Science of the Total Environment 749 (2020) 142313

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Peroxymonosulfate-enhanced photocatalysis by carbonyl-modified

g-C3N4 for effective degradation of the tetracycline hydrochloride
Yahui Shi a, Jinsong Li a, Dongjin Wan a,⁎, Jinhui Huang b, Yongde Liu a
a
School of Environmental Engineering, Henan University of Technology, Zhengzhou, Henan 450001, China
b
College of Environmental Science and Engineering, Hunan University, Changsha, Hunan 410082, 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

• The carbonyl-modified g-C3N4 is syn-

thesized via one-step calcination.
• The introduction of carbonyl accelerates
carrier's separation and PMS activation.
• The CO-C3N4 possesses higher photocat-
alytic activity than g-C3N4.
• The performance of CO-C3N4 is largely
promoted with the addition of PMS.
• O2•−, h+ and 1O2 mainly contribute to
TCH degradation relative to •OH and
SO4•−.

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

Article history: In this work, carbonyl-modified g-C3N4 (CO-C3N4) is prepared through one-step calcination of the melamine-
Received 17 June 2020 oxalic acid aggregates. The visible light-assisted photocatalytic degradation efficiency of the tetracycline hydro-
Received in revised form 15 August 2020 chloride (TCH) for CO-C3N4 is significantly enhanced by introducing the peroxymonosulfate (PMS), and the ap-
Accepted 7 September 2020
parent rate constant is greatly increased from 0.01966 min−1 in CO-C3N4/vis system to 0.07688 min−1 in CO-
Available online 12 September 2020
C3N4/PMS/vis system. It is found that carbonyl for CO-C3N4 might offer possible reactive sites for PMS activation
Editor: Yifeng Zhang and collection sites of photo-generated electrons, greatly accelerating carrier's separation for PMS activation. The
favorable conditions, such as the higher catalyst dosage, higher PMS amount and alkaline pH, contribute to TCH
Keywords: degradation. The deleterious effects of co-existing anions on the TCH degradation efficiency are ranked in a de-
Photocatalysis cline: H2PO− 2− − − −
4 > SO4 > HCO3 > NO3 > Cl , and it may be affected by the type and amounts of anions and active
Carbonyl-modified g-C3N4 radicals generated. The radical trapping tests and electron spin resonance (ESR) detection display that the O2•−,
Peroxymonosulfate activation h+, 1O2, •OH and SO4•− all contribute to TCH degradation. Meanwhile, possible degradation mechanism, interme-
TCH degradation diates and degradation pathway of TCH are revealed in CO-C3N4/PMS/vis system. This study will offer a new in-
sight for constructing PMS activation with carbonyl modified g-C3N4 photocatalysis system to achieve effective
treatment of organic wastewater.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction and Ghisi, 2014; Shi et al., 2020). Owing to its overuse, antibiotics
are frequently detected in water environment, including groundwa-
Antibiotics are intensively-applied chemicals for aquaculture ter (Szekeres et al., 2018), river water (Huang et al., 2019), surface
feeding and the treating of animal and human disease (Manzetti water (Danner et al., 2019) and drinking water (Sanganyado and
Gwenzi, 2019). Antibiotics exist for a long time in the environment,
⁎ Corresponding author. resulting in the spreading of antibiotic resistance, thereby
E-mail address: djwan@haut.edu.cn (D. Wan). destructing ecological systems and threatening human health.

https://doi.org/10.1016/j.scitotenv.2020.142313
0048-9697/© 2018 Elsevier B.V. All rights reserved.
Y. Shi, J. Li, D. Wan et al. Science of the Total Environment 749 (2020) 142313

Hence, it is urgent to explore the feasible and effective materials and/ degradation pathways of TCH in CO-C3N4/PMS/vis system were
or methods to eliminate antibiotics in water. discussed. Constructing PMS activation with carbonyl modified g-C3N4
Advanced oxidation processes (AOPs), with the advantage of com- photocatalysts for wastewater treatments will be a promising strategy.
plete decomposition of pollutants by generating active radicals, have
attracted much attention (Guan et al., 2013). AOPs typically include hy- 2. Experimental
droxyl (•OH) and sulfate (SO4•−) radicals. Compared with •OH, SO4•−
based AOPs are being research hot because of such merits: (1) SO4•− ex- 2.1. Materials
hibits the higher redox potential (E0 (SO4•−/SO2− 4 ) = 2.5–3.1VNHE) rel-
ative to •OH (E0 (•OH/H2O) = 1.8–2.7VVHE) (Shao et al., 2017); (2) the Peroxymonosulfate (2KHSO5·KHSO4·K2SO4, PMS) was from Alad-
half-life of 30–40 μs of SO4•− is longer relative to that of •OH (<1 μs) din Chemistry Co., Ltd., China. Melamine, oxalic acid dihydrate, rhoda-
(Lin and Zhang, 2017); (3) it is the independence of pH (Guan et al., mine B (RhB), Congo red (CR), methyl orange (MO), orange G (OG),
2013). The SO4•− expects be obtained via activation of peroxymonosul- tetracycline hydrochloride (TCH), sodium chloride (NaCl), sodium ni-
fate (PMS) via ultraviolet (UV), alkaline, ultrasound, heating, transition trate (NaNO3), sodium dihydrogen phosphate (NaH2PO4), sodium sul-
metal ions, metallic and metal-free catalysts (Wacławek et al., 2017). fate (Na2SO4), sodium bicarbonate (NaHCO3), p-benzoquinone (p-BQ),
Among them, UV, alkaline and thermal activation need the added methanol (CH3OH, MeOH), tert- butyl alcohol (C4H10O, TBA), disodium
chemicals or energy; the use of whether the homogeneous or heteroge- ethylenediaminetetraacetate (EDTA-2Na), hydrogen peroxide (H2O2)
neous metallic catalysts necessarily results in secondary pollution. and L-histidine (C6H9N3O2) were purchased from the Sino pharm
Allowing for economic cost and environmental impact, PMS activation Chemical Reagent Co., Ltd., China. Nitro tetrazolium blue chloride
using non-metal catalysts is promising, and several metal-free catalysts (NBT) and p-Hydroxybenzoic acid (p-HBA) were purchased from the
have been proposed, such as graphene (Duan et al., 2015), graphitic car- Macklin Co., Ltd., China. Benzoic acid (BA) was obtained from the Tianjin
bon nitride (g-C3N4) (Lin and Chen, 2016), carbon nanotubes (CNTs) Kemiou Chemical Reagent Co., Ltd., China. The solution pH was con-
(Lee et al., 2015) and activated carbon (Zhang et al., 2013). Duan et al. trolled by NaOH and H2SO4 with the concentration of 0.1 mol/L in Factor
(2015) reported that sulfur and nitrogen co-doped RGO exhibited re- experiments of pH.
markably improved activity in PMS activation for catalytic degradation
of phenol. Zhang et al. (2013) found that granular activated carbon
2.2. Preparation and characterization of CO-C3N4
(GAC) can activate PMS to degrade Acid Orange (AO7) with much
lower activation energy of 25.13 kJ/mol. Duan et al. (2016) studied
Melamine (6 g) and oxalic acid dihydrate (9 g), according to the
that the nanocarbons with diverse structure and dimensions for PMS ac-
molar ratio (2:3), were respectively dissolved in the de-ionized water.
tivation, and it was revealed that the radical and nonradical oxidations
Two above solutions were mixed for 2 h under electric stirring to obtain
functioned on diverse carbon catalysts, which was dependent on carbon
the white precipitates. Then the precipitate was filtered, washed and
structure.
dried at 60 °C. The precipitate was calcined in a muffle furnace (initial
Considering its characteristics of high specific surface area, good me-
temperature is 120 °C, 2.3 °C/min, 550 °C, 4 h). After being cooled,
chanical property and easy preparation, g-C3N4 is greatly attractive
dark brown products were obtained as CO-C3N4. Meanwhile, bulk g-
(Duan et al., 2020; He et al., 2020; Yi et al., 2020). Recently, g-C3N4-
C3N4 was obtained through a parallel process without addition of oxalic
based photocatalysis coupling with PMS activation has been utilized to
acid dihydrate.
degrade organic pollutants, in which PMS functions as the electron ac-
Characterization of both materials was provided in the Supplemen-
ceptor for formation of SO4•− (HSO− 5 + e
−
→ SO4•− + OH−) (Tao
tary Material.
et al., 2015). However, g-C3N4 suffers from poor photocatalytic activity
due to small specific surface area, poor separation of photogenerated
2.3. TCH degradation by CO-C3N4 activating PMS under visible light
carriers and weak light absorption (Wang et al., 2018, 2019a, 2019b).
In practice, several ways are used to modify g-C3N4 to improve PMS ac-
Briefly, the catalyst (20 mg) was dispersed into TCH solution
tivation for organic pollutant removal under visible light irradiation, in-
(10 mg/L, 100 mL) and stirred for 30 min in the dark to reach an
cluding nanostructure designing (g-C3N4 nanosheet) (Jiang et al., 2017),
adsorption-desorption equilibrium. The reaction was further conducted
constructing the heterojunctions with other semiconductors (PI/g-
via simultaneously adding PMS and turning on Xenon lamp (300 W,
C3N4, Co3O4/g-C3N4) (Gao et al., 2018a; Shao et al., 2017; Zhang et al.,
λ > 420 nm). Herein, unless otherwise specified, all experiments do
2018b), noble metal loading (Ag/g-C3N4) (Wang et al., 2017b), and cou-
not adjust initial pH. The aliquot of 2 mL was sampled at given times,
pling with activated carbon (g-C3N4/AC) (Dangwang Dikdim et al.,
and mixed with methanol of 2 mL at once. The sample was filtered
2019). As a matter of fact, the nonmetal doping (e.g., sulfur, nitrogen
using the microfiltration membrane (0.22 um) and determined at
and born co-doping) has been demonstrated to achieve high photocat-
357 nm by UV–vis spectrum analysis. The possible structure of TCH in-
alytic activity and PMS activation (Chen et al., 2019; Lin and Zhang,
termediates was analyzed through the high-performance liquid
2017). Such a carbon and oxygen co- doping g-C3N4 consists of earth-
chromatography-mass spectrometry (HPLC-MS) system in m/z range
abundant nonmetal elements, and can be simply synthesized by one-
of 50–500. The degradation of RhB (10 mg/L, 100 mL), CR (50 mg/L,
step preparation, making it a promising material with high photocata-
100 mL), OG (50 mg/L, 100 mL) and MO (50 mg/L, 100 mL) was mea-
lytic performance and PMS activation based on its sustainability. How-
sured respectively at 554 nm, 497 nm, 475 nm and 463 nm.
ever, for all we know, there are no studies on PMS activation by
All the degradation experiments were conducted in triplicate.
carbon and oxygen co-doping g-C3N4 under visible light irradiation so
far to remove TCH in water.
In this study, we have developed the non-metallic carbonyl modified 2.4. Photoelectrochemical experiments
g-C3N4 (CO-C3N4, i.e. C, O co-doping g-C3N4) with PMS effective activa-
tion for TCH degradation under visible light irradiation. CO-C3N4 was Details experiment process is presented in the Supplementary
characterized via various technologies, and its photocatalytic perfor- Material.
mance was investigated. The possible roles of carbonyl in CO-C3N4 for
PMS activation were revealed. Meanwhile, the effects of different factors 2.5. The quantification of the common free radicals (O2•−, •OH, SO4•−)
on TCH degradation by CO-C3N4 under visible light irradiation were
studied in details. Based on the radical trapping test, ESR results and Details quantification methods are given in the Supplementary
TCH intermediates analysis, the possible degradation mechanism and Material.

