Chemical Engineering Journal 434 (2022) 134732

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Chemical Engineering Journal

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Efficient degradation of tetracycline by persulfate activation with Fe, Co

and O co− doped g− C3N4: Performance, mechanism and toxicity
Zhibin Wu a, b, *, Zhijun Tong a, b, Yuanyuan Xie c, Haibo Sun a, b, Xiaomin Gong a, b,
Pufeng Qin a, b, *, Yunshan Liang a, b, *, Xingzhong Yuan d, Dongsheng Zou a, b, Longbo Jiang d
a
College of Resources and Environment, Hunan Agricultural University, Changsha 410128, PR China
b
Key Laboratory for Rural Ecosystem Health in the Dongting Lake Area of Hunan Province, Changsha 410128, PR China
c
PowerChina Zhongnan Engineering Corporation Limited, Changsha 410014, PR China
d
College of Environmental Science and Engineering, Hunan University, Changsha 410082, PR China

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

Keywords: In this work, the porously thin layered Fe, Co and O co − doped g − C3N4 (FCOCN) was synthesized as persulfate
Heteroatoms co− doped g− C3N4 (PS) activator for tetracycline (TC) degradation. The characterization demonstrated that Fe, Co and O doping
Persulfate activation could boost the specific surface area and modulate the electronic structure of g − C3N4. With addition of PS, the
Tetracycline
FCOCN2 exhibited the maximum TC removal efficiency of 90.1 % after 120 min reaction, and the kinetic con­
Degradation pathway
Products toxicity
stant was 2.67 times that of pure g–C3N4. Meanwhile, the removal ratio of total organic carbon and reaction
stoichiometric efficiency of PS could reach to 68.6% and 5.2%, respectively. When the addition of catalyst and PS
were 0.6 g/L and 10.5 mM, respectively, the lower pH and TC concentration, as well as higher temperature were
conducive to degradation reaction with activation energy at 23.88 kJ.mol− 1. As indicated by work function, a
lower internal electronic excitation energy barrier enhanced electron transfer, so the active species of •O2− , 1O2,
SO4•− , SO5•− and •OH could be favorably generated on over metal (II/III) redox shuttles, electron − rich O/N
and electron–deficient C active sites. The quantitative structure − toxicity relationship prediction of in­
termediates and the acute toxicity experiment showed that the toxicity of water treated for 60 min to V. fischeri,
E. coli and B. subtilis was significantly reduced. Moreover, after five consecutive degradation cycles, the removal
efficiency of TC still remained at 72.7%. Besides, even in matrices of tap water, river water, municipal waste­
water and medical wastewater, the elimination proportion of TC by FCOCN2/PS were 90.0%, 88.6%, 74.0% and
81.5%, respectively. Hence, the FCOCN2/PS system may be a promising alternative for highly effective treatment
of antibiotic contained wastewater and environmental protection.

1. Introduction
As the second–most antibiotic produced and consumed in the world,
tetracycline (TC) has been frequently applied in medical and animal
husbandry for bacterial infections treatment and livestock growth pro­
motion [1]. However, due to the poorly metabolizable property of TC in
vivo, vast majority of TC and its metabolites are discharged into water
body through excreta [2]. In hospital and pharmaceutical industry
wastewater, the concentration of TC could reach to 1077 mg/L, and
even after biochemical treatment, the level of TC still remains at 0.38 –
2.0 mg/L [3,4]. Moreover, the long − term residues of TC with stable
structure in water environment may destroy the aquatic ecosystem and
threaten the life health by inducing drug − resistant bacteria emergence
and genetic/biological toxicity [5]. Facing this urgent issue, enormous
efforts have been invested in developing efficient physicochemical
method, e.g., adsorption [6], flocculation [7], chemical oxidation [8,9],
etc., for removal of TC from effluent. Inherited from the classical
chemical oxidation, advanced oxidation process (AOPs) with strong
oxidizing free radicals has emerged as a promising alternative for
complete degradation of TC to low toxicity substances [10,11].
Among several available technologies, sulfate radical (SO4•− ) based
AOPs (SR–AOPs) has been regarded as an effective, eco − friendly and
adaptable technology for organic pollutants mineralization at the wide
pH range [12]. The SO4•− radical has a comparable or even higher
oxidation potential (SO4•− , 2.6 – 3.1 V vs. •OH, 1.8 – 2.7 V) and longer
half–lifespan (SO4•− , 30 – 40 μs vs. •OH, <1 μs) than •OH [13].

* Corresponding authors at: College of Resources and Environment, Hunan Agricultural University, Changsha 410128, PR China.
E-mail addresses: wzbaaa11@hunau.edu.cn, wzbaaa11@163.com (Z. Wu), qinpufeng@126.com (P. Qin), lyss3399@126.com (Y. Liang).

