of chlorine and nitryl [9,10]. Chlorine and nitryl sub­ catalysts is deemed as an efficient strategy to manipulate and tune band
stituents affect the distribution of electron cloud density on hydrocarbon gap and morphology, and all of which can influence the charge carrier
chains or benzene rings and the polarity of C-C or C bonds with other separation, ROS generation and photocatalytic activity [24]. According
atoms, resulting in poor biodegradability [11]. Therefore, the disposal of to ionic radius of Zn2+ (74 pm) [25] and In3+ (81 pm) [26], it is possible
ClNOCs pollutants, especially their transformation, dechlorination and to fabricate Zn1-xIn2x/3S solid solution, and the band structure can be
denitration, has important environmental significance. tuned by varying the feed ratio of Zn2+ to In3+ in order to realize proper
Photocatalysis based on reactive oxygen species (ROS) has been Eg and VB/CB potential for efficient charge separation and ROS
considered as an effective technique for the transformation and removal generation.
of chlorinated and nitrogenous organic pollutants from water due to In this study, Zn1-xIn2x/3S solid solution with controllable band

* Corresponding author.
E-mail address: [email protected] (F. Deng).
1
Yang Zheng and Xiufen Hu are co-first authors, and they almost equally contribute to the study.

https://doi.org/10.1016/j.seppur.2020.117726
Received 19 June 2020; Received in revised form 13 August 2020; Accepted 3 September 2020
Available online 20 September 2020
1383-5866/© 2020 Elsevier B.V. All rights reserved.
Y. Zheng et al. Separation and Purification Technology 255 (2021) 117726