2
Y. Shi, J. Li, D. Wan et al.
3. Results and discussion
3.1. Structure and morphology characterization
The crystal structure of the catalysts is characterized by XRD
(Fig. 1a). The g-C3N4 and CO-C3N4 exhibit similar XRD spectra, resulting
from graphite-like structure. A stronger peak at 27.4° is marked as the
(002) phase of aromatic segment interlayer stacking with interlayer dis-
tance of 0.326 nm (Liao et al., 2014; Shi et al., 2018). A weaker peak at
Fig. 1. (a) XRD patterns, (b) FTIR spectra, (c) Survey spectra, (d) C1s, (e) N1s and (f) O1s of XPS spectra of g-C3N4 and CO-C3N4, and (g) 13C solid state NMR spectrum of CO-C3N4.
3
Science of the Total Environment 749 (2020) 142313
13.1° is marked as the (100) phase of inplane structural packing motif
of tri-s-triazine unit (Shi et al., 2018; Yan, 2012). Obviously, the peaks
of CO-C3N4 are far weaker relative to those of g-C3N4, suggesting a
lower crystallinity degree for CO-C3N4. The overall stacked layer mor-
phologies of g-C3N4 and CO-C3N4 are present in Fig. 2 based on SEM
and TEM techniques, whereas the layer structure of CO-C3N4 with
some irregular holes is more clear and distinct compared with that of
g-C3N4, likely because of release of more gas (NH3 and CO) during calci-
nation of melamine-oxalic acid supramolecular aggregates.
Y. Shi, J. Li, D. Wan et al.
Fig. 2. SEM and TEM images of (a, b) g-C3N4 and (c, d) CO-C3N4.
Both g-C3N4 and CO-C3N4 have similar FTIR spectra (Fig. 1b), sug-
gesting the retention of tri-s-triazine-based structure (Gao et al.,
2018b). The broad peaks in range of 3500–3000 cm−1 are because of
the existence of NH2 or NH at the structure defect sites by the incom-
plete condensation (Guo et al., 2018; Shi et al., 2018). The strong ab-
sorption between 1800 cm−1 and 1100 cm−1 is owing to the
stretching vibration of the heptazine heterocyclic ring (C6N7), specifi-
cally for C\\N (1412, 1324 and 1242 cm−1) and C_N stretching
modes (1636 and 1574 cm−1) (Guo et al., 2018). A sharp peak at
814 cm−1 is marked as s-triazine ring mode. However, the characteristic
peaks of C_O bending vibration can be not found in the FTIR spectrum
of CO-C3N4, possibly because of similarity of C_O and C_N bending vi-
bration as well as the intrinsic limits from analytical instrument.
The elemental composition of materials is determined via the ele-
mental analysis (Table 1). The C/N value and O content of g-C3N4 are
0.577 and 9.342, respectively, while increase to 0.583 and 10.696 in
CO-C3N4, indicating the existence of characteristic carbon and oxygen
doping. The XPS is used to further analyze g-C3N4 and CO-C3N4. Three
elements including carbon, nitrogen and oxygen are found in g-C3N4
and CO-C3N4 materials (Fig. 1c), and there is no obvious shift of binding
energy of C1s and N1s core electrons, suggesting that g-C3N4 and CO-
C3N4 possess the similar chemical states of both C and N. As present
Table 1
Elemental analysis (EA) of materials.
N (wt%) C (wt%) H (wt%) C/N (at.) O (wt%)
g-C3N4 61.39 35.45 1.905 0.577 9.342
CO-C3N4 59.98 34.98 2.267 0.583 10.696
4
Science of the Total Environment 749 (2020) 142313
from Fig. 1d, C1s peaks at 288.40 eV and 284.80 eV of both materials fol-
low the sp2-hybridized C atoms (N-C=N) (Li et al., 2018b) and the C-
C/C=C bond (Gao et al., 2018b), respectively. Fig. 1e provides the fitting
of N1s into the four nitrogen chemical states at 398.70 eV, 400.42 eV,
401.02 eV and 404.59 eV, corresponding to the sp2-hybridized aromatic
N bonding to C atom (C=N-C), the tertiary N bonding to C atom (N-(C)
3), amino functions with hydrogen (C-N-H) related to structural defects,
and π excitation, respectively (Shi et al., 2018; Wei et al., 2016). As seen
in Fig. 1f, both g-C3N4 and CO-C3N4 possess O1s peak at 532 eV, owing to
H2O adsorbing on the surface or hydroxyl groups (Shi et al., 2019; Zhang
et al., 2018a). In addition, CO-C3N4 exhibits a new peak at 530.62 eV that
corresponds to the carbonyl groups (C=O) (Zhao et al., 2014). The solid
state 13C NMR spectrum of CO-C3N4 is performed to further confirm the
existence of carbonyl carbon. As presented in Fig. 1g, the characteristic
peak at δ 161.36 ppm corresponds to amide carbonyl, and it may be
formed by dehydration of amino in melamine and carbonyl in the bro-
ken oxalic acid during the calcination. Besides, it is worth noting that
characteristic peak at δ 121.40 ppm correspond to -N=C=O (isocya-
nate). Meanwhile, the surface element composition of g-C3N4 and CO-
C3N4 based on XPS is given in Table S1, in which the percentage of car-
bon increases from 39.31% (g-C3N4) to 41.27% (CO-C3N4), and the oxy-
gen percentage increases from 2.41% (g-C3N4) to 2.50% (CO-C3N4). Thus,
combined XPS results with EA analysis and 13C NMR spectrum, CO-C3N4
presents the characteristic carbon and oxygen doping by the existence
of carbonyl.
The N2 adsorption-desorption isotherms and pore size distributions
are given in Table S2 and Fig. 3. The N2 adsorption-desorption isotherms
of both materials can be marked as the type I with a hysteresis loop of
H3 type, suggesting that their mesoporous structures are from accumu-
lation of sheet-like particles, which accords with SEM and TEM results.
Y. Shi, J. Li, D. Wan et al.
Fig. 3. N2 adsorption-desorption isotherms and pore size distribution (inset) of materials.
BET surface area and pore volume of CO-C3N4 are 47.97 m2/g and
0.17 cm3/g, respectively, and those of g-C3N4 are 27.93 m2/g and
0.12 cm3/g, respectively. Introducing the oxalic acid dihydrate has
only slight influence on BET surface area, suggesting that the surface
area might not be a key factor to cause different photocatalytic perfor-
mance of g-C3N4 and CO-C3N4.
Fig. 4. (a) DRS, (b) (αhv)1/2 versus hv curves, (c) PL spectra and (d) the fluorescence decay curves of materials.
5
Science of the Total Environment 749 (2020) 142313
3.2. Optical property and photoluminescence
The diffused reflectance spectra (DRS) of both materials are pro-