https://doi.org/10.1016/j.cej.2022.134732
Received 30 October 2021; Received in revised form 2 January 2022; Accepted 12 January 2022
Available online 17 January 2022
1385-8947/© 2022 Elsevier B.V. All rights reserved.
Z. Wu et al.
Generally, it could be generated by activation of persulfates (PS), e.g.,
peroxymonosulfate (E0(HSO5–/SO42–) = 1.75 VNHE) or peroxydisulfate
(E0(S2O82–/SO42–) = 1.96 VNHE) through various approaches, including
light irradiation [14,15], thermal treatment [16], ultrasonic irradiation
[17], electro–chemistry [8], semiconductors [15], magnetic and non­
–magnetic carbon/transition metal catalysts [9,12,18]. Taking advan­
tage of no extra energy input, carbon (e.g., biochar, graphene, carbon
nanotubes, etc.) and transition metal (e.g., Fe2+, Ni2+, Co2+, Mn2+, etc.)
catalysts have been intensively investigated for PS activation, in which
free radicals (e.g., SO4•− , •OH, •O2− , etc.) and/or nonradical species (e.
g., 1O2, surface − bound complex, etc.) may be simultaneously generated
for organic pollutants degradation [19–22]. Nevertheless, a large num­
ber of previous studies have proved that the secondary pollution caused
by metal ions leaching and the limited catalytic capacity of pristine
carbon material are the intrinsic drawbacks [20,23]. Therefore, the
strategy of coupling transition metal species into carbon skeleton has
been attempted to tailor the carbon/transition metal catalysts properties
[24–26]. For instance, after Co embedded into N, S co − doped carbon,
the Co and doped N,S element have synergistic effect to improve the
Fermi energy and activity of C atoms, which makes C atoms could act as
catalytic active center with more positive charge [27]. Likewise, the
coordination of iron with N contained species (e. g., –NH2, –NH–, N–)
and carbonyl group (C = O) could provide more electron − rich sp2
carbon and variable chemical valenced iron as active sites to achieve
favorable nonradical and radical reaction in Fe@N − doped graphene −
like carbon/PS system [28].
Last several years, much attention have focused on the modification
of emerging graphitic carbon nitride (g − C3N4) as PS activator for
pollutants elimination [29]. g − C3N4, an earth − abundant carbon and
nitrogen elements conjugated polymer, has superior advantages of
unique two − dimensional structure, high stability, easy preparation and
environment friendly in cost − effectively catalytic application [30,31].
Moreover, the heptazine rings with N based ligands of six nitrogen lone
pair electrons in g − C3N4 could serve as electron donors for high­
–affinity coordination with metal ions, which can overcome poor elec­
tronic mobility and relatively low surface area (10 – 20 m2/g) of bulk g
− C3N4 [32,33]. Previous reports have proved that the metal doping in g
− C3N4 could not only modulate the electron density on g − C3N4 surface
through formation of Me − Nx (Me = Fe, Co, Mn, Cu, etc.) bond, but also
significantly enlarge the specific surface area and active sites for PS
activation and various pollutants degradation [32–36]. What particu­
larly striking is that when metal ions and non − metallic elements are co
− doped into g − C3N4, a synergistic effect of electronic reconstruction
could be obtained [37,38]. After formation of C − O − Cu − N bonds in
Cu, O co − doped g − C3N4, the electron − rich Cu, O sites and electron
− deficient C site could react with PS to generate metastable in­
termediates and 1O2 for synergistic decomposition of pollutant [39].
Therefore, inspired by such previous excellent works, Fe, Co and O are
expected to hybridize into g − C3N4 for PS activation, and to best our
knowledge, rare attention have been concerned on degradation pathway
and toxicity change of TC degradation over Fe, Co and O co − doped g −
C3N4.
Herein, Fe, Co and O co − doped g − C3N4 was synthesized via
one–step calcination method and the catalytic activity for PS activation
was measured by TC degradation. The physicochemical properties
including morphology structure, elemental composition, electro­
chemical properties, etc. of Fe, Co and O co − doped g − C3N4 are sys­
tematically characterized. The influence factors of PS dosage, solid
liquid ratio, initial TC concentration, reaction pH and temperature on TC
degradation were examined. The production of radicals and non −
radical, and degradation intermediates were detected to reflect the
degradation mechanism and pathways. In addition, the toxicity of
degradation intermediates, the treatment of real wastewater and the
reusability of Fe, Co and O co − doped g − C3N4 were measured to
evaluate its economic and environmental friendliness.
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Chemical Engineering Journal 434 (2022) 134732
2. Materials and methods
2.1. Materials
The Fe(NO3)3⋅9H2O (>98.5%), Co(NO3)2⋅6H2O (>99%), urea
(CH4N2O, > 99%) Na2S2O8 (PS, >90%) and tetracycline (TC, 99.5%)
were purchased from Macklin Reagent Network (Shanghai, China).
River water, municipal wastewater and medical wastewater were ob­
tained from Liuyang River, a Municipal Sewage Treatment Plants and a
Community Hospital, respectively, in Changsha, China. All other
analytical grade chemicals and the ultrapure water resistivity at 18.25
MΩ.cm were used throughout the experiments.
2.2. Synthesis of Fe, Co and O co − doped g − C3N4
The Fe, Co and O co − doped g − C3N4 were synthesized by a simple
calcination route with the mixture of urea, Fe3+ and Co2+. Briefly, 1
mmol metal sourcewith different mole ratio of Fe3+/Co2+ was mixed
with 18 g of urea and 10 ml ultrapure water in a 100 ml ceramic crucible
by ultrasonication for 30 min. Then, the suspensions were thoroughly
dried at 333 K, and subsequently heated at 823 K for 4 h under the
self–sustained atmosphere with a heating rate of 10 K/min in a muffle
furnace. The products with mole ratio Fe3+/Co2+ at 7:1, 9:1 and 11:1 are
denoted as FCOCN1, FCOCN2 and FCOCN3, respectively. For compari­
son, the Fe doped g − C3N4, Co doped g − C3N4 and pure g − C3N4 were
prepared in absent of Co2+, Fe3+ and metal (Fe3+ and Co2+) source,
respectively, which is referred to as FCN, CCN and CN, respectively.
Also, by setting Fe3+/Co2+ ration at 9:1, the CoFe sample was prepared
without urea and the Fe and Co co − doped g − C3N4 (FCCN2) was
synthesized under N2 atmosphere for investigation of catalytic degra­
dation discrepancy.
2.3. Characterization methods
The morphologies of the samples were observed using the environ­
mental scanning electron microscope (SEM, FEI QuANTA 200, USA),
and transmission electron micro − scopy (TEM, JEM − 3010, Japan).
The crystal structure was recorded by using X–ray diffraction (XRD)
patterns with Bruker AXS D8 Advance diffractometer with Cu–Ka beam
source (λ = 1.541 Å). The surface elemental composition were analyzed
by the X − ray photoelectron spectroscopy (XPS, Thermo Fisher Scien­
tific–K–Alpha 1063, UK) with a resolution of 0.5 eV. The ultraviolet
photoemission spectroscopy (UPS) were detected by a Thermo spec­
trometer (ESCALAB 250 XI). The Brunauere–Emmette–Teller (BET)
specific surface area and pore size were measured by using automatic
surface analyzer (Quantachrome, USA). The zeta potentials analysis of
FCOCN2 in water solution at pH 3.0–11.0 (adjusted by 0.1 M NaOH or
HCl) was determined with a zeta potential meter (Zetasizer Nano–ZS90,
Malvern). The electron spin resonance (ESR) signals were conducted on
a Bruker model ESR JES − FA200 spectrometer with trapping agent of
100 mM, in which •SO4− , •OH and •O2− radicals were spin − trapped by
5, 5 − dimethyl − l − pyrroline N − oxide (DMPO), and 1O2 was spin −
trapped by 2,2,6,6 − tetramethylpiperidine (TEMP). Electrochemical
properties measurements were performed on a CHI 660D electro­
chemical workstation (Chenhua, China) using a three–electrode cell
with the nanostructure materials on FTO as the working electrode,
saturated Ag/AgCl and platinum electrode as the counter electrode and
the reference electrode, respectively.
2.4. Catalytic performance evaluation
All the catalytic degradation experiments were carried out in the
dark. Typically, 60 mg catalysts was magnetically stirred with 100 ml TC
(15 mg/L) until it reaches the adsorption − desorption equilibrium.
After that, 250 mg PS was rapidly added into the solution to initiate TC
degradation process. In order to monitor the concentration change of TC
Z. Wu et al.
during the degradation process, 3 ml of sample solution was withdrawn
by pipette at a certain interval. After solid − liquid separation, the re­
sidual concentration of TC was measured at wavelength of 357 nm by
UV–vis spectrophotometer (UV − 2250, SHIMADZU Corporation,
Japan). The concentration before and after adsorption equilibrium was
defined as the initial concentration (C0) and post–adsorption concen­
tration (Ca). The total organic carbon (TOC) level of samples were
determined by using a TOC analyzer (TOC–2000, Shanghai Metash In­
struments Corporation. China). The PS concentration before and after
reaction was determined by UV–VIS spectrophotometer at 352 nm, in
which 0.1 ml sample was pretreated for 15 min by 2 g KI and 0.1 g
NaHCO3 in diluent with a total volume of 20 ml. All experiments were
run in triplicates and the results were reproducible within 5 % of relative
standard deviation. The generation and role of radicals SO4•− , •OH,