structures was synthesized by one-pot hydrothermal method. Different and their absorbance was determined at the wavelength of 600 nm to
feed ratios of Zn2+ to In3+ have significant effect on Eg, specific surface investigate E. coli growth in LB liquid nutrient media.
area and morphology of Zn1-xIn2x/3S solid solution. The feed ratio of Zn/ The effect of CAP, ceftriaxone sodium and their degradation solution
In in the synthesis of Zn1-xIn2x/3S solid solution was optimized. The on E. coli colony formation in solid culture media was also studied. First,
degradation efficiency and pathways of four selected ClNOCs (2NP, 2 g agar was mixed with 40 mL deionized water and 10 mL CAP, cef­
4NP, CAP and ceftriaxone sodium) by visible-light photocatalysis of Zn1- triaxone sodium, or their degradation solution to form transparent so­
xIn2x/3S solid solution were systematically investigated, which can help lution, sterilized at 121 ◦ C for 15 min and then solidified in culture dish.
to understand the universality of photocatalytic degradation activity, 10 μL bacterial solution was evenly coated on solid culture, and then
control of intermediate products and toxicity reduction. cultured in an incubator at 37 ◦ C for 9 h to study the effect of CAP,
ceftriaxone sodium, or their degradation solution on colonies of E. coli.
2. Experimental
3. Results and discussion
2.1. Synthesis of Zn1-xIn2x/3S solid solution
3.1. Controllable synthesis and structure regulation of Zn1-xIn2x/3S solid
Zn1-xIn2x/3S solid solution was obtained by one-pot hydrothermal solution with adjustable band structure
method. Stoichiometric amounts of zinc acetate dihydrate (Zn
(Ac)2⋅2H2O), thioacetamide (TAA) and InCl3⋅4H2O were dissolved in Fig. 1 showed the XRD of pure ZnS, pure In2S3 and Zn1-xIn2x/3S solid
ultrapure water, then the solution reacted at 170 ◦ C for 6 h in 100 mL solutions. Pure ZnS possesses cubic phase (JCPDS No. 05-0566), while
Teflon-lined autoclave. After restoring at room temperature, the prod­ pure In2S3 displays tetragonal phase (JCPDS No. 25-0390). The
ucts were separated by centrifugation and purified with water and diffraction peaks of pure ZnS at 2θ = 28.58, 47.52 and 56.43◦ corre­
ethanol, and were dried at 60 ◦ C for further characterization and use. sponded to (1 1 1), (2 2 0) and (3 1 1) planes, respectively. The diffraction
The x value was 0.2, 0.4, 0.6 and 0.8, thus the products were marked as peaks of pure In2S3 at 14.19, 27.41, 33.21, 43.59 and 47.76◦ were
Zn0.8In0.13S, Zn0.6In0.27S, Zn0.4In0.4S and Zn0.2In0.53S, respectively. As a ascribed to (1 0 3), (1 0 9), (0 0 1 2), (1 0 1 5) and (2 2 1 2) planes, respec­
control, pure ZnS and pure In2S3 were prepared as above experimental tively. Noticeably, the 28.58◦ and 47.52◦ diffraction peaks of ZnS were
conditions. gradually shifted to lower-angle direction (27.54◦ and 47.04◦ for
Zn0.2In0.53S) as the decrease content of Zn, indicating that the Zn1-xIn2x/
2.2. Photocatalytic experiments 3S samples are in form of solid solutions, instead of a mixture of ZnS and
In2S3 phases. The individual peaks gradually shifted to lower diffraction
The photocatalytic properties of Zn1-xIn2x/3S solid solution were angles than the corresponding peaks of pure materials, indicating
tested by degrading 2NP, ceftriaxone sodium, CAP and 4NP under a 300 different proportions of solid solution [29]. The successive shift of
W xenon lamp with a 420 nm optical filter. Before photocatalytic diffraction peaks to lower-angle is attributable to larger radius of In3+
degradation, 50 mg Zn1-xIn2x/3S solid solution was suspended in 100 mL (0.81 Å) than Zn2+ (0.74 Å).
2NP, ceftriaxone sodium, CAP or 4NP solution (10 mg/L) for 40 min in The X-ray photoelectron spectroscopy (XPS) provided detailed in­
the dark. Visible-light photocatalytic degradation was carried out for formation of chemical composition and chemical states of pure ZnS,
120 min, and sampling was repeated at intervals of 20 min and filtered pure In2S3 and Zn0.6In0.27S solid solution (Fig. 2). The whole survey
instantly. The absorbance of filtrate was determined by UV–vis spec­ spectrum of Zn0.6In0.27S manifested the presence of Zn, In and S element
trophotometer to monitor the concentration change. (Fig. 2c). The signal peaks at 1022.07 and 1045.12 eV were indexed to
To determine the active species in the photocatalysis of Zn1-xIn2x/3S Zn 2p3/2 and Zn 2p1/2, respectively (Fig. 2d), which represent Zn2+ in
solid solution, triethanolamine (TEOA), p-benzoquinone (BQ) and Zn0.6In0.27S solid solution. In the In 3d XPS spectrums (Fig. 2e), the
EDTA-2Na were added in the above photocatalytic system as the scav­ peaks at 445.11 and 452.65 eV are characteristics of In 3d5/2 and In 3d3/
engers of OH, superoxide radical ( O−2 ) and hole (h+), respectively 2, respectively. The splitting energy of 1.18 eV of S 2p3/2 and S 2p1/2 at
• •

[27,28]. The operating process was similar to the above. 161.84 and 163.02 eV certified the presence of S2− in Zn0.6In0.27S solid
To investigate the stability of Zn1-xIn2x/3S solid solution, Zn0.6In0.27S solution (Fig. 2f).
solid solution was utilized in degrading 10 mg/L 2NP aqueous solution The morphologies of ZnS, In2S3 and Zn1-xIn2x/3S samples were shown
for 120 min, then Zn0.6In0.27S solid solution was recovered from the in Fig. 3 and Fig. S1. The surface of pure ZnS particles is smooth, and
suspension and washed with water. The recovered Zn0.6In0.27S solid their diameters range from about 15 nm to 250 nm. Pure In2S3 was
solution was repeated for the subsequent photocatalytic cycles under the
same reaction condition.