vided in Fig. 4a. g-C3N4 has an adsorption edge of ~475 nm, whereas
CO-C3N4 possesses a wider and stronger light absorption across the
overall spectrum ranging from 300 to 800 nm. Meanwhile, absorption
edge of CO-C3N4 also shows red-shift likely because of the existence of
carbonyl groups. The optical absorption of semiconductor and its elec-
tronic structure are closely related (Yang et al., 2016), and the band
gap energy of semiconductors can be estimated based on Kubelka-
Munk transformation (αhv = A(hv-Eg)n/2). The n value for g-C3N4 (indi-
rect transition) is 4. According to the (αhv)1/2 versus hv curves in Fig. 4b,
the Eg value of CO-C3N4 is 1.91 eV, smaller than that of g-C3N4 (2.28 eV),
revealing that CO-C3N4 has improved light absorption performance.
The photoluminescence (PL) is adopted to investigate charge
carrier's recombination in semiconductors. As showed in Fig. 4c, both
g-C3N4 and CO-C3N4 exhibit the wide emission peaks in range of 400
to 700 nm. Obviously, CO-C3N4 shows diminished PL intensity relative
to g-C3N4 likely owing to the existence of carbonyl, and it has been re-
ported that the carbonyl can function as collection site of
photogenerated electrons, contributing to carriers separation (Kong
et al., 2019). In addition, the clearer layer structure for CO-C3N4 also
might contribute to separation and transfer of the carriers. Meanwhile,
the fluorescence decay time curves of both materials are provided
from Fig. 4d and Table 2. The lifetime of the photogenerated charges di-
rectly determines its reaction with H2O to generate reactive oxygen rad-
icals, or its mineralization efficiency by direct reaction with target
Y. Shi, J. Li, D. Wan et al.
Table 2
The lifespan of photogenerated charge of materials.
Samples τ1 τ2
ns Rel (%) ns Rel (%)
g-C3N4 1.0667 32.69 5.8883 67.31
CO-C3N4 0.6671 37.56 6.8000 62.44
pollutants. Specifically, the longer the photogenerated charge lifetime
is, more conductive its migration to reaction active sites is; the shorter
the photogenerated charges lifetime is, the higher its recombination
rate is (Zhao et al., 2014). The short life (τ1) and long life (τ2) in CO-
C3N4 are decreased and increased, respectively, along with increase of
τ1 percentage, causing an increase of its mean life. All in all, CO-C3N4
possesses higher separation ability of photogenerated charges, thus
contributing to its stronger photocatalytic performance.
3.3. Photoelectrochemical properties
In order to further evaluate the separation and transfer efficiencies of
the photogenerated charges of CO-C3N4, the photocurrent response and
the Nyquist plot are measured. In the Fig. 5a, the photocurrent density of
CO-C3N4 is obviously higher than that of g-C3N4, indicating the excellent
separation efficiency of the photogenerated electron-hole pairs of CO-
C3N4. The Nyquist plot in the Fig. 5b presents that CO-C3N4 has a
lower charge transfer resistance with a smaller semi-circle than those
of g-C3N4, suggesting that CO-C3N4 possesses a faster charge transfer
by effectively separating electron and holes (Dong et al., 2020a; Li
et al., 2018a).
The Mott-Schottky (M-S) plots of g-C3N4 and CO-C3N4 materials are
tested at 1000 Hz in the dark to investigate the semiconductor nature.
The flat band potential (VFB) from the x-intercept of the M-S plot can
be used to approximately estimate the conduction band potential
(VCB) or the valence band potential (VVB) in the n-type or p-type
Fig. 5. (a) Transient photocurrent response, (b) EIS Nyquist in the dark, (c) the M-S plots at a frequency of 1000 Hz in the dark and (d) valence band XPS spectra of materials.
Science of the Total Environment 749 (2020) 142313
semiconductor, respectively (Dong et al., 2020b, 2020c). As seen in
Fig. 5c, both g-C3N4 and CO-C3N4 show positive slopes in the linear re-
mean (ns) gion, confirming that they are n-type semiconductors. The VFB values
of g-C3N4 and CO-C3N4 are respectively −0.60 and −0.58 V (vs. SCE),
corresponding to −0.36 and −0.34 V (vs. NHE). Meanwhile, the valence
4.3121
band XPS (VB-XPS) is performed (Fig. 5d), and the valence band (EVB) of
4.4965
g-C3N4 and CO-C3N4 are 1.97 and 1.55 eV, respectively. According to the
Mott-Schottky and VB-XPS, energy band gap of g-C3N4 and CO-C3N4 can
be calculated to 2.33 and 1.89 eV, which is basically consistent with their
estimated band gap from the Tauc plots (Fig. 4b).
3.4. Photocatalytic performance with PMS and stability
The photocatalytic performance of materials is evaluated by
degrading TCH in presence of PMS (Fig. 6a). The blank experiments in-
dicate that visible light irradiation alone barely degrade TCH, whereas
PMS alone is capable of degrading TCH (58.12%). For the control exper-
iments, before introducing the PMS and irradiation, it achieves an
adsorption-desorption balance in the dark for 30 min. Both g-C3N4
and CO-C3N4 exhibit no great adsorption toward TCH. After adding
PMS without the irradiation, TCH degradation is clearly improved
from 71.34% (CN + PMS) to 85.71% (CO-CN + PMS), suggesting car-
bonyl great reactivity on PMS activation without irradiation. It was
found that C_O groups act as principal reactive sites to activate PMS
(Guo et al., 2018; Wei et al., 2016). Specifically, Guo et al. (2018) studied
the catalytic properties of the graphitic carbon nitride modified mag-
netic carbon nanocomposites (Fe3O4@C/g-C3N4) in activating PMS for
degradation of Acid Orange 7, and proposed that the C_O groups on
the carbon surface of Fe3O4@C functioned as the principal active sites
for PMS activation. Wei et al. (2016) found that the delocalized elec-
trons from the triazine units of g-C3N4, especially the C_O groups had
a high chemical activity and could be transferred to activate the PMS
to produce radicals in g-C3N4/AC + PMS system. Further, the photocat-
alytic activity of g-C3N4 and CO-C3N4 is compared via TCH degradation
6
Y. Shi, J. Li, D. Wan et al. Science of the Total Environment 749 (2020) 142313