SO5•− , •O2− and 1O2 was investigated by radical capture experiment.
The FCOCN2 after reaction was collected centrifugation and washed
with water to remove residual impurities, and then dried at 60 ◦C for
recycling.
2.5. Analysis of degradation intermediates and toxicity measurement
The degradation intermediates of TC during catalytic process were
detected by high performance liquid chromatography mass spectrom­
etry (HPLC − MS, Thermo Scientific Q Exactive, USA). The theoretical
toxicity of degradation intermediates was predicted by Toxicity Esti­
mation Software Tool program (T.E.S.T., version 5.1.1) depended on
Quantitative Structure Activity Relationships (QSAR) method. The real
toxic effects of solution samples at different degradation time on
bioluminescence inhibition of V. fischeri (NRRL B − 11177) was per­
formed according to standard biotest (ISO11348 − 3, 2007). The effect
of TC and degradation intermediates on E. coli and B. subtilis growth was
evaluated by colony method. 100 μL of bacteria solution in logarithmic
growth period that had been diluted 103 times was evenly spread on the
agar plate containing 10% TC degradation liquid for 12 h culture at
37 ◦ C. Before that, all solution samples were treated by adding ascorbic
acid for termination of degradation reaction.
3. Results and discussions
3.1. Characterization
The X − ray diffraction patterns (XRD) of pristine CN, FCN, CCN and
FCOCN samples were presented in Fig. 1. As can be seen, two typical
polymeric layered structure peaks of g − C3N4 locate at diffraction angle
Fig. 1. XRD patterns of various catalysts.
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Chemical Engineering Journal 434 (2022) 134732
of 2θ = 13.0◦ and 27.5◦ , which correspond to the (1 0 0) and (0 0 2) facets
with d − spacing of 0.68 nm and 0.32 nm, respectively, agreeing with g
− C3N4 reported elsewhere [40]. These two characteristic peaks are
arisen from the structural packing of tri − s − triazine units in the lattice
plane and the stacking of sp2 hybrid orbitals for conjugated aromatic
system, respectively [32]. Compared with CN patterns, the main peak of
(0 0 2) plane for doped CN is still preserved, suggesting that the doping
has not essential effect on graphitic stacking of g − C3N4. But it is worth
noting that the position of (0 0 2) diffraction peak for FCOCN has been
slightly blue − shifted from to 2θ = 27.3◦ (Fig. S1, Supporting Infor­
mation), implying the expansion of interlayer distances after interstitial
sites doping of heteroatom into in − planar g − C3N4 [32,36].
Furthermore, after Fe, Co and O co − doped into the CN, the peak in­
tensity of (1 0 0) plane is greatly decreased and even disappeared. During
reaction process, the heteroatoms of Fe, Co and O may exhibit the
inhibitory effect and host–guest interaction with carbon − nitrogen
framework, in which the in − plane structure of CN could be partially
fragmented into smaller crystallites, leading to the formation of edge
defects and in − plane cavities as new active sites for redox reaction
[34]. Interestingly, there are no impurity peaks belonging to Fe or Co
species, e.g., oxides, which suggests that the Fe and Co are appropriately
coordinated into the host of g − C3N4 in the form of Fe − Nx and Co − Nx
bonds [38].
The morphological features of CN, FCN, CCN and FCOCN2 were
observed by scanning electron microscopy (SEM). As illustrated in
Fig. 2a, the pure CN presents loosely thin flake network with abundant
porous resulted from gas release in self − polymerization of urea. After
doping of heteroatoms into CN, the FCN (Fig. 2b), CCN (Fig. 2c) and
FCOCN2 (Fig. 2d) tend to display small sheets with irregular wrinkles,
which may be ascribed to the disruption and inhibition poly­
condensation reaction for the formation of smaller microparticles
[41,42]. This change in morphological structure will significantly pro­
mote the exposure of redox–active centers and the accessibility of per­
sulfate and pollutant, so as to improve catalytic activity for pollutants
degradation [43]. Especially, FCOCN2 (Fig. 2d and 2e) exhibits relative
laminar stacked phase with porous composited of thin wrinkles, indi­
cating the successful co − doping of Fe, Co and O into g − C3N4. It can
also be confirmed by energy dispersive spectrum (EDS) of FCOCN2
(Fig. 2f). The signals of C, N, Fe, Co and O elements are clearly detected,
and all of them are uniformly distributed on FCOCN2 surface supported
by elemental mapping analysis. The doping of O element is mainly
ascribed to the oxidation of C and N, in which the interactions of Fe, Co
with urea molecules could capture oxygen into g − C3N4 structure[34].
Further detailed structure of CN, FCN, CCN and FCOCN2 were
characterized by transmission electron microscopy (TEM). The crinkly
CN (Fig. 3a) exhibits very thin silk − veil morphology with numerous
irregular pore. As revealed in Fig. 3b, the bulk FCN presents thickly
stacked block characteristics with remarkable decrease in particle size,
agreeing with SEM observations. After implantation of Co into CN
(Fig. 3c), the framework of CCN turns to become more loose with more
pores, which could provide more edge defects and in − plane cavities as
redox active site for PS activation and pollutant degradation [41]. In
Fig. 3d, the above − mentioned porous morphology of aggregated
irregular block − based flakiness with wrinkles and curls could be
clearly observed in FCOCN2. Furthermore, as illustrated in Fig. S2
(Supporting Information), high resolution TEM images (HRTEM) and
selected–area electron diffraction (SAED) patterns exhibit that all CN,
FCN, CCN and FCOCN2 have the similar chaotic diffraction ripple and
amorphous diffraction ring, and no other diffraction owing to iron and/
or cobalt oxide nanoparticles could be observed in FCOCN2, which
verifies that Fe and Co are substantially doped into the g − C3N4.
The surface chemical composition and elements valence states of
FCOCN2 sample were analyzed by X − ray photoelectron spectroscopy
(XPS) technique. As presented in survey scan spectra (Fig. 4a), the ele­
ments of C 1 s, N 1 s, O 1 s, Fe 2p and Co 2p are observed at binding
energies of 288.1 eV, 398.7 eV, 532.0 eV, 710.0 eV and 785.1 eV,
Z. Wu et al.
Fig. 2. The SEM images of CN (a), FCN (b), CCN (c), FCOCN2 (d, e) and the EDS spectra of FCOCN2 (f) and corresponding element mapping.
respectively. From Fig. 4b, the de–convoluted peaks of C 1 s are found at
binding energies of 284.7 eV, 286.5 eV and 288.8 eV, which are
attributed to the C − C, N − C − O and N − C = N moieties respectively
[39]. The high–resolution spectra of N 1 s (Fig. 4c) can be split into four
convex peaks ascribing to sp2 hybridized aromatic nitrogen of C = N–C
(398.7 eV), tertiary nitrogen of N–(C)3 linking structural motif C6N7
(400.2 eV), amino groups of C–NH2 (401.1 eV) and the π–excitations
(404.6 eV) [44,45]. Fig. 4d shows the O 1 s spectrum that contains three
kinds of oxygen species at binding energies of 530.8 eV (C − O), 531.9
eV (–OH) and 533.3 eV (O − M) [39]. The presence of oxygenated in­
gredients suggests that the O atoms have directly inserted in lattice of g
− C3N4 by connecting with C atoms, which is resulted from the
incomplete polymerization and disruption of aromatic layers stacking
degree after metal doping [46]. Further analysis of Fe 2p and Co 2p
spectrum with shakeup satellite peaks (Fe 2p: 715.7 eV and 718.8 eV, Co
2p: 787.6 eV and 804.0 eV) are depicted in Fig. 4e and Fig. 4f, respec­
tively. The binding energies of Fe 2p3/2 and Fe 2p1/2 with Gaussian
curves fitting at 709.7 eV and 723.7 eV are ascribed to Fe2+, and two
other peaks at 712.0 eV and 730.8 eV are attributed to Fe3+ [47].
Analogously, the electronic configuration of Co 2p3/2 and Co 2p1/2 at
binding energy of 779.5 eV and 793.8 eV belong to the Co3+ state, while
that at 782.4 eV and 799.5 eV correspond to the Co2+ state [32]. These
results indicate that Fe and Co in doped g − C3N4 exist in the form of
mixed valence states due to the reduction of Fe3+/Co3+ by reducing
agents (i.e., CO and CNH2). The presence of Fe3+/Fe2+ and Co3+/Co2+
redox shuttles may act as the active sites in PS activation via inter­
–valence electron transfer. Furthermore, since the greater electronega­
tivity of N (3.04) than that of Co (1.88), Fe (1.83) and C (2.55), the Co
and Fe atoms could partially substitute for C atom to form Co − Nx
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Chemical Engineering Journal 434 (2022) 134732
(782.4 eV) and Fe − Nx (709.7 eV) bonds by hybridization of empty orbit
of dopants and lone pair electrons of N, which is consistent with pre­
vious researches [36,48]. Therefore, the Fe, Co accompanied O atoms
have been successfully inserted into the interstitial position of CN.
The specific surface area and porosity of CN, FCN, CCN and FCOCN2
were measured by conducting N2 adsorption–desorption isotherms, and
the results are demonstrated in Fig. 5a. Evidently, all tested samples
exhibit the type IV isotherms with hysteresis loops of H3 in the range of
relative pressure (P/P0) from 0.8 to 1.0, hinting the formation of mes­
opore in CN, FCN, CCN and FCOCN2 [49]. Moreover, the doped samples
show stronger adsorption capacity than pure g − C3N4 towards N2,
which suggests that all doped specimens have significantly increased
