Journal of Hazardous Materials 420 (2021) 126686

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Journal of Hazardous Materials

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

Facile construction of dual heterojunction CoO@TiO2/MXene hybrid with

efficient and stable catalytic activity for phenol degradation with
peroxymonosulfate under visible light irradiation
Mingmei Ding a, b, c, Wang Ao a, c, Hang Xu a, c, *, Wei Chen a, c, Lin Tao a, c, Zhen Shen a, c,
Huihong Liu a, c, Chunhui Lu d, Zongli Xie b, **
a
Ministry of Education Key Laboratory of Integrated Regulation and Resource Development on Shallow Lakes, Hohai University, Nanjing 210098, PR China
b
CSIRO Manufacturing, Private Bag 10, Clayton South, VIC 3169, Australia
c
College of Environment, Hohai University, Nanjing 210098, PR China
d
State Key Laboratory of Hydrology-Water Resources and Hydraulic Engineering, Hohai University, Nanjing 210098, PR China

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

Editor: Dr. B. Lee Photocatalysis and peroxymonosulfate (PMS) based advanced oxidation processes (AOP) are emerging tech­
nology for the degradation of refractory organic pollutant in the field of water treatment. Here we report a novel
Keywords: CoO@TiO2/MXene (CTM) hybrid through a facile sonication-hydrothermal method for efficient degradation of
Dual heterojunction phenol via an integrated PMS activation-photocatalysis process. Benefiting from the proper position and superior
Photocatalysis
suitability of the band structure, a dual interfacial charge transport channel was constructed, boosting the
Peroxymonosulfate activation
separation of photo-generated charge carriers and generating sufficient potential difference for redox reaction.
MXene
Cobalt monoxide Accordingly, the CTM hybrid not only possessed the outstanding photocatalytic activity but also dramatically
accelerated PMS activation to generate considerable reactive radicals. As a result, over 96% phenol degradation
was achieved in the 10% CTM/PMS/Vis system within 15 min. The radical quenching test and EPR analysis
1
reveal that SO•−
4 , O2 and O2 were predominant reactive species involved in the catalytic process. Moreover, the
•−

damaged chemical structure of CoO during PMS activation could be healed by the photo-actuated Co(II)
regeneration to allow for continuous and stable catalytic process. This study offers a promising perspective for
the rational design of competent and stable hybrid heterojunction catalyst to construct PMS activation-
photocatalysis processes for the efficient degradation of organic contaminants.

1. Introduction
Advanced oxidation processes (AOPs) using highly reactive oxidizing
radicals such as hydroxyl and sulfate radicals have gained extensive
research attention for the degradation of refractory pollutant in waste­
water (Ahn et al., 2016; Oturan and Aaron, 2014). Due to the consid­
erable merits of sulfate radical (SO•− 4 ) including the higher redox
potential, wide range of pH applicability and long half-life period, per­
oxymonosulfate (PMS) based AOP have gained popularity as a prom­
ising alternative to the traditional Fenton process recently (Chen et al.,
2019b; Xu et al., 2018; Zhang et al., 2014). It is well known that the
transition metal ions (such as Co (II) and Fe (II) ions) can efficiently
activate PMS for the generation of SO•− 4 (Zhang et al., 2014; Liu et al.,
2018; Shao et al., 2017). However, the ion leaching in conventional
homogeneous system causing the secondary pollution due to the toxicity
and potential carcinogenicity prevents its practical application (Chen
et al., 2019a). Encouragingly, the heterogeneous catalysts provide a new
way for the PMS activation owing to the advantages of excellent stability
and recyclability (Su et al., 2016; Ding et al., 2013). Among them, cobalt
monoxide (CoO) with abundant Co(II) active sites is considered as a
promising PMS activator (Xie et al., 2020; Zhang et al., 2017b). How­
ever, the deactivation of CoO induced by the rapid transformation from
Co(II) to inactive Co(III) during catalysis process is major challenge for
its further practical application. Therefore, it is highly desirable to

* Corresponding author at: Ministry of Education Key Laboratory of Integrated Regulation and Resource Development on Shallow Lakes, Hohai University, Nanjing
210098, PR China.
** Corresponding author.
E-mail addresses: xuhang810826@hhu.edu.cn (H. Xu), zongli.xie@csiro.au (Z. Xie).