Fig. 6. (a) TCH degradation efficiency by different catalysts under different systems, (b) the corresponding kinetic constants, (c) the cycling tests and (d) the influence of different water
sources on TCH degradation efficiency in CO-C3N4/PMS/vis system. Conditions: [Cat.] = 0.2 g/L, [TCH]0 = 10 mg/L, [PMS] = 200 mg/L, λ > 420 nm, ambient temperature.

only under visible light irradiation. 71.60% TCH degradation within
60 min can be achieved in CO-CN + vis system, which is greatly higher
than that of CN + vis system (23.71%). It is speculated that CO-C3N4
possesses the improved photocatalytic activity likely owing to existence
of carbonyl (Kong et al., 2019; Zhang et al., 2016). Kong et al. (2019)
prepared one new carbonyl linked g-C3N4 through CO2-assisted thermal
polymerization of urea, and it was found that the = C=O groups func-
tioned as the collection sites of photogenerated electrons, thus contrib-
uting to the carriers separation. In addition, the higher surface area of
CO-C3N4 can provide more surface reaction sites; meanwhile the more
distinct layered porous structure of CO-C3N4 also facilitates TCH diffu-
sion and improves the reaction kinetics. With PMS adding, TCH degra-
dation is greatly increased up to 97.77% within 40 min. Such results
indicate that CO-C3N4 is more capable of activating PMS, and meanwhile
visible light irradiation also contributes to PMS activation by CO-C3N4,
which is ascribed to carbonyl: (1) it may be the main reactive sites to
activate PMS; (2) it is the collection site of the photogenerated electrons
and contributes to PMS activation into the active radicals. TCH degrada-
tion accords well with the pseudo-first-order kinetics in different sys-
tems (Zhang et al., 2019a), and corresponding rate constants are given
in Fig. 6b, which are calculated to be 0.01466 (R2 = 0.99551, PMS),
0.01872 (R2 = 0.99251, PMS + vis), 0.0045 (R2 = 0.99958, CN + vis),
0.02096 (R2 = 0.98777, CN + PMS), 0.02952 (R2 = 0.98934,
CN + PMS + vis), 0.01966 (R2 = 0.95738, CO-CN + vis), 0.03146
(R2 = 0.94269, CO-CN + PMS) and 0.07668 min−1 (R2 = 0.9644, CO-
CN + PMS + vis), respectively. Those results indicate that PMS largely
improves TCH photocatalytic degradation efficiency of CO-C3N4. A com-
parison of TCH degradation efficiency in CO-C3N4/PMS/vis system with
recently reported studies are provided in Table 3. Meanwhile, the re-
moval efficiencies of TOC and COD in the TCH solution are also mea-
sured. As given in Fig. S1, the removal efficiencies of TOC and COD in
CO-C3N4/PMS/vis system are higher than those in g-C3N4/PMS/vis

Table 3
The comparison with other reported studies for TCH degradation.

Photocatalyst Pollutant Concentration Dosage Time Degradation efficiency Light source Reference
(mg/L) (g/L) (min) (%)

ZnS-SnS2 TC 10 0.3 120 93.46 300 W XL (λ ≥ 420 nm) (Xia et al., 2020)
MnO2/CNK-OH-Mn TC 10 0.5 120 96.7 (H2O2) 300 W XL (λ ≥ 400 nm) (Zhang et al., 2020)
CuInS2/Bi2WO6 TCH 10 0.3 120 92.4 300 W XL (λ ≥ 420 nm) (Lu et al., 2019)
Ag/AgIn5S8 TCH 10 0.3 120 95.3 300 W XL (λ ≥ 400 nm) (Deng et al., 2018)
SnFe2O4/ZnFe2O4 TC 10 0.3 120 93.2 300 W XL (λ ≥ 400 nm) (Wang et al., 2020)
α-ZnTcPc/g-C3N4 TC 30 1.5 120 91.43 XL (λ ≥ 400 nm) (He et al., 2019)
ZnTCPP/g-C3N4 TC 30 1.5 120 80.3 XL (λ ≥ 400 nm) (Ma et al., 2019)
CO-C3N4 TCH 10 0.2 60 97.77 (PMS) 300 W XL (λ ≥ 420 nm) This work

XL: Xenon lamp; MnO2/CNK-OH-Mn: MnO2/Mn-modified alkalinized g-C3N4.

7
Y. Shi, J. Li, D. Wan et al. Science of the Total Environment 749 (2020) 142313

system, about 38.26% of TOC and 25% of COD can be removed for 5 h vis-
ible light irradiation. Those results indicate that CO-C3N4/PMS/vis sys-
tem shows excellent TCH degradation performance with favorable
mineralization ability and potential application prospects.
Cycling tests are conducted to evaluate the stability of CO-C3N4/
PMS/vis system (Fig. 6c). TCH degradation efficiency by CO-C3N4 pre-
sents the gradually decreasing trend, which is because of possible
blocking of active site by TCH degradation intermediates. Gratifyingly,
TCH degradation efficiency still can achieve up to 85.63% after five cy-
cling, suggesting the satisfactory reusability of CO-C3N4. Meanwhile,
XRD and FTIR comparison of the fresh and reused CO-C3N4 are provided
in Fig. S2, and there are no obvious change in the composition and struc-
ture for the reused sample, further indicating high stability and reusabil-
ity of catalyst (Deng et al., 2017a, 2017b).
3.5. The influence of different water sources
Considering the practical application, three kinds of water sources
are used as reaction solution for TCH degradation in CO-C3N4/PMS/vis
system, including tap water (Zhengzhou Running-water Company),
lake water (Henan University of Technology) and reclaimed water
(Wulongkou Sewage Treatment Plant, Zhengzhou). Deionized water is
used for comparison. Three kinds of water sources are treated as the sol-
vents and then mixed with TCH to study the photocatalytic activity of
CO-C3N4/PMS/vis system and evaluate whether different water sources
will affect the photocatalytic performance. As presented in Fig. 6d, TCH
degradation efficiencies in the deionized water, tap water, lake water
and reclaimed water are respectively 98.69%, 90.69%, 84.24% and
80.84%. Notably, TCH degradation efficiencies in real samples are

Fig. 7. Factors on the TCH degradation efficiency in CO-C3N4/PMS/vis system: (a) the initial TCH concentration, (b) catalyst dosage, (c) PMS concentration, (d) initial pH and (e) anions
(5 mM); (f) the degradation of other pollutants in the CO-C3N4/PMS/Vis system. Conditions: [RhB]0 = 10 mg/L, [CR]0 = 50 mg/L, [MO]0 = 50 mg/L, [OG]0 = 50 mg/L, [PMS] =
200 mg/L, [Cat.] = 0.2 g/L, λ > 420 nm, ambient temperature.