specific surface area. According to the model of Brunauere–Emmette–­
Teller (BET), the specific surface area of CN, FCN, CCN and FCOCN2 are
calculated to be 28.59 m2/g, 36.70 m2/g, 51.56 m2/g and 55.66 m2/g,
respectively. The improvement in specific surface area may be associ­
ated to the promotion of secondary particles formation caused by doping
inhibitory effect on crystal growth of g − C3N4, which could benefit the
adsorption and diffusion of PS and pollutant molecules with more
exposed active sites [5]. The related porosity distribution calculated by
original density functional theory are depicted in Fig. 5b. It can be
observed that doped samples show broader pore size distribution be­
tween 0 and 180 nm, and the FCOCN2 has the largest pore volume
among them. Concretely, the average pore volume of CN, FCN, CCN and
FCOCN2 is 0.142 cm3/g, 0.159 cm3/g, 0.287 cm3/g and 0.325 cm3/g,
respectively, and the corresponding pore size is 19.76 nm, 17.36 nm,
22.18 nm 23.35 nm, respectively. Besides, the average particle size of
CN, FCN, CCN and FCOCN2 is estimated to be 209.88 nm, 163.49 nm,
116.38 nm and 107.79 nm, respectively, which confirms the
Z. Wu et al.
Fig. 3. TEM image of CN (a), FCN (b), CCN (c) and FCOCN2 (d).
fragmentation of g − C3N4 into secondary particles by doping inhibitory
effect.
3.2. Catalytic performance evaluation
The effects of several factors including doping ratio, PS dosage,
catalysts dosage, initial TC concentration, pH and temperature on TC
degradation efficiency were investigated. As demonstrated in Fig. 6a,
the removal efficiency of TC is only 30.3% in presence of PS without
catalyst, which implies that the oxidation ability of the inactive PS is too
weak to decompose TC. As the addition of catalysts, the degradation
efficiency of TC is significantly enhanced, in which the TC removal ef­
ficiency of CN, FCN, CCN, FCOCN1, FCOCN2 and FCOCN3 is 65.2%,
79.3%, 68.8%, 83.9%, 90.1% and 87.4%, respectively, after catalytic
reaction for 120 min, implying that catalysts and PS may have a syn­
ergistic effect on TC removal. The synergistic factor (SF) can be calcu­
lated by the formula of SF = TC removed by (catalyst + PS) / (TC removed
by catalyst adsorption + TC removed by PS) [43]. Accordingly, the SF
value for CN, FCN, CCN, FCOCN1, FCOCN2 and FCOCN3 is 1.21, 1.62,
1.15, 1.66, 1.68 and 1.64, respectively. All SF values are large than 1,
verifying the superior synergistic effect the between catalysts and PS
[50]. As previously reported, the conjugated graphite structure of pure
g − C3N4 could promote TC degradation by PS via electron transfer
pathway [36]. But, the catalytic efficiency is still limited due to the lack
of free − flowing π electrons in carbon and nitrogen conjugated system
and the confined transfer of electrons in the two–dimensional plane
[21,51]. Benefiting from the improvement of surface aperture channels
for reactant, i.e., PS and TC mass transfer diffusion, and the increase of
accessible active sites, the degradation efficiency of TC is remarkably
advanced in doped g − C3N4/PS, especially in FCOCN2/PS system.
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Chemical Engineering Journal 434 (2022) 134732
However, the excessive Fe (FCOCN3) or Co (FCOCN1) will occupy a part
of active sites of Co (or Fe), leading to the weakened PS activation re­
action for TC decomposition [38,52]. Therefore, the optimum doping
ratio of Fe/CO is selected at 9:1 in the follow–up study. As presented in
Fig. S3 and Fig.S4 (Supporting Information), the FCOCN2 with best
catalytic ability among doped g − C3N4 samples also has the higher TC
removal efficiency than CoFe (80.9%) prepared without urea and
FCCN2 (84.0%) prepared under N2 (Fig.S4), indicating that the co −
doping of Fe, Co and O has the synergistic effect on PS activation for TC
removal over g − C3N4.
The catalytic degradation rates of TC were obtained by fitting tested
data with the Langmuir–Hinshelwood (L–H) first–order model as
equation of − ln(C/Ca) = k1t, where Ca and C was TC concentration at
time of t = 0 and intervals (min), respectively, k1 was the pseudo − first
− order kinetic constant (min− 1). As presented in Fig. 7a, the degrada­
tion rates of all samples are in the following order: CN < CCN < FCN <
FCOCN1 < FCOCN3 < FCOCN2. It is apparently that FCOCN catalysts
exhibit greatly higher kinetic constant than the CN, FCN and CCN.
Among them, the k1 value of FCOCN2 towards TC degradation is 0.021
min− 1, which is about 2.67 times, 1.60 times and 2.18 times that of pure
CN (0.009 min− 1), FCN (0.015 min− 1) and CCN (0.011 min− 1),
respectively. Furthermore, it is also much higher than both value of
0.016 min− 1 for CoFe (Fig. S3, Supporting Information) and negative
value for FCCN2 that may be caused by the continuous desorption of
massive adsorbed TC (66.7% adsorptive removal) on FCCN2 (prepared
under N2) during degradation process, which indicates that the syner­
gistic doping of Fe, Co and O plays an important role in enhancing
catalytic activity of g–C3N4. By coupling of Fe, Co and O into CN, more
active centers on surface with improved pore structure could be ach­
ieved for PS activation, reactive species generation and TC
Z. Wu et al.
Fig. 4. The XPS spectra of FCOCN2 sample: (a) survey spectrum, (b) C 1 s, (c) N 1 s, (d) O 1 s, (e) Fe 2p and (f) Co 2p.
disintegration. In order to quantitatively understand the PS utilization
over catalysts, the parameter of reaction stoichiometric efficiency (RSE)
was calculated by equation of RSE = Δn(TC)/Δn(PS), where Δn(TC) and
Δn(PS) was the mole change of TC and PS after reaction [53]. Accord­
ingly, the RSE are 3.1%, 1.9%, 1.9% and 5.2% for CN, FCN, CCN and
FCOCN2, respectively. The higher RSE of FCOCN2 compared with the
other three suggests that FCOCN2 is an efficient catalyst for PS activa­
tion. As summarized in Table S1 (Supporting Information), the FCOCN2
has the comparable and/or even better TC removal performance than
Fe0 [2], γ–Fe2O3/CeO2 [53], Fe3O4 [54], magnetic biochar [55],
Co–biochar [56] and few–layer g–C3N4/Vis–light [57] in terms of
degradation efficiency, reaction rate constant and TOC removal
(68.6%), demonstrating that it may be a desirable catalyst to activate PS
for TC mineralization in wastewater treatment.
The dosage of oxidant was a key direct factor in determining the
6
Chemical Engineering Journal 434 (2022) 134732
amount of produced free radical species. As shown in Fig. 6b, effects of
oxidant dosage on catalytic degradation of TC over FCOCN2 were
investigated by adding different amount of PS from 100 mg to 300 mg. It
can be observed that the degradation efficiency of TC is firstly increased
and then slightly decreased. When added amount of oxidant is 250 mg,
the maximal TC degradation efficiency is obtained. As presented in
Fig. 7b, the corresponding apparent degradation rate firstly increases
from 0.013 min− 1 to 0.016 min− 1 and then marginally decreases to
0.015 min− 1. Generally, the increasing dosage of PS would provide more
opportunities for collision between PS and surface active sites, which
allows more reactive oxygen species (i.e., SO4•− , •OH) to be produced
for TC degradation. However, when the added PS is excessive, the
generated SO4•− and •OH would be further quenched by extra PS
forming the SO5•− with relatively weak oxidation ability by Eqs. (1) and
(2) [2]. Besides, the superfluous SO4•− also have self − quenching effect
Z. Wu et al.
Fig. 5. The N2 ad-desorption isotherms (a) and pore-size-distribution (b)
of samples.
as Eqs. (3) and (4) [25].
HSO−5 + SO4 ∙− → SO5 ∙− + H + + SO−4
HSO−5 + ∙OH→ SO5 ∙− + H2 O
SO4 ∙− + SO4 ∙− → S2 O2−8
S2 O2−8 + SO4 ∙− → S2 O8 ∙− + SO2−4
Effect of added catalyst dosage of FCOCN2 on the removal process of
TC by PS is illustrated in Fig. 6c and Fig. 7c. Apparently, after reaction
for 120 min, the degradation process with amount of FCOCN2 at 60 mg
achieves the best catalytic performance towards TC degradation effi­
ciency of 83.6% and kinetic constant of 0.014 min− 1. Under the a con­
stant of PS addition amount(250 mg) and the relatively low dosage
range of catalyst (20 mg to 60 mg), the increase amount of FCOCN2 can
provide more redox active sites for PS activation. Numerous previous
studies have declared that the increase in active sites with increasing
catalysts dosage is favorable to accelerate the production of free radicals
for pollutants decomposition [32,36]. However, as the dosage of
FCOCN2 further increase to 80 mg, the degradation efficiency of TC is
slightly reduced, which may be attributed to that a large amount of
FCOCN2 provides excessive divalent metal ion, resulting in the strong
scavenging effect of SO4•− [58]. Moreover, Exorbitant density of C≡N
group in FCOCN2 could induce scavenging effect on SO4•− (C≡N +
SO4•− →C = N•+ + SO42− ) [33].
The influence of initial TC concentration in the range of 5 mg/L to 25
mg/L on its degradation efficiency in FCOCN2/PS system was investi­
gated. As presented in Fig. 6d, the removal percentage of TC
Chemical Engineering Journal 434 (2022) 134732
significantly decreases from 85.1% to 73.3% with initial concentration
of TC increases. Also, the corresponding degradation rate constant
(Fig. 7d) is reduced from 0.020 min− 1 to 0.012 min− 1, suggesting that
the degradation process is seriously depended on the initial concentra­