https://doi.org/10.1016/j.jhazmat.2021.126686
Received 12 April 2021; Received in revised form 26 June 2021; Accepted 16 July 2021
Available online 18 July 2021
0304-3894/© 2021 Elsevier B.V. All rights reserved.
M. Ding et al.
develop a suitable approach for the regeneration of the chemical
structure of CoO to hinder the deterioration of its catalytic activity.
Photocatalysis, as a sustainable and eco-friendly technology, also
offers a promising platform for the organic contaminant degradation by
energy conversion (Zhang et al., 2017b, 2017a; Tang et al., 2020). It is
generally recognized that separation and transportation of the light
absorption-induced electron–hole pairs are the core step dominating the
photocatalysis process. However, the conventional semiconductors
(such as TiO2, C3N4 and BiVO4) usually suffer from the rapid recombi­
nation of photo-generated charges, leading to the low photon conversion
efficiency (Gao et al., 2018; Golshan et al., 2018; Yan et al., 2016; Zeng
et al., 2020). MXene, as a new class of two dimensional (2D) materials,
has gained enormous attention since its first discovery by Yury Gogotsi’s
team (Anasori et al., 2017; Zeng et al., 2021). Due to its excellent metal
conductivity, hydrophilic surface, good stability and superior bending
stiffness, MXene has been widely investigated in the field of water pu­
rification (Ding et al., 2020; Guo et al., 2015), electromagnetic shielding
(Han et al., 2016), electrochemical energy storage (Hu et al., 2016; Ling
et al., 2014) and catalysis (Luo et al., 2019; Ran et al., 2017). It has been
reported that Ti3C2 MXene can be partially converted into crystalline
TiO2 under oxidizing condition owing to the considerable exposure of
titanium atoms on the MXene surface (Su et al., 2016; Huang et al.,
2019). Benefiting from the tunable Fermi level and the outstanding
electrical conductivity (Naguib et al., 2014), MXene could serve as the
electron trapper to boost the separation and transport of
photo-generated carriers in TiO2 by the interfacial heterojunctions,
which could significantly improve the visible-light photocatalytic ac­
tivity (Wang et al., 2020b, 2020a; Li et al., 2018a). Thus, the TiO2/M­
Xene composite has attracted increasing attention in the field of water
treatment for photocatalytic degradation of contaminant (Miao et al.,
2020; Shahzad et al., 2018). Although some exciting results have been
reported, further enhancing the catalytic performance is still imperative
to advance the wide application of the photocatalysis.
In recent years, the strategy of consuming photo-generated electrons
by PMS molecules has been identified an effective approach to simul­
taneously suppress the recombination of charge carriers and activate
PMS, which would accelerate the generation of reactive species (Wang
et al., 2018; Lim et al., 2018). In addition, constructing binary hetero­
junctions by coupling appropriate semiconductors also demonstrates a
great prospect in the design of efficient photocatalyst, in which the
photo-induced carriers are efficiently separated via the inter
cross-sectional charge transfer, thus leading to the high redox potential
for controlling reduction and oxidation reactions (Wang et al., 2020a,
2020b). In view of these, we hypothesized that incorporating CoO into
TiO2/MXene composite to construct a dual charge transport channel
may provide an ideal platform to simultaneously realize the integration
of PMS activation and photocatalysis to achieve in-situ regeneration of
active sites of Co(II), leading to the fast reaction kinetics and stable
catalytic process.
Herein, we reported for the first time the fabrication of a new hier­
archical CoO@TiO2/MXene hybrid catalyst with the dual heterojunction
through a facile sonication-hydrothermal approach. The prepared
CoO@TiO2/MXene catalyst featured significant self-healing ability from
the destructed chemical structure and exhibited excellent and stable
catalytic performance for the degradation of phenol by integrating the
photocatalysis and the PMS activation process. The effect of CoO con­
tent, catalyst and PMS dosage, phenol concentration, initial pH value
and the coexisting anions on the phenol degradation were explored in
detail. Moreover, the possible catalytic mechanism was proposed based
on systematic investigation of the photoelectrochemical tests, determi­
nation of reactive radicals and band gap structure analysis.
2
Journal of Hazardous Materials 420 (2021) 126686
2. Materials and methods
2.1. Chemicals and reagents
Ti3AlC2 (MAX) powder (purity ≥ 98%, 300 mesh) was obtained
from Mingshan Company (Nanjing, China). PMS (KHSO5⋅0.5KHSO4⋅0.5
K2SO4), 5,5-Dimethyl-1-pyrroline N-oxide (DMPO), benzoquinone (p-