8
Y. Shi, J. Li, D. Wan et al.
lower than that in deionized water because of the existence of compet-
itive or quenching substances (e.g., ions and natural organic substances)
(Qin et al., 2020), whereas they are still satisfactory. Thus, CO-C3N4/
PMS/vis system exhibits great potential for realistic wastewater
treatment.
3.6. Factors on the photocatalytic degradation with PMS
The influence of various conditions on TCH degradation by CO-C3N4
are investigated in Fig. 7a–e. As observed in Fig. 7a, TCH degradation ef-
ficiency is decreased from 97.77% to 79.77% for 60 min with TCH initial
concentration increasing from 10 mg/L to 40 mg/L. It may be that a
higher TCH concentration will need a longer time to achieve same deg-
radation efficiency because of same reactive radicals generated by the
same amounts of CO-C3N4 and PMS.
Fig. 7b gives the effect of catalyst dosage on TCH degradation effi-
ciency. Specifically, TCH degradation is greatly improved with catalyst
dosage increasing from 0.1 g/L to 0.2 g/L, which is because of the in-
creased availability of active sites in the catalysts to react with PMS, gen-
erating more reactive radicals (Dangwang Dikdim et al., 2019).
Nevertheless, increasing catalyst dosage to 0.4 g/L has no improvement
on TCH degradation efficiency, possibly due to the obstruction of light
penetration at the higher catalyst dosage, reducing the surface area of
catalysts exposed to irradiation (Dangwang Dikdim et al., 2019).
Different PMS amounts (0.05 g/L–0.4 g/L) show the similar effect on
TCH degradation efficiency, especially for 0.2 g/L and 0.4 g/L (Fig. 7c). Al-
though higher PMS concentration is expected to form more reactive
radicals, the amount of photogenerated electrons produced by certain
catalyst dosage might be not enough for PMS activation (Wang et al.,
2017a; Wang et al., 2017b). Besides, Dangwang Dikdim et al. (2019) re-
ported that the excessive PMS could quench SO4•− to form SO5•− with
lower reactivity (E0 = 1.1 V).
Fig. 7d presents TCH degradation efficiencies by CO-C3N4/PMS/vis
system at different initial pH. With initial pH increasing from 3.0 to
11.3, there is no obvious influence on TCH adsorption efficiency. Mean-
while, CO-C3N4/PMS/vis system under different initial pH shows satis-
factory TCH degradation efficiencies; while it is worth noting that TCH
degradation rates with the initial pH of 3.0–9.0 are similar, which
might be owing to PMS acidification. The pH change after reaction in
CO-C3N4/PMS/vis system is provided in Fig. S3, and the final pH is
2.88, 3.47, 4.52, 5.36 and 10.48, respectively. The pKa of PMS is 9.4
(HSO− 5 → SO5
2−
+ H+, pKa = 9.4), and when the pH of solutions is
below 9.4, PMS mainly occurs by the H2SO5 type, and PMS activation
is inhibited (Ren et al., 2014). As a result, TCH degradation efficiency is
highest at initial pH 11.3, which is owing to that PMS is better
decomposed to more reactive radicals under alkaline conditions for
the enhanced TCH degradation efficiency.
Fig. 8. (a) TCH degradation in the presence of different scavengers and (b) the corresponding kinetic constants in CO-C3N4/PMS/vis system. Conditions: [Cat.] = 0.2 g/L, [TCH]0 = 10 mg/L,
[PMS] = 200 mg/L, λ > 420 nm, ambient temperature.
9
Science of the Total Environment 749 (2020) 142313
The influence of anions on TCH degradation is given in Fig. 7e. It is
known that adding HCO− −
3 /H2PO4 can cause the higher pH in the solu-
tion compared to the addition of Cl−, NO− 2−
3 and SO4 , while such
above anions cause inhibition effects on TCH degradation efficiency in
an increase: Cl− < NO− −
3 < HCO3 < SO4
2−
< H2PO− 4 , which indicates
that pH change caused by anions in the solution is not main reason
and it may be ascribed to anions competition with TCH for the active
sites and their quenching effects on the radicals. Specifically, Cl− can
react with SO4•− to form chloride radicals (Cl•) with weaker oxidizing
(Wang et al., 2014); NO− 2− −
3 , phosphate ions (HPO4 /H2PO4 ) and HCO3
−
−
exhibit the quenching effects on SO4• and/or •OH (Wang et al.,
2017b; Zhang et al., 2018a). Totally, the order of the inhibition efficien-
cies by various anions in this study differs from the other studies (Gao
et al., 2018a; Wang et al., 2017b; Zhang et al., 2018a), and it is closely re-
lated to the concentration of anions and types and amounts of reactive
radicals generated in those studies (Dangwang Dikdim et al., 2019;
Gao et al., 2018a; Wang et al., 2017b). Specifically, Wang et al.
(2017b) reported that Cl− had the inhibitory effect at low concentra-
tions and presented the acceleration effect over a critical concentration
for BPA degradation in 10% Ag/mpg-C3N4/PMS/vis system.
Different organic dyes are also adopted to study the universal appli-
cability of CO-C3N4 (Fig. 7f). RhB, CR, MO and OG are effectively de-
graded up to 99.85%, 98.20%, 97.33% and 98.03% in 60 min,
respectively, indicating that CO-C3N4/PMs/vis system possesses excel-
lent versatility toward multiple pollutants degradation.
3.7. Active species detection and mechanism insights
The reactive oxygen species (ROS), the photogenerated electron
(e−) and hole (h+) may exhibit roles for TCH degradation in such CO-
C3N4/PMs/vis system. Active species trapping tests are carried out by
using various scavengers, in which p-BQ, EDTA-Na, L-histidine and
TBA are used to trap O2•−, h+, 1O2 and •OH, and MeOH is adopted to
trap both SO4•− and •OH. As showed in Fig. 8 and Table 4, the inhibition
rates of p-BQ, EDTA-Na, L-histidine, MeOH and TBA toward TCH degra-
dation are respectively 90.61%, 92.99%, 82.14%, 44.75% and 23.41%, and
thus the role of SO4•− for TCH degradation is 21.34%. The results indicate
that O2•−, h+, 1O2, •OH and SO4•− all contribute to TCH degradation in
CO-C3N4/PMS/vis system, of which O2•−, h+ and 1O2 are the dominant
oxidized species.
To further verify the reactive species produced in CO-C3N4/PMS/vis
system, ESR tests using DMPO, BMPO and TEMP as spin-trapping agents
is conducted under dark and visible light irradiation. There occur no sig-
nals of active species in PMS/vis system without catalysts (Fig. S4). For
the CO-C3N4/PMS/vis system (Fig. 9a), no ESR signals occur without
adding PMS under dark condition, and the SO4•− and •OH signals
occur under visible light irradiation and PMS. The h+ in CO-C3N4
Y. Shi, J. Li, D. Wan et al. Science of the Total Environment 749 (2020) 142313

Table 4 that of •OH (0.0199 mmol/L) and SO4•− (0.0112 mmol/L) at 60 min in
The trapping agents, reactive species trapped, and the kinetic constants by the trapped re- CO-C3N4/PMS/vis system. The amount of SO4•− is lower during the reac-
active species.
tion, varying over the range of 0.0016–0.0112 mmol/L. This is likely
Trapping agents Reactive species k (min−1) Inhibition rate (%) owing to the transformation from SO4•− to •OH during the reaction.
blank – 0.04994 (R2 = 0.97083) 0 Herein, the proposed degradation mechanism for TCH in CO-C3N4/
p-BQ O2•− 0.00469 (R2 = 0.95985) 90.61 PMS/vis system is schematized in Fig. 10. Firstly, in the non-radical pro-
EDTA-2Na h+ 0.00350 (R2 = 0.99619) 92.99 cess, the oxidant PMS is able to degrade part of TCH (Eq. (1)). Secondly,
1
L-histidine O2 0.00892 (R2 = 0.90109) 82.14
in the radical process without irradiation, g-C3N4 possesses electron-
MeOH SO•− + •OH 0.02759 (R2 = 0.91261) 44.75
TBA •OH 0.03825 (R2 = 0.96785) 23.41 rich properties (Wei et al., 2016), the delocalized electrons from the tri-
azine units of g-C3N4, especially the C_O groups have a high chemical
Note: TCH degradation in the presence of different scavengers follows pseudo-first-order
kinetics, and the fitting correlation coefficients (R2) are given.
activity and could be transferred to activate PMS to produce •OH and
SO4•− radicals, and degrade TCH to various intermediates (Eqs. (2)–
(3)). Thirdly, after visible light irradiation, CO-C3N4 is excited to produce
(EVB = 1.55 eV) cannot react with H2O molecule or OH− to generate h+ and e− in its VB and CB, respectively (Eq. (4)). The e− can reduce the
•OH (E(•OH/OH−) = 1.99 eV, E(•OH/H2O) = 2.37 eV) (Chang et al., adsorbed O2 to O2•− (Eq. (5)), and also can be trapped by the PMS to
2015), whereas reaction between H2O/OH− and SO4•− (+2.5–3.1 produce SO4•− (Eq. (2)). The formed O2•− and SO4•− further are trans-
VNHE) can produce •OH (Tang et al., 2015). The •OH signals show clearly formed via a series of reactions to form •OH and 1O2 (Eqs. (6)–(9)).
stronger intensity than SO4•− signals. Meanwhile, O2•− and 1O2 signals Meanwhile, the h+ can either directly degrade TCH or react with PMS
also are found in CO-C3N4/PMS/vis system (Fig. 9b–c), which is owing to to form SO4•− (Eqs. (10)–(11)).
that e− in CO-C3N4 (ECB = −0.34 eV) is able to trap O2 to form O2•− (E HSO5 − þ TCH ! Products ð1Þ
(O2/O2•−) = −0.33 eV), and O2•− further reacts with •OH to form 1O2
− − − −
(Wang et al., 2014; Zhang et al., 2018a). Obviously, both O2•− and 1O2 HSO5 þe ! SO4 ˙ þ OH ð2Þ
signals are greatly stronger than •OH and SO4•− signals, indicating that
O2•− and 1O2 should be the dominant oxidized radicals in CO-C3N4/ HSO5 − þ e− ! SO4 2− þ ˙OH ð3Þ
PMS/vis system.
þ
To further quantify the concentration of common free radicals (O2•−, CO−C3 N4 þ hv ! h þ e− ð4Þ
•OH and SO4•−) in CO-C3N4/PMS/vis system, NBT, BA and p-HBA are
used as the indicators of O2•− (Li et al., 2019), •OH (Joo et al., 2005) O2 þ e− ! O2 ˙− ð5Þ
and SO4•− (Oh et al., 2017), respectively. As showed in Fig. S5, the
amount of the formed O2•− (0.0497 mmol/L) is greatly stronger than O2 ˙− þ e− þ 2Hþ ! H2 O2 ð6Þ

Fig. 9. The ESR spectra of CO-C3N4 in the presence of PMS under visible light irradiation by using (a) DMPO, (b) BMPO and (c) TEMP as the trapping agents. Conditions: [Cat.] = 0.2 g/L,
[PMS] = 200 mg/L, [DMPO] = [BMPO] = [TEMP] = 100 mM, λ > 420 nm, ambient temperature.