tion of TC. Theoretically, under a fixed dosage of catalyst and PS, the
total yields of radicals are at constant. When initial TC concentration is
low, the higher ratio of radicals to TC would make the greater proba­
bility for radicals attacking TC molecules, and thus the higher TC
degradation efficiency can be obtained. Conversely, the strong
competitive reaction between TC molecules with limited free radicals
and the coverage of redox active sites by adsorbed TC could cause less
removal of TC at a specific reaction time [6,11]. Therefore, at lower
initial TC concentration, the consumption rate of radicals could be lower
than their generation rate, which is beneficial to the degradation of TC.
As pH was one of most important factors affecting the decomposition
of organic pollutants in PS/catalysts system, the effect of pH on removal
efficiencies and degradation rate constant of TC over FCOCN2 by PS are
investigated in Fig. 6e and Fig. 7e. Apparently, the removal process of
TC is significantly depended on initial solution pH, in which the
degradation efficiency drastically decreases from 91.7% to 74.3% with
pH increasing from 3.0 to 11.0. Correspondingly, the degradation ki­
netic constant of TC decreases from 0.026 min− 1 to 0.011 min− 1. which
is extremely consistent with the result that acidic condition favors the
degradation of TC reported by Pi et al. [9]. Generally, under acidic
condition, SO4•− is the dominant active species that may be produced in
large quantities for TC degradation through the extra acid–catalytic
pathway via Eqs. (5) and (6) [28,59]. However, when under alkaline
condition, SO4•− is prone to react with OH− forming •OH as Eqs. (8)
[32]. The •OH radical has a relative lower oxidative potential than
SO4•− , 1.8 – 2.7 V vs. 2.5 – 3.1 V for destruction of chemical bond of TC.
Also, as the concentration of OH− increasing, the •OH can further
interact with OH− to form H2O, causing the annihilation of free radicals
and weakened degradation efficiency of TC over FCOCN2 [59]. Besides,
as presented in Fig. S5 (Supporting Information), the pH of point of zero
charge (pHPZC) of FCOCN2 is estimated to be 9.1 by zeta potential
measurement. It means that the surface of FCOCN2 is more positive
charge when pH gets lower and lower than pHPZC, and vice versa. Thus,
the oxidant of HSO5– could be effectively adsorbed on positive charged
FCOCN2 by electrostatic attraction for radical generation at pH < 9.1,
(1)
while that the opposite due to the presence of electrostatic repulsion
between HSO5– and negative charged FCOCN2 at pH > 9.1 [50]. Simi­
(2)
larly, since the major species of TC in solution are H4TC+ (pH < 3.4),
H3TC (3.4 < pH < 7.6), H2TC– (7.6 < pH < 9.0) and HTC2– (pH > 9.0)
(3)
[60], the electrostatic attraction between TC and FCOCN2 would be
become stronger at lower pH. This can be confirmed by the fact that the
(4)
adsorptive removal efficiency of TC on FCOCN2 is higher at lower pH
except pH 3.0 (Fig. S5, Supporting Information). The special case may be
due to that dominant adsorption driving forces i.e., π – π interactions, are
greatly weakened at pH 3.0. Therefore, the influence of pH on PS acti­
vation for TC removal is achieved by affecting the generation of free
radicals and the adsorptive diffusion of reactants.
S2 O2−8 + H +
→HS2 O−8 (5)
HS2 O−8 →SO4 ∙ + SO2−4 + H+ (6)
Since temperature was another crucial factor affecting chemical re­
action, the influence of temperature on PS activation for TC degradation
was investigated. As depicted in Fig. 6f, the degradation performance of
TC via PS activation over FCOCN2 is extremely depended on reaction
temperature. In detail, the degradation efficiency of TC in PS/FCOCN2
system is 86.3% (30 ◦ C), 93.9% (40 ◦ C) and 96.9% (50 ◦ C) after 120 min
catalytic reaction. Furthermore, the degradation rate constant (Fig. 7g)
increases from 0.018 min− 1 to 0.034 min− 1, which indicates endo­
thermic feature of PS activation initiated by FCOCN2 [61]. Thus, tem­
perature increasing can directly promote the fission of O − O bond in PS
7
Z. Wu et al.
Fig. 6. The catalytic degradation performance of TC by different catalysts (a), and the effects of PS dosage (b), FCOCN2 dosage (c), initial TC concentration (d), pH
(e) and temperature on TC degradation in FCOCN2/PS system.
for generation radicals of SO4•− , •OH, etc., and accelerate electron −
transfer for TC degradation over FCOCN2 [2,30]. Besides, the activation
energy (Ea) was calculated by according Arrhenius equation of lnk1 = lnA
– Ea/RT, where A was the pre–exponential factor (min− 1), T was the
temperature (K) and R was universal gas constant (8.314 J.mol− 1.K− 1)
[18]. As presented Fig. 7f, the value of Ea is computed to be 23.88 kJ.
mol− 1, which is lower than that of Co@N/S − doped carbon (44.5 kJ.
mol− 1) [27], NiFe2− xCoxO4 − reduced graphene oxide (39.62 kJ.mol− 1)
[24], S − doped g − C3N4 (38.6 kJ.mol− 1) [13] and Pd/g − C3N4 (33.7
kJ.mol− 1) [30] in PS activation. This lower activation energy suggests
that the PS activation for TC degradation by FCOCN2 is favorable.
3.3. Mechanism of catalytic degradation
To get insights into the generation of active species, quenching ex­
periments were performed by using chemical agents of methanol
8
Chemical Engineering Journal 434 (2022) 134732
(MeOH), tert–butyl alcohol (t–BuOH), phenol, p − benzoquinone (p −
BQ) and furfuryl alcohol (FFA) as scavengers. Generally, MeOH can
quench both SO4•− (kSO4•− = 1.0 × 107 M− 1s− 1) and •OH (k•OH = 1.0 ×
109 M− 1s− 1,) radicals, while t–BuOH can only trap •OH (k•OH = 5.2 ×
108 M− 1s− 1) [25]. The phenol could simultaneously capture SO4•−
(kSO4•− = 8.8 × 109 M− 1s− 1), •OH (k•OH = 6.6 × 109 M− 1s− 1,) and
SO5•− (kSO5•− = 1.0 × 1010 M− 1s− 1) [62]. The p − BQ and FFA were
commonly considered as quencher for •O2− (k•O2− = 1.0 × 109 M− 1 s− 1)
and single oxygen (1O2, k1O2 = 1.0 × 108 M− 1s− 1), respectively [63]. As
presented in Fig. 8a and Fig. S6 (Supporting Information), the degra­
dation efficiency and pseudo − first − order kinetic constant of TC are
suppressed to different degrees after introduction of scavengers. In
detail, the addition of MeOH and t–BuOH makes the TC removal effi­
ciency decrease from 90.1% to 68.2% and 75.6%, respectively, and the
kinetic constant reduce from 0.021 min− 1 to 0.009 min− 1 and 0.013
min− 1, respectively. This result suggests that both SO4•− and •OH are
Z. Wu et al.
Fig. 7. The observed pseudo-first-order rate constant of TC degradation with different catalysts (a), PS dosage (b), FCOCN-2 dosage (c), TC concentration (d), pH (e)
and temperature (g): inset is the Arrhenius plot (f).
generated and involved in the TC degradation process by FCOCN − 2/PS
system. Furthermore, the phenol exhibits a greater inhibitory effect on
TC removal than MeOH, in which the removal efficiency and kinetic
constant decreases to 27.1% and 0.003 min− 1, respectively, indicating
that SO5•− is also generated over FCOCN2 for TC degradation. Obvi­
ously, the oxidation of TC is almost completely terminated by addition of
p − BQ, implying that •O2− plays the most important role in TC
degradation by FCOCN − 2/PS system. Besides, the presence of FFA
significantly inhibits the degradation of TC with 48.4% reduction in
removal efficiency and the corresponding kinetic constant is drastically
reduced to 0.004 min− 1, which suggests that 1O2 makes a significant
contribution to TC degradation. As previously reported, the nonradical
of 1O2 could be generated from the self − decomposition of PS and the
reaction of PS with carbonyl moieties on skeleton of g–C3N4 [34,37,64].
More convincing evidence for the production of SO4•− , •OH, •O2−
and 1O2 species were supported by electron spin resonance (ESR) mea­
surements. Previous literature have reported that the SO5•− is hardly be
detected by ESR technology due to extremely weak signal [62].
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Chemical Engineering Journal 434 (2022) 134732
Therefore, SO5•− was not detected by ESR in this study. During ESR tests
for SO4•− , •OH, •O2− and 1O2 species detection, the radical spin trap­
ping agent of 5–dimethyl–1–pyrroline–N–oxide (DMPO) is used for the
detection of SO4•− , •OH and •O2− radicals, and 2, 2, 6, 6 − tetrame­
thylpiperidine (TEMP) is applied for 1O2 specie observation. As shown in
Fig. 8b − d, in the absence of FCOCN (PS alone, 0 min), no noticeable
signal can be observed, indicating that the generation of radicals by self
− decomposition of PS is negligible. In contrast, very clear signals were
detected in presence of both PS and FCOCN catalyst, and intensities of
signals were significantly enhanced with the prolongation of reaction
time. The characteristic signals with intensity ratio of 1:2:2:1 could be
ascribed to DMPO–•OH (with hyperfine couplings of αN = αβ− H = 14.9
G), and other peaks with much lower intensity than DMPO–•OH are
belonged to DMPO–SO4• (with hyperfine splitting constants of αN =
13.2 G, αH1 = 9.6 G, αH2 = 1.48 G and αH3 = 0.78 G) (Fig. 8b) [25]. As
presented in Fig. 8c, four characteristic signals of DMPO–•O2− adducts
(with hyperfine splitting constants of αN = 14.3 G, αH1 = 11.2 G, and αH2
= 1.3 G) could also be observed in ethanol [28]. In addition, the strong
Z. Wu et al. Chemical Engineering Journal 434 (2022) 134732