2.3. The quantification of OH and O−2 radicals

• •

The quantification of OH in photocatalytic process was determined

•

by benzoic acid oxidation. The oxidation amount of benzoic acid was

determined by the calibration of p-hydroxybenzoic acid in the degra­
dation solution and the yield of OH was calculated. The yield of O−2 can
• •

be quantitatively calculated by monitoring the reduction of NBT.

2.4. Toxicity evaluation

All instruments used in the experiment were sterilized. First, 25 g LB

broth was dissolved in 1000 mL ultrapure water and disinfected at
121 ◦ C for 15 min to obtain LB broth medium. First, 50 mL LB broth
medium, 10 mL CAP or ceftriaxone sodium degradation solution at
different time and 100 μL E. coli were added in 100 mL conical flasks,
and then sealed and cultured in an incubator at 37 ◦ C. At different in­ Fig. 1. XRD patterns of Zn1-xIn2x/3S solid solutions, where x has values of 0,
cubation period, 3 mL bacterial solution was taken out from conical flask 0.2, 0.4, 0.6, 0.8 and 1, respectively.

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Y. Zheng et al. Separation and Purification Technology 255 (2021) 117726

Fig. 2. XPS of survey spectrum of (a) pure ZnS, (b) pure In2S3, (c) Zn0.6In0.27S, and (d) Zn 2p, (e) In 3d and (f) S 2p of Zn0.6In0.27S solid solution.

composed of ultrathin nanosheet with thickness of about 5 nm (Fig. S1). In the above formula, n = 2; α, h and υ, are the absorption co­
Interestingly, Zn0.8In0.13S, Zn0.6In0.27S, Zn0.4In0.4S and Zn0.2In0.53S solid efficients, Planck’s constant and optical frequency [30,31]. The Eg
solution showed two kinds of morphology: spherical nanoparticles and values of Zn1-xIn2x/3S decreased with x increasing (Table 1), however,
nano-sheets, and with increasing the content of indium, the number of the Zn0.6In0.27S had the best photocatalytic performance, indicating that
spherical nanoparticles decreased (Fig. 3). Their TEM images further band energy is not primary factor in determining photocatalytic activity.
confirmed the spherical and nano-sheet structures, which were consis­
tent with the SEM results. Two distinct lattice fringes of Zn0.8In0.13S,
Zn0.6In0.27S, Zn0.4In0.4S and Zn0.2In0.53S solid solution in the HRTEM 3.2. Photocatalytic performance of Zn1-xIn2x/3S solid solution and
slightly increased with increasing the content of indium, which are close photocatalytic mechanism
to the ZnS (1 1 1) and In2S3 (1 0 9) planes (Fig. 3f). The XRD and HRTEM
of Zn0.8In0.13S, Zn0.6In0.27S, Zn0.4In0.4S and Zn0.2In0.53S samples jointly The visible-light photocatalytic activity of Zn1-xIn2x/3S (x = 0–1)
confirmed the formation of Zn1-xIn2x/3S solid solutions (Fig. 3). Zn1- solid solution were assessed by degrading 2NP aqueous solution
(Fig. 5a). The 2NP degradation efficiency by photocatalysis of ZnS and
xIn2x/3S solid solutions are mesoporous materials (Fig. S2), and the
specific surface area are related with × value. In case of x = 0.4, In2S3 was 57.31% and 62.59% after 120 min, respectively. The photo­
Zn0.6In0.27S solid solution has the maximum specific surface area catalytic activities of Zn1-xIn2x/3S solid solution boosted with increasing
(Table S1). x from 0 to 0.4, and reached the maximum value of 97.10% at x = 0.4
The UV–Vis DRS spectra were utilized to investigate the effect of In (Zn0.6In0.27S). Further increasing x value led to a decline in photo­
substitution on the light absorption and band gap energies (Eg) of Zn1- catalytic performance of Zn1-xIn2x/3S solid solution instead, indicating
the highest photocatalytic performance of Zn0.6In0.27S among the series
xIn2x/3S (0 < x < 1) solid solutions (Fig. 4). Pure ZnS had strong UV
absorption with steep edges at about 380 nm, while pure In2S3 exhibited of Zn1-xIn2x/3S (x = 0–1) solid solutions. Moreover, Zn0.6In0.27S is highly
strong visible-light absorption with absorption edge at 670 nm. The stable after repeated use (Fig. S4).
absorption edges of the Zn1-xIn2x/3S (0 < x < 1) solid solutions were According to the previous report, the separation of photon-generated
located between those of ZnS and In2S3, and the absorption edges were charge carrier is an important factor in influencing photocatalytic ac­
monotonically shifted to longer wavelengths as the × increases, which tivity, thus fluorescence (PL) and photocurrents of Zn1-xIn2x/3S (x = 0–1)
also indicates the formation of Zn1-xIn2x/3S homogeneous solid solution. solid solution were measured (Fig. 5b and c). As a rule, for photo­
The band gap energies (Eg) of Zn1-xIn2x/3S (x = 0–1) solid solutions were catalytic materials, the lower PL intensity or higher photocurrent
determined according to the tangent lines of the (αhυ)2 versus hυ curves response means lower degree of photogenerated e− -h+ recombination.
derived from equation (1) (Fig. 4b). In Fig. 4b, the Eg values of Zn1-xIn2x/ The photocurrent intensity of ZnS is the minimum, while its PL intensity
is the highest. With increasing x value, the PL intensity of Zn1-xIn2x/3S (x
3S (x = 0–1) solid solutions are dependent on their composition, and Eg
values of Zn1-xIn2x/3S (x = 0–1) decreased with increasing x. The ECB = 0–1) decreased (Fig. 5b), while the photocurrent intensity of Zn1-
(conduction band) which calculated from Eq. (2) and EVB (valence band) xIn2x/3S (x = 0–1) increased (Fig. 5c), suggesting that the charge sepa­
potential (determined by XPS, Fig. S3) of pure ZnS, pure In2S3 and Zn1- ration becomes more efficient. The photocurrent intensity of In2S3 is 3.3
times that of Zn0.6In0.27S.
xIn2x/3S solid solution were summarized in Table 1.
Although the charge separation and transfer of pure In2S3 are more
(αhυ)n = k(hυ − Eg ) (1) efficient than Zn1-xIn2x/3S, the photocatalytic activities of pure In2S3 are
still lower than those of Zn1-xIn2x/3S, which are not consistent with most
ECB = EVB − Eg (2) of reports that more efficient charge separation and transfer lead to
higher photocatalytic activity [32–34]. For exploring the underlying