10
Y. Shi, J. Li, D. Wan et al.
Fig. 10. The possible degradation mechanism for TCH in CO-C3N4/PMS/vis system.
H2 O2 þ e− ! OH− þ ˙OH
SO4 ˙− þ OH− ! SO4 2− þ ˙OH
O2 ˙− þ ˙OH ! 1 O2 þ OH−
þ
h þ HSO5 − ! SO5 ˙− þ Hþ
2SO5 ˙− ! 2SO4 ˙− þ O2
Overall, the above reactive species, including h+, O2•−,1O2, •OH and
SO4•−, contribute together to the TCH degradation.
3.8. The possible pathway of TCH degradation in CO-C3N4/PMS/vis system
The analysis of intermediate products of TCH degradation in CO-
C3N4/PMS/vis system based on the HPLC-MS is conducted, and the
results are given from Fig. S6 and Table S3. Several intermediates
with the proposed m/z values of 476, 433, 429, 386, 362, 361, 320,
318, 274, 258, 242, 238, 124 and 61 are found in mass spectrometry.
It is known that TCH mainly contains the dimethyl amine structure
(A), ketone-amide-enol system (B) and phenol-acetone system (C),
and those structures are prone to group removal, dehydration, dehy-
drogenation and heterogeneous rearrangement (Dalmázio et al.,
2007; Jiao et al., 2008; Wang et al., 2011; Zhang et al., 2019b). Herein,
based on the analyzed intermediates, three potential routes of TCH
degradation are presented (Fig. 11). Both the I and II routes present
TCH decomposition process via a gradual removal of amine groups,
fracture of C\\C double bonds and attack of α-position of carbonyl,
which are similar to the previous reports (Gao et al., 2019). For the
III routes, •OH firstly replaces the hydrogen of -N(CH 3 ) 2 (Tang
et al., 2017), then removes -CH3 and -CONH2, and further is oxidized
to open loop and decarburized. It is worth noting that there are other
ion peaks in MS, which is due to the non-selective oxidation charac-
teristic of photocatalysis. Meanwhile, based on TOC results (Fig. S1),
it is supposed that the majority of organic carbon compounds are
converted to inorganic carbon in CO-C3N4/PMS/vis system. Hence,
at last, all the intermediates will be decomposed to small molecules,
like H2O, CO2, NH+ 4 , etc.
Science of the Total Environment 749 (2020) 142313
ð7Þ 4. Conclusions
In our work, CO-C3N4 is obtained through one-step calcination
ð8Þ
using melamine-oxalic acid aggregates as precursors, and has
greater photocatalytic performance than g-C3N4. With PMS adding,
ð9Þ TCH photocatalytic degradation efficiency by CO-C3N4 is greatly im-
proved and the corresponding apparent rate constant is improved
ð10Þ from 0.01966 min−1 to 0.07688 min−1. The enhanced activity may
be attributed to the stronger absorption of visible light and faster
separation of photogenerated carriers, which greatly contributes to
ð11Þ PMS activation into active radicals. Radical trapping tests and ESR
detection indicate that the O 2 •− , h+ and 1O 2 play the dominant
roles rather than •OH and SO4 •− for TCH degradation in CO-C3N 4/
PMS/vis system. Therefore, PMS activation with carbonyl-modified
g-C 3N 4 seems to be a greatly promising approach for wastewater
purification.
CRediT authorship contribution statement
Yahui Shi: Validation, Formal analysis, Visualization, Writing - Orig-
inal Draft.
Jingsong Li: Conceptualization, Methodology, Resources, Data
Curation.
Dongjin Wan: Conceptualization, Methodology, Resources, Data
Curation, Writing - Review & Editing, Funding acquisition.
Jinhui Huang: Resources, Supervision.
Yongde Liu: Resources, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
This study was supported by the National Natural Science Founda-
tion of China (51878251, 51578222) and the Doctoral Scientific Re-
search Start-up Foundation from Henan University of Technology
(2020BS005).
11
Y. Shi, J. Li, D. Wan et al. Science of the Total Environment 749 (2020) 142313

Fig. 11. The possible TCH degradation pathways in CO-C3N4/PMS/vis system.

Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.scitotenv.2020.142313.
References
Chang, F., Li, C., Luo, J., Xie, Y., Deng, B., Hu, X., 2015. Enhanced visible-light-driven photo-
catalytic performance of porous graphitic carbon nitride. Appl. Surf. Sci. 358,
270–277.
Chen, X., Duan, X., Oh, W.-D., Zhang, P.-H., Guan, C.-T., Zhu, Y.-A., Lim, T.-T., 2019. Insights
into nitrogen and boron-co-doped graphene toward high-performance peroxymono-
sulfate activation: maneuverable N-B bonding configurations and oxidation path-
ways. Appl. Catal. B Environ. 253, 419–432.
Dalmázio, I., Almeida, M.O., Augusti, R., Alves, T.M.A., 2007. Monitoring the degradation of
tetracycline by ozone in aqueous medium via atmospheric pressure ionization mass
spectrometry. J. Am. Soc. Mass Spectrom. 18, 679–687.
Dangwang Dikdim, J.M., Gong, Y., Noumi, G.B., Sieliechi, J.M., Zhao, X., Ma, N., Yang, M.,
Tchatchueng, J.B., 2019. Peroxymonosulfate improved photocatalytic degradation of
atrazine by activated carbon/graphitic carbon nitride composite under visible light ir-
radiation. Chemosphere 217, 833–842.
Danner, M.-C., Robertson, A., Behrends, V., Reiss, J., 2019. Antibiotic pollution in surface
fresh waters: occurrence and effects. Sci. Total Environ. 664, 793–804.
Deng, F., Zhong, F., Lin, D., Zhao, L., Liu, Y., Huang, J., Luo, X., Luo, S., Dionysiou, D.D., 2017a.
One-step hydrothermal fabrication of visible-light-responsive AgInS2/SnIn4S8
heterojunction for highly-efficient photocatalytic treatment of organic pollutants
and real pharmaceutical industry wastewater. Appl. Catal. B Environ. 219, 163–172.
Deng, F., Zhong, F., Zhao, L., Luo, X., Luo, S., Dionysiou, D.D., 2017b. One-step in situ hydro-
thermal fabrication of octahedral CdS/SnIn4S8 nano-heterojunction for highly effi-
cient photocatalytic treatment of nitrophenol and real pharmaceutical wastewater.
J. Hazard. Mater. 340, 85–95.