Fig. 8. (a) Trapping experiment for the catalytic degradation of TC over FCOCN2, (b) the ESR spectra of DMPO-•OH and DMPO-SO4•− , (c) DMPO− •O2− and
(d) TEMP-1O2 in FCOCN-2/PS system.

1:1:1 triplet signal corresponding to TEMP− 1O2 compounds (with hy­ could serve as electron acceptor to interact with PS for SO5•− and •O2−
perfine coupling constants of αN = 17.24 G) are observed in Fig. 8d, radical production (Eqs. (12) and (13)), in which SO5•− and •O2− can
demonstrating the production of abundant 1O2 [64]. Combining the further transferred to 1O2 via direct oxidation or recombination (Eqs.
quenching experiment and ESR test, it can be confirmed that SO4•− , (14) and (15)) [34,37,65]. Moreover, due to structural defects of C − O
•OH, •O2− , 1O2 as well as SO5•− radicals are responsible for TC oxida­ − Fe − N (and/or C − O − Co − N) covalency in matrix, the intervalence
tion in FCOCN/PS system. electron transfer of Eqs. (16) could be promoted with redox potential
As known, PS can be heterogeneously activated by transition metal (E0) of Co3+/Co2+ and Fe3+/Fe2+ at + 1.82 V and + 0.77 V, respectively,
through O–O (SO4 − SO4) bond–breaking [23,61]. The XPS analysis has which is facilitate to maintain the stable electronic state redistribution of
identified that iron and cobalt doped in g–C3N4 are in the form of Fe(III)/ Fe and Co for high activity [22,33]. Finally, the TC could be progres­
Fe(II) and Co(III)/Co(II), which plays an indispensable role in PS acti­ sively degraded to small molecules and even CO2 by oxidation of SO4•− ,
vation. As shown in Fig. 9a, the HSO5− produced from Eqs. (7) could SO5•− , •OH, •O2− and 1O2 active species [62].
interact with Fe(III)/Co(III) doped in g–C3N4 yielding radicals of •O2−
S2 O2−8 + H2 O→HSO−5 + HSO−4 (7)
and SO5•− as Eqs. (12) and (13), and meanwhile the Fe(III)/Co(III) is
reduced to Fe(II)/Co(II) [34,64]. Then the Fe(II)/Co(II) would further
Fe(II)/Co(II) − OER − g − C3 N4ER + HSO−5 →Fe(III)/Co(III) − O − g − C3 N4
react with HSO5− as Eqs. (8) and (11) to generate radicals (•O2− and
SO4•− ) and Fe(III)/Co(III) [10,11,52]. Recent reports have shown that + SO−4 ∙ + OH− (8)
the pure g − C3N4 has the ability to activate PS in an electron − transfer
mediated non − radical pathway, in which the pyridinic N with lone pair SO−4 ∙ + H2 O → ∙OH + SO2−4 + H+ (9)
electrons can act as electron donors for reduction of PS, and C atoms
adjacent to N atoms can play as electron acceptors to oxide PS [31]. In SO−4 ∙ + OH− → SO2−4 + ∙OH (10)
present work, the co − doping of iron, cobalt and oxygen could alter the
electronegativity of substrate C, which may boost PS activation via Fe(II)/Co(II) − OER − g − C3 N4ER + 2HSO−5 →Fe(III)/Co(III) − O − g
synergistic effect of radical and non − radical way [37]. During poly­ − C3 N4 + 2HSO−4 + ∙O−2 (11)
merization process, the O was firstly doped into g − C3N4 by replacing 2
− coordinated N, then Fe and Co were bonded with C and finally evolved
ED
Fe(III)/Co(III) − O − g− C3 N4 + HSO−5 + H2 O→Fe(II)/Co(II) − O − g
into C − O − Fe − N and C − O − Co − N bond [39]. Thus, the catalytic − C3 N4 + SO2−4 + 3H + + ∙O−2 (12)
centers of electron − rich O (OER) and adjacent electron–deficient C
(EDC) are formed. The electron − rich O and pyridinic N (NER) with high Fe(III)/Co(III) − O − g− ED
C3 N4 + HSO−5 →Fe(II)/Co(II) − O − g
electron density could act as electron donor for SO4•− , •OH and •O2− − C3 N4 + SO5 ∙ + H +
−
(13)
radicals production (Eqs. (7)–(11)), and the electron–deficient C (EDC)