BQ) and 2,2,6,6-Tetramethyl-4-piperidone (4-oxo-TEMP) were pur­
chased from Sinopharm Chemical Reagent Co., Ltd. (Beijing, China).
NaN3 was bought from Aladdin, China. Hydrofluoric acid (HF, 48%),
methanol (MeOH), tertbutyl alcohol (TBA), disodium ethylenedi­
aminetetraacetate (EDTA-2Na), Co(NO3)2⋅6H2O, CoO and TiO2 were
purchased from Sigma-Aldrich (Beijing, China). All chemical reagents
are of analytical grade without further purification.
2.2. Synthesis of MXene, TiO2/MXene and CoO@TiO2/MXene catalyst
The Ti3C2Tx MXene was prepared by using Ti3AlC2 as precursor and
48% HF as etchant, following the procedures as reported in our previous
study (Ding et al., 2020). The hierarchical CoO@TiO2/MXenes (CTM)
hybrid were synthesized by a facial sonication - hydrothermal method.
Briefly, 0.5 g of Ti3C2Tx MXene particles were dispersed in 25 mL DI
water under ultrasonication for 30 min to form a homogeneous solution.
1 mL Co(NO3)2⋅6H2O solution with the concentration of 0.2 M was then
slowly added into above suspension under stirring and sonicated for
another 30 min. Subsequently, the above mixture was subjected to hy­
drothermal treatment at 100 ◦ C for 12 h. After the reaction, the
as-prepared materials were washed with DI water by centrifugation for 3
times, and dried at 80 ◦ C for 24 h. The products are labeled as x CTM,
where x represents 5%, 10% and 20 wt% according to the designed ratio
of CoO relative to the whole catalyst. Additionally, TiO2/MXene (TM)
was synthesized using the similar method without addition of Co
(NO3)2⋅6H2O.
2.3. Characterization
The X-ray diffractometer (XRD, Bruker, AXS D8-Focus, Germany)
was used to determine the crystal phase of the samples within the 2θ
range of 5–70◦ at a scanning step of 1 ◦ C/min. High resolution trans­
mission electron microscopy (HR-TEM, FEI Tecnai G2 F20, Japan) and
Field emission-scanning electron microscopy (FE-SEM, TecnaiF30,
Hitachi, Japan) were employed to characterize the morphology and
texture of the as-prepared samples. Energy Dispersive Spectrometer
(EDS) equipped on the HR-TEM performed to analyze the elemental
components of samples. N2 adsorption– desorption apparatus (Quan­
tachrome Autosorb-1 Analyser) was applied to determine the pore size
distribution and Brunauer-Emmett-Teller (BET) surface area of the cat­
alysts. A zeta sizer (Nano Z, Malvern) was employed to determine the
zeta potential of the catalysts. X-ray photoelectron spectroscopy (XPS)
was carried out using a ESCALAB 250Xi X-ray photoelectron spec­
trometer with a 100-eV Al-Kα X-ray radiation to evaluate the chemical
components and valence states of sample surface. The diffuse reflectance
UV–Vis spectra of catalysts was recorded on a UV–Vis spectrophotom­
eter (Hitachi 3010, Japan) by employing BaSO4 as the standard refer­
ence. Ultraviolet photoelectron spectroscopy (UPS) analysis was
performed on an unfiltered He I (21.22 eV) gas discharge lamp with total
instrumental energy resolution of 100 meV. Electrochemical impedance
spectroscopy (EIS) and the transient photocurrent responses were tested
on a Gamry instrument with a standard three-electrode system, where
the catalyst dip-coated FTO glass was used as working electrode, Pt wire
was used as the counter electrode, and Ag/AgCl electrode was used as
the reference electrode. 0.1 M Na2SO4 solution was served as the elec­
trolyte with an adjusted pH of 7, and the visible light (> 420 nm) was
provided by a 300 W Xenon lamp. The involved free radicals were
detected by the electron paramagnetic resonance (EPR, Bruker EMX 10/
12 spectrometer), where the 5,5-Dimethyl-1-pyrroline N-oxide (DMPO)
M. Ding et al.
or 2,2,6,6-Tetramethyl-4-piperidone (4-oxo-TEMP) was used as spin-
trapping agent.
2.4. Catalytic performance testing
The catalytic performance of CTM and TM catalysts was evaluated in
the integrated PMS activation-photocatalysis process for phenol degra­
dation. In a typical catalytic activity test, 20 mg catalyst was added into
100 mL of phenol solution (20 mg L− 1). The mixture was continuously
stirred under dark condition for 30 min to attain the adsorption -
desorption equilibrium. Next, 20 mg of PMS was added and the obtained
mixture was immediately irradiated by a 300 W Xenon lamp with a UV
cutoff filter (λ > 420 nm) to trigger the degradation. At each sampling
interval, 1 mL of aqueous aliquot was withdrawn and filtered by a 0.22
µm polyethersulfone syringe filter prior to the analysis.
The phenol concentration was measured by the ultra-high-
performance liquid chromatography (HPLC, Agilent) equipped with a
reversed phase Diamonsil C18 column under UV wavelength of 254 nm.
The mobile phase was a mixture of methanol and ultrapure water (vol/