12
Y. Shi, J. Li, D. Wan et al.
Deng, F., Zhao, L., Luo, X., Luo, S., Dionysiou, D.D., 2018. Highly efficient visible-light pho-
tocatalytic performance of Ag/AgIn5S8 for degradation of tetracycline hydrochloride
and treatment of real pharmaceutical industry wastewater. Chem. Eng. J. 333,
423–433.
Dong, H., Hong, S., Zhang, P., Yu, S., Wang, Y., Yuan, S., Li, H., Sun, J., Chen, G., Li, C., 2020a.
Metal-free Z-scheme 2D/2D VdW heterojunction for high-efficiency and durable
photocatalytic H2 production. Chem. Eng. J. 395, 125150.
Dong, H., Xiao, M., Yu, S., Wu, H., Wang, Y., Sun, J., Chen, G., Li, C., 2020b. Insight into the
activity and stability of RhxP Nano-species supported on g-C3N4 for photocatalytic
H2 production. ACS Catal. 10, 458–462.
Dong, H., Zhang, X., Li, J., Zhou, P., Yu, S., Song, N., Liu, C., Che, G., Li, C., 2020c. Construction
of morphology-controlled nonmetal 2D/3D homojunction towards enhancing photo-
catalytic activity and mechanism insight. Appl. Catal. B Environ. 263, 118270.
Duan, X., O’Donnell, K., Sun, H., Wang, Y., Wang, S., 2015. Sulfur and nitrogen co-doped
graphene for metal-free catalytic oxidation reactions. Small 11, 3036–3044.
Duan, X., Ao, Z., Zhou, L., Sun, H., Wang, G., Wang, S., 2016. Occurrence of radical and
nonradical pathways from carbocatalysts for aqueous and nonaqueous catalytic oxi-
dation. Appl. Catal. B Environ. 188, 98–105.
Duan, Y., Deng, L., Shi, Z., Liu, X., Zeng, H., Zhang, H., Crittenden, J., 2020. Efficient sulfadi-
azine degradation via in-situ epitaxial grow of Graphitic Carbon Nitride (g-C3N4) on
carbon dots heterostructures under visible light irradiation: synthesis, mechanisms
and toxicity evaluation. J. Colloid Interface Sci. 561, 696–707.
Gao, H., Yang, H., Xu, J., Zhang, S., Li, J., 2018a. Strongly coupled g-C3N4 nanosheets- Co3O4
quantum dots as 2D/0D Heterostructure composite for peroxymonosulfate activa-
tion. Small 14, 1801353.
Gao, Y., Zhu, Y., Lyu, L., Zeng, Q., Hu, C., 2018b. Electronic structure modulation of graphitic
carbon nitride by oxygen doping for enhanced catalytic degradation of organic pol-
lutants through peroxymonosulfate activation. Environ. Sci. Technol. 52.
Gao, X., Ma, C., Liu, Y., Xing, L., Yan, Y., 2019. Self-induced Fenton reaction constructed by
Fe(III) grafted BiVO4 nanosheets with improved photocatalytic performance and
mechanism insight. Appl. Surf. Sci. 467-468, 673–683.
Guan, Y.-H., Ma, J., Ren, Y.-M., Liu, Y.-L., Xiao, J.-Y., Lin, L.-q., Zhang, C., 2013. Efficient deg-
radation of atrazine by magnetic porous copper ferrite catalyzed peroxymonosulfate
oxidation via the formation of hydroxyl and sulfate radicals. Water Res. 47,
5431–5438.
Guo, F., Lu, J., Liu, Q., Zhang, P., Zhang, A., Cai, Y., Wang, Q., 2018. Degradation of Acid Or-
ange 7 by peroxymonosulfate activated with the recyclable nanocomposites of g-
C3N4 modified magnetic carbon. Chemosphere 205, 297–307.
He, Y., Huang, Z., Ma, Z., Yao, B., Liu, H., Hu, L., Zhao, Q., Yang, Q., Liu, D., Du, D., 2019.
Highly efficient photocatalytic performance and mechanism of α-ZnTcPc/g-C3N4
composites for methylene blue and tetracycline degradation under visible light irra-
diation. Appl. Surf. Sci. 498, 143834.
He, Y.Q., Zhang, F., Ma, B., Xu, N., Binnah Junior, L., Yao, B., Yang, Q., Liu, D., Ma, Z., 2020.
Remarkably enhanced visible-light photocatalytic hydrogen evolution and antibiotic
degradation over g-C3N4 nanosheets decorated by using nickel phosphide and gold
nanoparticles as cocatalysts. Appl. Surf. Sci. 517, 146187.
Huang, Y.-H., Liu, Y., Du, P.-P., Zeng, L.-J., Mo, C.-H., Li, Y.-W., Lü, H., Cai, Q.-Y., 2019. Occur-
rence and distribution of antibiotics and antibiotic resistant genes in water and sed-
iments of urban rivers with black-odor water in Guangzhou, South China. Sci. Total
Environ. 670, 170–180.
Jiang, X., Li, J., Fang, J., Gao, L., Cai, W., Li, X., Xu, A., Ruan, X., 2017. The photocatalytic per-
formance of g-C3N4 from melamine hydrochloride for dyes degradation with peroxy-
monosulfate. J. Photochem. Photobiol. A Chem. 336, 54–62.
Jiao, S., Zheng, S., Yin, D., Wang, L., Chen, L., 2008. Aqueous photolysis of tetracycline and
toxicity of photolytic products to luminescent bacteria. Chemosphere 73, 377–382.
Joo, S.H., Feitz, A.J., Sedlak, D.L., Waite, T.D., 2005. Quantification of the oxidizing capacity
of nanoparticulate zero-valent iron. Environ. Sci. Technol. 39, 1263–1268.
Kong, L., Yan, J., Liu, S.F., 2019. Carbonyl linked carbon nitride loading few layered MoS2
for boosting photocatalytic hydrogen generation. ACS Sustain. Chem. Eng. 7,
1389–1398.
Lee, H., Lee, H.-J., Jeong, J., Lee, J., Park, N.-B., Lee, C., 2015. Activation of persulfates by car-
bon nanotubes: oxidation of organic compounds by nonradical mechanism. Chem.
Eng. J. 266, 28–33.
Li, C., Yu, S., Dong, H., Liu, C., Wu, H., Che, H., Chen, G., 2018a. Z-scheme mesoporous
photocatalyst constructed by modification of Sn3O4 nanoclusters on g-C3N4 nano-
sheets with improved photocatalytic performance and mechanism insight. Appl.
Catal. B Environ. 238, 284–293.
Li, Y., Ho, W., Lv, K., Zhu, B., Lee, S.C., 2018b. Carbon vacancy-induced enhancement of the
visible light-driven photocatalytic oxidation of NO over g-C3N4 nanosheets. Appl.
Surf. Sci. 430, 380–389.
Li, H., Deng, F., Zheng, Y., Hua, L., Qu, C., Luo, X., 2019. Visible-light-driven Z-scheme rGO/
Bi2S3–BiOBr heterojunctions with tunable exposed BiOBr (102) facets for efficient
synchronous photocatalytic degradation of 2-nitrophenol and Cr(VI) reduction. Envi-
ron. Sci.: Nano 6, 3670–3683.
Liao, Y., Zhu, S., Ma, J., Sun, Z., Di, Z., 2014. Tailoring the morphology of g-C3N4 by self-
assembly towards high photocatalytic performance. Chemcatchem 6, 3419–3425.
Lin, K.-Y.A., Chen, Y.-C., 2016. Accelerated decomposition of Oxone using graphene-like
carbon nitride with visible light irradiation for enhanced decolorization in water.
J. Taiwan Inst. Chem. Eng. 60, 423–429.
Lin, K.-Y.A., Zhang, Z.-Y., 2017. Degradation of bisphenol A using peroxymonosulfate acti-
vated by one-step prepared sulfur-doped carbon nitride as a metal-free heteroge-
neous catalyst. Chem. Eng. J. 313, 1320–1327.
Lu, X., Che, W., Hu, X., Wang, Y., Zhang, A., Deng, F., Luo, S., Dionysiou, D.D., 2019. The fac-
ile fabrication of novel visible-light-driven Z-scheme CuInS2/Bi2WO6 heterojunction
with intimate interface contact by in situ hydrothermal growth strategy for extraor-
dinary photocatalytic performance. Chem. Eng. J. 356, 819–829.
13
Science of the Total Environment 749 (2020) 142313
Ma, Z., Zeng, C., Hu, L., Zhao, Q., Yang, Q., Niu, J., Yao, B., He, Y., 2019. A high-performance
photocatalyst of ZnTCPP sensitized porous graphitic carbon nitride for antibiotic deg-
radation under visible light irradiation. Appl. Surf. Sci. 484, 489–500.
Manzetti, S., Ghisi, R., 2014. The environmental release and fate of antibiotics. Mar. Pollut.
Bull. 79, 7–15.
Oh, W.-D., Dong, Z., Ronn, G., Lim, T.-T., 2017. Surface-active bismuth ferrite as superior
peroxymonosulfate activator for aqueous sulfamethoxazole removal: performance,
mechanism and quantification of sulfate radical. J. Hazard. Mater. 325, 71–81.
Qin, F., Peng, Y., Song, G., Fang, Q., Wang, R., Zhang, C., Zeng, G., Huang, D., Lai, C., Zhou, Y.,
Tan, X., Cheng, M., Liu, S., 2020. Degradation of sulfamethazine by biochar-supported
bimetallic oxide/persulfate system in natural water: performance and reaction mech-
anism. J. Hazard. Mater. 398, 122816.
Ren, H.T., Jia, S.Y., Wu, Y., Wu, S.H., Han, X., 2014. Improved photochemical reactivities of