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Y. Zheng et al. Separation and Purification Technology 255 (2021) 117726

Fig. 3. SEM (a, b, c and d), TEM (e, f, g and h) and HRTEM (i, j, k and l) images of Zn0.8In0.13S, Zn0.6In0.27S, Zn0.4In0.4S and Zn0.2In0.53S solid solution.

Fig. 4. (a) UV–vis diffuse reflectance spectra, (b) plots of (αhυ)2 versus hυ of Zn1-xIn2x/3S solid solutions with x values from 0 to 1.

reason, the active species in the photocatalytic process of Zn1-xIn2x/3S and OH and h+ also played minor parts in photocatalysis of Zn0.6In0.27S
•

solid solution were explored. As depicted in Fig. 5d, the 2NP degradation solid solution. Moreover, the above results also can be supported by
efficiency decreased dramatically to from 97.10% to 5.61% in presence theory [35,36]. In scheme 1, the VB of Zn0.6In0.27S solid solution is
of BQ. When IPA and TEOA were added in the photocatalytic system, slightly positive than the standard redox potential of OH/OH− (+1.99 V
•

2NP degradation efficiency decreased to 74.31% and 79.92%, respec­ vs. NHE), and CB of the Zn0.6In0.27S is much more negative than the
tively. These results demonstrated that O−2 was primary active species, standard redox potential of O2/ O−2 , thus the e− in CB of the Zn0.6In0.27S
• •

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Y. Zheng et al. Separation and Purification Technology 255 (2021) 117726