vol, 65/35) with a flow rate of 1.0 mL/min. 20 μL volume of solution was
injected and measured at 30 ℃. Total organic carbon (TOC) was eval­
uated by the micro TOC analyzer (Elementar, Germany) to determine
the mineralization of phenol.
3. Results and discussion
3.1. Characterization of materials
Fig. 1 shows the synthesis strategy of hierarchical CTM hybrid.
Firstly, the precursor of Ti3AlC2 phase was etched by HF to eliminate the
aluminum layer and form the Ti3C2Tx MXene bulk with the typical
accordion-like multi-layer structure. The successful formation of MXene
was confirmed by a slight shift of the (002) plane to lower angle and the
disappearance of the diffraction peaks around 39◦ in the XRD patterns
(Fig. S1) (Natarajan et al., 2018). The CTM catalyst was then fabricated
by the sonication-hydrothermal process, in which the MXene bulk was
partially converted to TiO2 nanoparticles, and the CoO nanoparticles
were simultaneously generated and uniformly decorated on the MXene
surface, forming a hierarchical structure. It was noted that the TiO2
nanoparticles were closely connected to the unoxidized MXene nano­
sheets via the amorphous carbon“binder”. The ICP-OES analysis iden­
tifies that the actual content of CoO in 5% CTM, 10%CTM and 20%CTM
catalysts is 2.21, 5.39 and 11.42 wt%, respectively.
XRD pattern was used to investigate the structure and components of
CTM composite and the results are shown in Fig. 2a. Comparing with the
Fig. 1. Schematic illustration for the synthesis strategy of CoO@TiO2/MXene hybrid.
3
Journal of Hazardous Materials 420 (2021) 126686
pristine MXene, TiO2/MXene (TM) composite showed weaker XRD
spectra of MXene centered at 8.6◦ and 18.2◦ , while new peaks located at
25.2◦ , 37.7◦ and 47.6◦ appeared, corresponding to the (101), (004) and
(200) planes of anatase TiO2. This confirms the partial oxidization of
MXene into nanocrystalline anatase in TM sample. For Co incorporated
10%CTM sample, the XRD spectra centered at 36.2◦ and 41.9◦ which
corresponds to the (111) and (200) planes of CoO were detected, sug­
gesting the presence of crystalline CoO nanoparticles. The XPS survey
spectra of 10%CTM hybrid in Fig. S2 showed the appearance of Co peak
and the increased intensity of O peak compared to pristine MXene,
indicating the successful introduction of Co and the implantation of
additional oxygen species. Furthermore, the high-resolution Co 2p
spectra of 10%CTM (Fig. 2b) could be fitted into two peaks at 781.5 and
787.3 eV, which were assigned to Co (II) and the satellite peak (Savio
et al., 2016; Yan et al., 2018; Chang et al., 2017; Liu and Shao, 2017;
Meng et al., 2017), confirming the existence of CoO.
Raman spectroscopy was employed to validate the partial conversion
of MXene into TiO2 and amorphous carbon (Fig. 2c). The A1g modes of
MXene at 189 cm− 1 (ω2) and 711 cm− 1 (ω3) could be assigned to the
out-of-plane vibrations of Ti and C atoms. After the sonication-
hydrothermal process, both TM and 10%CTM catalysts showed
distinct Raman bands of anatase TiO2 at 156, 399, 515 and 633 cm− 1,
which are corelated to Eg(1), B1g(1), A1g & B1g(2) and the Eg(3) vibrational
modes, respectively (Huang et al., 2019; Gao et al., 2015). Moreover,
two carbon-related broad peaks between 1350 cm− 1 and 1600 cm− 1 are
the characteristic for the D band and G band. The intensity ratios of D-
and G-band (ID/IG) for TM and 10%CTM were 0.866 and 0.922,
respectively, revealing the formation of highly disordered carbon layer.
Fig. 2d shows N2 adsorption-desorption isotherms of MXene, TM and
10%CTM catalysts. All catalysts exhibited a typical type IV curve with a
hysteresis loop for mesoporous material. When compared with the pure
MXene (10.4 m2 g− 1), the BET specific surface areas of TM and 10%CTM
catalysts were increased to 41.3 m2 g− 1 and 47.6 m2 g− 1, respectively.
The high surface area could benefit the exposure of adsorption/reaction
sites for PMS activation and photocatalysis. The corresponding pore size
distribution was obtained by the BJH method using the desorption data.
The pore size of 10% CTM is distributed in the range of 1.2–21.5 nm
with two distinct pore sizes of ~2.6 nm and ~20 nm (insert of Fig. 2d).
The morphology of CoO@TiO2/MXene catalyst was further analyzed
by the electron microscopy. As shown in Fig. 1 and Fig. S3, SEM images
indicates the TM, 5%CTM and 10%CTM catalyst maintained the layered
structure and exhibited a rougher surface compared to the pristine
MXene owing to the formation of small particles on the nanosheet sur­
face. However, when the CoO loading was further increased in 20%
CTM, the aggregation of large particles and fragmentized nanosheets
M. Ding et al.