10
Z. Wu et al. Chemical Engineering Journal 434 (2022) 134732

Fig. 9. (a) Schematic depiction of PS activation over FCOCN2 for TC removal; (b) electrochemical impedance spectroscopy (EIS) response and (c) linear-sweep
voltammograms (LSV) under different conditions.

2∙O−2 + 2H2 O → 1 O2 + H2 O2 + 2OH− (14)

Table 1
Electrochemical parameters of equivalent circuit elements for the samples.
2SO−5 ∙ + H2 O→ 2HSO−4 1
+ 1.5 O2 (15)
Parameters CN FCN CCN FCOCN2

Co(III) + Fe(II)→ Fe(III) + Co(II) ΔE = 1.05 V (16) R1(Ω) 11.9 11.28 11.74 12.06
R2(Ω) 637.6 563.9 635.4 364.0
The promotion of electron − transfer over FCOCN2 for PS activation CPE1-T 2.9746e-5 2.3441e-5 3.0819e-5 1.9682e-5
was further identified by ultraviolet photoemission spectroscopy (UPS) CPE1-P 0.87847 0.89423 0.87127 0.89156
and electrochemical measurements including electrochemical imped­ Ws1-R(Ω) 1218 1013 1176 1245
Ws1-T 0.046017 0.04468 0.046022 0.049862
ance spectroscopy (EIS), cyclic voltammograms (CV) and linear sweep
Ws1-P 0.83084 0.8414 0.83353 0.75735
voltammetry (LSV). Previous reports have clarified that the oxygenated Chi-squared 0.00106 0.00083 0.00105 0.00062
species could withdraw electrons from C–N = C skeleton and then in­
crease the thickness of space–charge region for charges migration
[51,57]. As presented in Fig. S7 (Supporting Information), the work resistance (R2) value of FCOCN2 is estimated to be 364.0 Ω based on the
function (Φ) related to minimum energy for inner electrons escaping of fitting of Nyquist plots to equivalent circuit diagram, which is much
CN, FCN, CCN and FCOCN2 are investigated by UPS on the basis of Φ = lower than that of CN (637.6 Ω), FCN (563.9 Ω) and CCN (635.4 Ω). The
hν − |Ecutoff – EF|, where hν denotes the energy of excited photon applied lowest R2 value of FCOCN2 also suggests that FCOCN2 possesses a better
for detection (He I: 21.21 eV), Ecutoff represents the secondary electron conductivity for electron − transfer, which is consistent with the
cut–off energy, EF is the Fermi levels that is set at 0 eV [66]. It can be calculation result of the work function. Fig. S8 (Supporting Information)
found that the Ecutoff of CN, FCN, CCN and FCOCN2 is 16.27 eV, 16.20 shows the CV curves of CN, FCN, CCN and FCOCN2 electrodes within the
eV, 16.17 eV and 16.36 eV, respectively. Therefore, the corresponding voltage region of − 1.5 to 1.5 V. Apparently, the FCOCN2 presents an
values of Φ are calculated to be 4.94 eV, 5.01 eV, 5.04 eV and 4.85 eV, enhanced current intensity compared to the other three electrodes,
respectively. The lower work function of FCOCN2 suggests that elec­ indicating that FCOCN2 retains a higher reversible redox capacity for PS
trons of FCOCN2 have a lower excitation energy barrier and are more activation due to the fast electron circulation [23]. Furthermore, to
likely to be motivated than the other three due to the electrons accu­ understand the interaction of FCOCN2 with reactants of PS and TC, the
mulation of O species after Fe, Co and O co–doping [67]. Fig. 9b presents linear sweep voltammetry (LSV) curves were measured in the presence
EIS Nyquist plots with a simulated equivalent circuit, in which R1 is and/or absence of PS. As can be found in Fig. 9c, the FCOCN2 has a
overall electrolyte resistance, R2 is charge transfer resistance connected larger current density due to the preferable conductivity. With the
in series with the Warburg impedance (Ws1), CPE1 is constant phase addition of PS, the current of the FCOCN2 electrode is significantly
angle element [68]. It can be found that the arc diameter of FCOCN2 is enhanced, demonstrating the promoted electron transfer between PS
smaller than that of other samples, indicating the superior charge and FCOCN2 in presence of redox shuttles, electron − enriched and
transfer ability of FCOCN2. As listed in Table 1, the charge − transfer deficient sites [29,49]. After injection of TC, the current of is further