Table 1 sodium was further investigated (Fig. 6a). The adsorption of 2-nitrophe­
The Eg, EVB and ECB values of pure ZnS, pure In2S3 and Zn1-xIn2x/3S (x = 0–1) nol, 4-nitrophenol and CAP on Zn0.6In0.27S solid solution was less than
solid solutions. 10%, and photocatalytic degradation played a vital role in the removal
Samples Eg (eV) EVB (eV) ECB (eV) of 2-nitrophenol, 4-nitrophenol and CAP. The removal efficiency of 2-
ZnS 3.33 1.24 − 2.09
nitrophenol, 4-nitrophenol and CAP by Zn0.6In0.27S solid solution was
Zn0.8In0.13S 2.89 1.76 − 1.13 97.1%, 89.76% and 96.01% after 120 min visible-light photocatalysis,
Zn0.6In0.27S 2.74 2.02 − 0.72 respectively. Zn0.6In0.27S solid solution showed high adsorption capacity
Zn0.4In0.4S 2.56 1.72 − 0.84 for ceftriaxone sodium, and about 40% of ceftriaxone sodium was
Zn0.2In0.57S 2.39 1.40 0.99
−
adsorbed on Zn0.6In0.27S solid solution after 40 min in the dark. After 5
In2S3 2.00 1.82 − 0.18
min photocatalysis, the removal efficiency of ceftriaxone sodium can
reach 85.82% due to the rapid degradation of ceftriaxone sodium, and
has excellent reduction ability to reduce the O2 to O−2 , while h+ has
•
then the removal efficiency of ceftriaxone sodium was almost not
relatively weak oxidation ability. changed. The rapid degradation of ceftriaxone sodium in the first 5 min
In order to give insight to the higher photocatalytic activities of Zn1- and no obvious change after 5 min photocatalysis were attributed to the
xIn2x/3S, the yield of reactive oxygen species were calculated quantita­ unstable quaternary heterocycles, five-membrary heterocycles and six-
tively [37]. The yield of O−2 was quantified through the change of nitro-
•

blue tetrazolium (NBT) concentration due to their reaction, and the

relationship between the NBT consumed and the O−2 produced is 1: 4.
•

OH can react with excessive benzoic acid in a stable way to generate p-

•

hydroxy benzoic acid, m-hydroxy benzoic acid and o-hydroxy benzoic

acid, the ratio of production of these three products is 1.7: 2.3: 1.2,
respectively. The yield of p-hydroxybenzoic acid can be determined by
high performance liquid chromatography, and then the yield of OH was
•

quantitatively calculated according to their relationship. The yield of

O−2 and OH radicals was also compared between pure In2S3 and
• •

Zn0.6In0.27S (Fig. 5e and f). After 120 min visible-light irradiation, the
OH and O−2 yield of Zn0.6In0.27S is 6.715 × 10− 4 and 3.901 × 10− 5 mol/
• •

L, respectively. The OH and O−2 yield of pure In2S3 is 4.029 × 10− 4 and
• •

− 5
2.132 × 10 mol/L, respectively. The higher generation capacity of
Zn0.6In0.27S for OH and O−2 radicals than pure In2S3 was put down to
• •

proper Eg and enhanced oxidizing capacity of h+ in VB, thus leading to

higher photocatalytic activity.

3.3. The universality of photocatalytic degradation activity, control of

intermediate products and toxicity reduction

Scheme 1. Possible photocatalytic mechanism of Zn0.6In0.27S for degradation

The photocatalytic performance of Zn0.6In0.27S solid solution for the
of organic pollutants.
degradation of 2-nitrophenol, 4-nitrophenol, CAP and ceftriaxone

Fig. 5. (a) The photocatalytic activity of Zn1-xIn2x/3S (x = 0–1) solid solutions in degrading aqueous 2NP; (b) PL spectra and (c) photocurrent of pure ZnS, pure In2S3
and Zn1-xIn2x/3S(x = 0–1) solid solutions; (d) Effect of different scavengers on the 2NP photodegradation by Zn0.6In0.27S solid solution under visible-light irradiation;
The comparison of OH (e) and O−2 (f) production between pure In2S3 and Zn0.6In0.27S solid solution.
• •