Fig. 2. (a) XRD pattern of pure MXene, TM and 10%CTM catalysts, (b) High-resolution Co 2p XPS spectra of the 10%CTM. (c) Raman spectra of pure MXene and 10%
CTM. (d) N2 adsorption-desorption isotherms of TM, 10% CTM and pure MXene catalysts (insert shows the pore size distribution of 10% CTM catalyst).
were observed. Fig. S4 displays the serious aggregation of pure CoO
particles. TEM images manifest that abundant nanoparticles were
decorated on the nanosheet surface 10%CTM (Fig. 3a), illustrating the
structure evolution compared to pure MXene. EDS elemental mapping of
10%CTM in Fig. 3c displays that Ti, C, O and F species are well
distributed in the whole area, while the Co element are aggregated as the
uniformly dispersed clusters with the size of 10–20 nm. As revealed by
the HRTEM images (Fig. 3b), the interlayer spacing of 0.35 nm could be
ascribed to the exposure of (101) facets of anatase TiO2, which was
interconnected with the MXene substrate by the amorphous carbon. This
will favor the migration of photoinduced electrons and the formation of
the Schottky junction. Additionally, the inter-planar distance of 0.19 nm
corresponding to the (200) plane of CoO, further confirms the presence
of CoO. These findings validate the hierarchical nanostructure with CoO
uniformly anchoring on TiO2/MXene composite, benefiting construction
of the dual charge transport channel.
3.2. Catalytic performance and stability
3.2.1. Catalytic performance
In this work, to evaluate the catalytic activity of CTM hybrid in
conjunction with photocatalysis and PMS activation for phenol degra­
dation, a series of control experiments were conducted initially. As
shown in Fig. 4a, negligible degradation towards phenol was observed
when only PMS or visible light was used, revealing that PMS or visible
light irradiation alone is limited in generating reactive radicals. Simi­
larly, when the catalyst alone was added into the phenol solution
without PMS and visible light, there was negligible change in the phenol
concentration, suggesting a negligible adsorption of catalysts for phenol
(Fig. S5). As a comparison, the integration of photocatalysis and PMS
activation shows enhancing effect for phenol degradation. When using
CoO alone as catalyst, the phenol removal efficiencies in the CoO/PMS,
CoO /Vis and CoO /PMS/Vis systems were 41.9%, 22.6% and 56.6%,
4
Journal of Hazardous Materials 420 (2021) 126686
respectively (Fig. S6). Furthermore, MXene alone exhibited weak cata­
lytic activity for the phenol degradation in the constructed MXene/PMS,
MXene/Vis and MXene/PMS/Vis systems, wherein the corresponding
removal efficiencies of phenol after 15 min were 16.4%, 3.6% and
17.3%, respectively, which demonstrates the limited activity of pristine
MXene for the PMS activation and photocatalysis. After partial oxida­
tion, the TM catalyst showed improved degradation efficiency of phenol
under visible light irradiation (27.6%). The degradation efficiency was
further enhanced in the integrated TM/PMS/Vis catalytic system
(38.2%) (Fig. S6). However, almost no phenol degradation was observed
in the commercial TiO2/Vis system owing to the rapid recombination of
photo-induced carriers (Fig. S7). The higher photocatalytic property of
TM composite compared to commercial TiO2 could be ascribed to the
“bridge” effect of carbon layer, whereby the photo-generated electrons
could be fast captured and transported from the conduction band of TiO2
to MXene nanosheets, and thereby forming the Schottky junction and
hindering the charge-recombination process (Wang et al., 2020b, 2020a;
Li et al., 2018b, 2018a; Peng et al., 2018; Zhang et al., 2016). Addi­
tionally, the TM catalyst displayed limited catalytic activity for PMS
activation without visible light irradiation, leading to lower phenol
removal (18.8%). By contrast, the degradation efficiency of phenol was
significantly improved when the 10%CTM hybrid was used as the
catalyst. In 15 min, the 10%CTM/PMS, 10%CTM/Vis and 10%
CTM/PMS/Vis systems achieved the phenol degradation of 67.2%,
47.7% and 96.6%, respectively. This result indicates that the 10%CTM
possessed dual catalytic activity for both the photocatalysis and PMS
activation, which results in the considerable generation of reactive
radicals for organic contaminant degradation. The superior catalytic
performance of 10%CTM could be explained as follows: Firstly, the
higher BET surface area is beneficial to the exposure of considerable
active sites for the dual catalysis process. Secondly, the formation of
heterojunction in the catalyst would serve as the charge transfer chan­
nels for the efficiently separation and migration of photogenerated
M. Ding et al. Journal of Hazardous Materials 420 (2021) 126686