Ag2O/g-C3N4 in phenol degradation under UV and visible light. Ind. Eng. Chem. Res.
53, 17645–17653.
Sanganyado, E., Gwenzi, W., 2019. Antibiotic resistance in drinking water systems: occur-
rence, removal, and human health risks. Sci. Total Environ. 669, 785–797.
Shao, H., Zhao, X., Wang, Y., Mao, R., Wang, Y., Qiao, M., Zhao, S., Zhu, Y., 2017. Synergetic
activation of peroxymonosulfate by Co3O4 modified g-C3N4 for enhanced degradation
of diclofenac sodium under visible light irradiation. Appl. Catal. B Environ. 218,
810–818.
Shi, Y., Huang, J., Zeng, G., Cheng, W., Yu, H., Gu, Y., Shi, L., Yi, K., 2018. Stable, metal-free,
visible-light-driven photocatalyst for efficient removal of pollutants: mechanism of
action. J. Colloid Interface Sci. 531, 433–443.
Shi, Y., Huang, J., Zeng, G., Cheng, W., Hu, J., Shi, L., Yi, K., 2019. Evaluation of self-cleaning
performance of the modified g-C3N4 and GO based PVDF membrane toward oil-in-
water separation under visible-light. Chemosphere 230, 40–50.
Shi, Y., Wan, D., Huang, J., Liu, Y., Li, J., 2020. Stable LBL self-assembly coating porous mem-
brane with 3D heterostructure for enhanced water treatment under visible light irra-
diation. Chemosphere 252, 126581.
Szekeres, E., Chiriac, C.M., Baricz, A., Szőke-Nagy, T., Lung, I., Soran, M.-L., Rudi, K., Dragos,
N., Coman, C., 2018. Investigating antibiotics, antibiotic resistance genes, and micro-
bial contaminants in groundwater in relation to the proximity of urban areas. Envi-
ron. Pollut. 236, 734–744.
Tang, D., Zhang, G., Guo, S., 2015. Efficient activation of peroxymonosulfate by manganese
oxide for the degradation of azo dye at ambient condition. J. Colloid Interface Sci. 454,
44–51.
Tang, X., Ni, L., Han, J., Wang, Y., 2017. Preparation and characterization of ternary mag-
netic g-C3N4 composite photocatalysts for removal of tetracycline under visible
light. Chin. J. Catal. 38, 447–457.
Tao, Y., Ni, Q., Wei, M., Xia, D., Li, X., Xu, A., 2015. Metal-free activation of peroxymonosul-
fate by g-C3N4 under visible light irradiation for the degradation of organic dyes. RSC
Adv. 5, 44128–44136.
Wacławek, S., Lutze, H.V., Grübel, K., Padil, V.V.T., Černík, M., Dionysiou, D.D., 2017. Chem-
istry of persulfates in water and wastewater treatment: a review. Chem. Eng. J. 330,
44–62.
Wang, Y., Zhang, H., Zhang, J., Lu, C., Huang, Q., Wu, J., Liu, F., 2011. Degradation of tetra-
cycline in aqueous media by ozonation in an internal loop-lift reactor. J. Hazard.
Mater. 192, 35–43.
Wang, S., Li, D., Cheng, S., Yang, S., Yuan, G., He, H., 2014. Synthesis and characterization of
g-C3N4/Ag3VO4 composites with significantly enhanced visible-light photocatalytic
activity for triphenylmethane dye degradation. Appl. Catal. B Environ. 144, 885–892.
Wang, G., Chen, S., Quan, X., Yu, H., Zhang, Y., 2017a. Enhanced activation of peroxymono-
sulfate by nitrogen doped porous carbon for effective removal of organic pollutants.
Carbon 115, 730–739.
Wang, Y., Zhao, X., Cao, D., Wang, Y., Zhu, Y., 2017b. Peroxymonosulfate enhanced visible
light photocatalytic degradation bisphenol a by single-atom dispersed Ag mesopo-
rous g-C3N4 hybrid. Appl. Catal. B Environ. 211, 79–88.
Wang, M., Guo, P., Zhang, Y., Lv, C., Liu, T., Chai, T., Xie, Y., Wang, Y., Zhu, T., 2018. Synthesis
of hollow lantern-like Eu(III)-doped g-C3N4 with enhanced visible light photocata-
lytic perfomance for organic degradation. J. Hazard. Mater. 349, 224–233.
Wang, M., Jin, C., Li, Z., You, M., Zhang, Y., Zhu, T., 2019a. The effects of bismuth (III) dop-
ing and ultrathin nanosheets construction on the photocatalytic performance of gra-
phitic carbon nitride for antibiotic degradation. J. Colloid Interface Sci. 533, 513–525.
Wang, M., Li, Z., Tian, L., Xie, Y., Han, J., Liu, T., Jin, C., Wu, Z., 2019b. A facile synthesis of
nano-layer structured g-C3N4 with efficient organic degradation and hydrogen evolu-
tion using a MDN energetic material as the starting precursor. Int. J. Hydrog. Energy
44, 4102–4113.
Wang, J., Zhang, Q., Deng, F., Luo, X., Dionysiou, D.D., 2020. Rapid toxicity elimination of
organic pollutants by the photocatalysis of environment-friendly and magnetically
recoverable step-scheme SnFe2O4/ZnFe2O4 nano-heterojunctions. Chem. Eng. J. 379,
122264.
Wei, M., Gao, L., Li, J., Fang, J., Cai, W., Li, X., Xu, A., 2016. Activation of peroxymonosulfate
by graphitic carbon nitride loaded on activated carbon for organic pollutants degra-
dation. J. Hazard. Mater. 316, 60–68.
Xia, B., Deng, F., Zhang, S., Hua, L., Luo, X., Ao, M., 2020. Design and synthesis of robust Z-
scheme ZnS-SnS2 n-n heterojunctions for highly efficient degradation of pharmaceu-
tical pollutants: performance, valence/conduction band offset photocatalytic mecha-
nisms and toxicity evaluation. J. Hazard. Mater. 392, 122345.
Yan, Hongjian, 2012. Soft-templating synthesis of mesoporous graphitic carbon nitride
with enhanced photocatalytic H2 evolution under visible light. Chem. Commun. 48,
3430–3432.
Yang, X., Qian, F., Zou, G., Li, M., Lu, J., Li, Y., Bao, M., 2016. Facile fabrication of acidified g-
C3N4/g-C3N4 hybrids with enhanced photocatalysis performance under visible light
irradiation. Appl. Catal. B Environ. 193, 22–35.
Y. Shi, J. Li, D. Wan et al.
Yi, X., Yuan, J., Tang, H., Du, Y., Hassan, B., Yin, K., Chen, Y., Liu, X., 2020. Embedding few-
layer Ti3C2Tx into alkalized g-C3N4 nanosheets for efficient photocatalytic degrada-
tion. J. Colloid Interface Sci. 571, 297–306.
Zhang, J., Shao, X., Shi, C., Yang, S., 2013. Decolorization of Acid Orange 7 with peroxymo-
nosulfate oxidation catalyzed by granular activated carbon. Chem. Eng. J. 232,
259–265.
Zhang, J.-J., Ge, J.-M., Wang, H.-H., Wei, X., Li, X.-H., Chen, J.-S., 2016. Activating oxygen
molecules over carbonyl-modified graphitic carbon nitride: merging supramolecular
oxidation with photocatalysis in a metal-free catalyst for oxidative coupling of
amines into imines. Chemcatchem 8, 3441–3445.
Zhang, J., Zhao, X., Wang, Y., Gong, Y., Cao, D., Qiao, M., 2018a. Peroxymonosulfate-
enhanced visible light photocatalytic degradation of bisphenol A by perylene
imide-modified g-C3N4. Appl. Catal. B Environ. 237, 976–985.
Zhang, J., Zhao, X., Wang, Y., Gong, Y., Cao, D., Qiao, M., 2018b. Peroxymonosulfate-
enhanced visible light photocatalytic degradation of bisphenol A by perylene
imide-modified g-C3N4. Appl. Catal. B Environ. 237, 976–985.
14
Science of the Total Environment 749 (2020) 142313
Zhang, C., Wang, W., Duan, A., Zeng, G., Huang, D., Lai, C., Tan, X., Cheng, M., Wang, R.,
Zhou, C., Xiong, W., Yang, Y., 2019a. Adsorption behavior of engineered carbons and
carbon nanomaterials for metal endocrine disruptors: experiments and theoretical
calculation. Chemosphere 222, 184–194.
Zhang, C., Zeng, G., Huang, D., Lai, C., Chen, M., Cheng, M., Tang, W., Tang, L., Dong, H.,
Huang, B., Tan, X., Wang, R., 2019b. Biochar for environmental management: mitigat-
ing greenhouse gas emissions, contaminant treatment, and potential negative im-
pacts. Chem. Eng. J. 373, 902–922.
Zhang, Q., Peng, Y., Deng, F., Wang, M., Chen, D., 2020. Porous Z-scheme MnO2/Mn- mod-
ified alkalinized g-C3N4 heterojunction with excellent Fenton-like photocatalytic ac-
tivity for efficient degradation of pharmaceutical pollutants. Sep. Purif. Technol.
246, 116890.
Zhao, H., Yu, H., Quan, X., Chen, S., Zhang, Y., Zhao, H., Wang, H., 2014. Fabrication of
atomic single layer graphitic-C3N4 and its high performance of photocatalytic disin-
fection under visible light irradiation. Appl. Catal. B Environ. 152-153, 46–50.