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Y. Zheng et al. Separation and Purification Technology 255 (2021) 117726

Fig. 6. (a) The degradation of 2-nitrophenol, 4-nitrophenol, CAP and ceftriaxone sodium by visible-light photocatalysis of Zn0.6In0.27S solid solution; (b) The
concentration of NO−3 in the final degradation solution of 2-nitrophenol, 4-nitrophenol, CAP and ceftriaxone sodium; (c) The concentration of released Cl− during the
degradation processes of CAP.

membrary heterocycles of ceftriaxone sodium, and the formation of through a series of processes including hydrolysis of ester groups, frac­
stable intermediate products. The fate of nitrogen and chlorine in the ture of C-N bond and hydrogenation. On the other hand, the formation
photocatalysis was also investigated. As shown in Fig. 6b, NO−3 ions were of M7 can also be ascribed to the breakage of C-N bond and hydroge­
detected in the final degradation solution by anionic chromatography, nation of M5 molecules. Afterwards, M7 (m/z = 232.2) loses a portion of
and the concentration of NO−3 ions was 2.912, 1.703, 0.619 and 0.667 H2O to form M8, and the further breakage of C– – C bonds leads to the
mg/L in the final degradation solution of 2-nitrophenol, 4-nitrophenol, formation of M9. Cyclohexanone (M13, m/z = 97.1) was formed via the
CAP and ceftriaxone sodium, respectively. Besides, the concentration of denitrification and further attack of reactive species on M9. Eventually,
released Cl− during the degradation processes of CAP was measured. the carbocyclic ring of M13 was opened to form acetic acid and other
The concentration of Cl− in the CAP degradation solution increases with small molecules. Pathway 2 via double point attack: some OH radicals
•

photocatalysis time, and reaches 2.005 mg/L after 2 h (Fig. 6c). The attack the aromatic ring of CAP molecules, while other OH radicals
•

above results provided direct evidence for efficient dechloridation and attacks the C atom on the branched chain, resulting in the formation of
denitrification. The mineralization efficiency of 2NP, 4NP, CAP and M11. M11 was further attacked by O–2, OH and h+ radicals, and un­
• •

ceftriaxone sodium was also determined (Fig. 7), and the mineralization dergoes a series of oxidation and hydrogenation to form acetic acid
efficiency of 2NP, 4NP, CAP and ceftriaxone sodium after 7 h photo­ (M14).
catalysis reached 63%, 51%, 44.3% and 59.2% after photocatalysis, In Fig. 9, ceftriaxone sodium (M1) could be degraded to M2 (m/z =
respectively. 114.2), M3 (m/z = 143.2), M4 (m/z = 165.2) and M5 (m/z = 190.7) due
The degradation intermediates of CAP, ceftriaxone sodium, 4NP and to bond ruptures at the dashed lines in the M1 molecule. M1 also can be
2NP were analyzed by high performance liquid chromatography-mass degraded to M2 and M6 (m/z = 495.1). M6 was further demethylated and
spectroscopy (HPLC-MS) and possible degradation pathways were decarboxylated to form M7 (m/z = 419.0). Afterwards, M7 degraded to
deduced. As described in Fig. 8, two possible degradation pathways of M8 via the loss of methoxy group. Then the fragment at m/z 320.9 (M9)
CAP occur via unit point attack and double point attack of hydroxyl appeared due to opening of quaternion ring and loss of small molecules
radical ( OH). Pathway 1 via unit point attack: hydroxyl radicals ( OH) from M8. Finally, M9 molecule was further fragmented into M10 (m/z =
• •

attack CAP molecules to form three hydroxylation products which are 143.2) and M11.
isomers (M12, M22 and M32). Subsequently, M3 and M4 molecules were Fig. 10 shows HPLC-MS spectra of intermediate products of 2-nitro­
formed by the cleavage of C-C bond of M22 and M32 molecules, respec­ phenol (M1). The m/z peaks at 62.1, 129.2, 173.2, 369.1 and 413.0 were
tively. At the same time, M12 reacts with M3 to form M6 (m/z = 487.0) main intermediates in the degradation of 2NP (M1). The m/z at 413.0
molecule. Besides, M12 can also take off two Cl to form M5. Then, M6 and 369.1 are the ion peaks of [3M1-4H]+ and [3M1-4H-NO2]+,
takes off CH2Cl2 to form M10 by breaking C-C bond, and then forms M7 respectively. A series of isomers M2 (M1− 6
2 , m/z = 173.2) were formed by