11
Z. Wu et al. Chemical Engineering Journal 434 (2022) 134732

strengthened, in which the TC acts as an electron donor, PS acts as an The last one could be further transformed to P17 (m/z = 397) with
electron acceptor, and the electrode of FCOCN2 with high conductivity fracture of double bond at C10 − 10a, and then due to the deamidation
serves as an electron transport channel allowing active species genera­ and oxidative ring opening of quinone group, the P18 (m/z = 329)
tion for oxidative degradation of TC [19]. would be obtained [78]. Finally, all reaction intermediates are decom­
posed into CO2, H2O and NH4+ under the strong oxidation of radicals.
Previous reports have been proved that many intermediates gener­
3.4. Possible degradation pathway and products toxicity
ated in degradation process might have higher potential toxicity than it
itself [14,70]. Therefore, the acute toxicities of TC and transformation
To gain insight into reaction pathway in TC degradation process,
products were predicted by using toxicity estimation software tool (T.E.
high performance liquid chromatography mass spectrometry (HPLC −
S.T.) based on the quantitative structure − activity relationship (QSAR)
MS) measurements are employed to detect intermediates (Fig. S9, Sup­
method, and the aquatic toxicities of treated water were evaluated by of
porting Information). It can be found that the characteristic peak of TC
luminescence change of V. fisheri, growth inhibition of E. coli and
(m/z = 445) is disappeared after reaction, and eighteen major degra­
B. subtilis. According to Globally Harmonized System of Classification
dation transient products with m/z values of 510, 499, 467, 443, 431,
and Labeling of Chemicals (GHS), the chemicals are divided into four
397, 375, 363, 329, 307, 301, 295, 284, 261, 227, 165, 159, 132 are
categories of very toxic, toxic, harmful and not harmful. As presented in
detected during TC decomposition. Under the attack of SO4− •, •OH,
Fig. 11a, the lethal concentration 50% (LC50, 48 h) of TC is 0.17 mg/L
O2− •, SO5− • and 1O2 species, the double bond, amine group, and
towards Daphnia magna, indicating that TC has the very toxic property,
phenolic groups of TC are most vulnerable. As presented in Fig. 10, the
which may cause potential adverse effects on Daphnia magna. Also, it
probable structures of intermediates and degradation pathway of TC are
can be seen that the acute toxicities of degradation intermediates are
proposed. By demethylation of an amino group connected the C4 atom,
lower than that of TC reflecting from the higher LC50 values. Especially,
the intermediate P1 with m/z of 431 is generated, and then it can be
the products of P5, P11, P15, P16 and P17 are classified as not harmful
evolved into P2 (m/z = 363) and P6 (m/z = 375) through de–amidation
category. Except for P6, the developmental toxicities (Fig. 11b) of other
[20,69,70]. After decarboxylation, C–N bond cleavage, ring opening,
degradation intermediates is equivalent to and/or even lower than that
and/or hydroxylation reaction, the P2 is gradually decomposed into P3
of TC, and P5 is identified as developmental non − toxicant. Fig. 11c
(m/z = 307), P4 (m/z = 295) and P5 (m/z = 227) [71,72]. Meanwhile,
exhibits the bioaccumulation factor of intermediate products, in which
the P7 (m/z = 307) that generated by the loss of hydroxyl, amino and
more than half of the degradation intermediates have lower bio −
methyl groups, and the fracture of C = O bond of P6, could be converted
concentration ability than TC ascribing to hydroxylation reaction.
to P8 (m/z = 132) via ring opening [73]. Furthermore, TC can also be
Similarly, the mutagenicity of overwhelming majority of intermediates
decomposited into P9 (m/z = 443) as a result of the dehydroxylation of
have been reduced and even altered to negative status as shown in
C6 atom, and then compounds of P10 (m/z = 301) and P11 (m/z = 165)
Fig. 11d, indicating the lower genotoxicity of these products than TC.
could be generated from P9 (m/z = 443) due to the destruction of cyclic
The actual effect of TC aqueous solutions at different degradation time
hydrocarbon structure [40,74]. After that, the P12 (m/z = 261) and P13
on the luminescence inhibition of V. fisheri is shown in Fig. S10 (Sup­
(m/z = 159) are successively generated via ring opening reaction and
porting Information). It can be found that the luminescence inhibition
methyl/hydroxyl groups loss, respectively [75,76]. In addition to the
rate of solutions for V. fisheri is gradually increased from 66.8% to 90.4
above reactions, when the C = C bond at C6a – C7 position of TC is
% in the first 40 min due to some toxic intermediates, e.g. P8, P13, etc.,
broken for ketone group and carboxylic group formation, the P14 (m/z
was generated in the early stage as predicted by T.E.S.T Software.
= 465), P15 (m/z = 510) and P16 (m/z = 499) could be formed [1,77].

Fig. 10. Proposed degradation pathways and intermediates of TC by FCOCN2.

12
Z. Wu et al.
Fig. 11. Prediction of acute toxicity for daphnia magna (a), developmental toxicity (b), bioaccumulation factor (c) and mutagenicity (d) of main TC degradation
intermediates by T.E.S.T. based on consensus method.
Fortunately, with further mineralization of such intermediates, the in­
hibition rate is drastically decreased to 34.5%, which is very consistent
with the results reported by Shen et al [5]. It also can be confirmed by
comprehensive toxicity of treated solution to E. coli and B. subtilis
growth. As exhibited in Fig. S11 (Supporting Information), the number
of colonies of E. coli and B. subtilis grown on agar plate containing TC
degradation solution (60 min) are comparable with that of blank sample
without TC. Therefore, it can be concluded that although some toxic
intermediates were produced in the degradation process, the compre­
hensive toxicity of all intermediates is significantly decreased with the
extension of degradation time, indicating the great ability of FCOCN2
for efficient decomposition and detoxification of TC.
3.5. Reusability and application potential of FCOCN2
The reusability of the catalyst was an important feature to reflect the
durability of catalyst for sustainable application. Therefore, the reuse
experiment of FCOCN2 for TC degradation in presence of PS was con­
ducted, and the changes of structural components before and after re­
action were detected to evaluate the catalytic stability of FCOCN2. From
Fig. 12a, it can be found that the catalytic activity of FCOCN2 for TC
decomposition has a slight decrease after five consecutive cycles, in
which the degradation efficiency of TC is 72.7% in fifth cycle. This
unremarkable reduction may be attributed to the residual adsorption of
intermediates on surface of FCOCN2 retarding the interaction between
PS and active sites [36,42,65]. As presented in Fig. 12b, the XRD
diffraction pattern of recycled FCOCN2 has the similar peaks to fresh
one, indicating that no obvious change occurs in the phase and structure
of FCOCN2 after catalytic reaction. Further information is supported by
XPS investigation. The survey scan spectra (Fig. 12c) demonstrates that
the recycled FCOCN2 contains the same elements of C 1 s, N 1 s, O 1 s, Fe
2p and Co 2p as fresh FCOCN2. However, the corresponding binding
energies are slightly shifted to 288.2 eV, 399.1 eV, 531.1 eV, 709.1 eV
and 786.1 eV, respectively, indicating that all elements are involved in
13
Chemical Engineering Journal 434 (2022) 134732
activation of PS for TC degradation. Also, the signal intensity of O 1 s for
recycled FCOCN2 is stronger than that for fresh one, which confirms that
some oxygen containing degradation intermediates of TC still remains
on the surface of FCOCN2. From high resolution spectrum of Fig. 12b −
f, it can be found that all species contained C, N, O, Fe and Co belonging
to fresh FCOCN2 can be identified, implying that FCOCN2 has no
qualitative change in the composition after reaction. Furthermore, the
metal leaching concentration detected by inductively coupled plasma
mass spectrometer (ICP–MS) after catalytic reaction is also very low. The
leaching concentration Fe and Co is only 0.075 mg/L and 0.032 mg/L,
respectively, demonstrating that Fe and Co are firmly integrated into
FCOCN2. To reveal the practical application potential of FCOCN2 in
wastewater treatment, the tap water, river water, municipal wastewater
and medical wastewater were applied as background matrices of TC
solution for degradation. As illustrated in Table 2, the TOC removal
proportion by FCOCN2/PS system in tap water, river water, municipal
wastewater and medical wastewater is 19.0 %, 34.2 %, 6.9 % and 4.7 %,
respectively. Compared with that in ultrapure water (Table S1, Sup­
porting Information), the drastic reduction of TOC removal ratio in
actual water matrices may be caused by the complex impact of high
background TOC level, organic matter competition, ions interference
and so on [53]. Thus, more reaction time, PS dosage and catalysts usage
may be needed in terms of efficient removal of TOC from actual
wastewater. Gratifyingly, the corresponding TC degradation efficiency
is 90.0%, 88.6%, 74.0%, 81.5%, respectively, which demonstrates the
very powerful ability of FCOCN2/PS for disintegration of TC structure in
actual wastewater. Therefore, the FCOCN2/PS system has great appli­
cation potential in pretreatment and/or advanced treatment of anti­
biotic contained wastewater with acceptable catalyst stability and
reusability.
4. Conclusions
Porously thin layered Fe, Co and O co − doped g − C3N4 catalysts
Z. Wu et al. Chemical Engineering Journal 434 (2022) 134732

Fig. 12. The repeated catalytic experiments of TC in FCOCN2/PS system (a) and the XRD pattern (b), survey XPS spectrum (c), C 1 s (d), N 1 s (e), O 1 s (f), Fe 2p (g)
and Co 2p (h) of FCOCN2 after catalytic reaction.

14
Z. Wu et al. Chemical Engineering Journal 434 (2022) 134732

Table 2 [4] K. Li, A. Yediler, M. Yang, S. Schulte-Hostede, M.H. Wong, Ozonation of

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