Fig. 7. TOC change of (a) 2NP, (b) 4NP, (c) CAP and (d) ceftriaxone sodium.

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Fig. 8. (a) LC-MS and (b) possible degradation path diagrams of CAP.

the attack of OH radicals on the o-position and p-position of the benzene isomers M14 and M24 (m/z = 159.1), respectively. Afterwards, the nitro
•

ring of M1 molecule. M12, M22, M32, M42, M52 and M62 could react with O–2 group of M14 and M24 were reduced to amino, and M5 (M15 and M25, m/z =
•

1 2
radicals to form M3 and M3 along with the elimination of H2O molecules. 129.2) was formed, while M15 was further degraded to ethylene glycol
M13 and M23 are isomers, and they were further hydrogenated to form (M6, m/z = 62.1) under the further attack of O–2, OH and h+ radicals.
• •

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Y. Zheng et al. Separation and Purification Technology 255 (2021) 117726

Fig. 9. (a) LC-MS and (b) possible degradation path diagrams of ceftriaxone sodium.

During the degradation of 4NP, there were five main intermediate were [3M1-2NO2-2OH]+ and [3M1-NO2-OH]+, respectively. The
products of 4NP with the peaks of m/z at 62.2, 97.1, 113.2, 128.1 and possible degradation path was described in Fig. 10b. The benzene ring of
173.2 (Fig. 11). It is worth noting that m/z at 138.2 is the molecular ion M11 was attacked by OH radicals to form three isomers: M12, M22 and M32
•

peaks of 4NP (M11), and the relatively weak peaks at 293.3 and 353.5 (M2, m/z = 173.2). Subsequently, M2 takes off H2O to form M3, and was

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Fig. 10. (a) LC-MS and (b) possible degradation path diagrams of 2NP.

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Fig. 11. (a) LC-MS and (b) possible degradation path diagrams of 4NP.

hydrogenated gradually to produce M5 (m/z = 128.1). M5 was finally original CAP solution and ceftriaxone sodium, there was almost no
degraded to ethylene glycol (M6, m/z = 62.2). On the other hand, M11 can obvious E. coli growth, indicating high toxicity of CAP and ceftriaxone
be converted to its isomer M21, and M21 was hydrogenated to M7 (m/z = sodium to E. coli. With increasing degradation time, there was a great
113.2, the m/z peaks of 195.1 were [2M7-2H]+). M7 was further increases in OD600, suggesting dramatic decreases in toxicity. However,
deammoniated to form M8 (m/z = 97.1) and finally degraded to the OD600 value in solution medium containing CAP degradation solu­
ethylene glycol (M6). tion at 120 min was still lower than that of control group, suggesting that
To confirm the toxicity reduction of organic pollutants by the pho­ the photocatalysis of Zn1-xIn2x/3S solid solution can greatly alleviate the
tocatalysis of Zn1-xIn2x/3S solid solution, CAP and ceftriaxone sodium toxicity of CAP and ceftriaxone sodium, but cannot eliminate toxicity
degradation solution were taken as examples to investigate their effect owing to the formation of stable intermediate products, which was also
of on E. coli growth. The E. coli growth curves in culture medium con­ confirmed by E. coli colony growth in different solid media (Fig. S5).
taining CAP and ceftriaxone sodium degradation solution at different
degradation time was shown in Fig. 12. In culture medium containing

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Fig. 12. Growth curve of E. coli in culture medium containing CAP, ceftriaxone sodium and their degradation solution.

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