Fig. 3. (a) TEM image, (b) HRTEM image and (c) STEM image and EDS elemental mapping of 10%CTM.

Fig. 4. (a) Degradation efficiency of phenol and (b) the values of degradation kinetics constants of phenol in different systems over 15 min. Conditions: [phenol] =
20 mg L− 1, [PMS] = 0.2 g L− 1, [catalyst] = 0.2 g L− 1, initial pH 7, λ > 420 nm, and T = 25 ◦ C.

5
M. Ding et al.
carriers, thus facilitating the integrated PMS activation-photocatalysis
process.
It is worth noting, despite achieving 96.6% of phenol degradation,
the TOC removal in the 10%CTM/PMS/Vis system was only 50.7%
within 15 min (Fig. S8), indicating the formation of the reaction in­
termediates in the solution. Furthermore, the kinetic study reveals that
the phenol degradation follow the pseudo-first-order model, and the
corresponding k values of different systems are displayed in Fig. 4b. The
k values for phenol degradation in the 10%CTM /PMS system are higher
than those in the TM /PMS system, suggesting that CoO plays important
role in the PMS activation to produce free radicals. In addition, the
higher k value of the 10%CTM/Vis system compared to that of TM/Vis
system also confirms the improved photocatalytic activity of 10%CTM,
which is mainly contributed to the rapid interfacial charge transfer at
the hybrid heterojunction. Remarkably, 10%CTM/PMS/Vis system
exhibited outstanding catalytic performance for the phenol degradation,
even surpassing other catalytic system reported in the previous studies
(Table S1). These findings highlight the significant reactivity of CTM for
the integrated catalytic process combining PMS activation and
Fig. 5. Effect of the (a) Co content, (b) catalyst (10% CTM) dosage, (b) PMS dosage, (d) phenol concentration (e) pH and (d) coexisting anions on the removal of
phenol. Conditions: [phenol] = 20 mg L− 1, [PMS] = 0.2 g L− 1, [catalyst] = 0.2 g L− 1, initial pH 7, λ > 420 nm, T = 25 ◦ C, [ions] = 10 mM, unless other­
wise specified.
6
Journal of Hazardous Materials 420 (2021) 126686
photocatalysis.
3.2.2. Effect of operating parameters and the catalyst stability
Fig. 5a shows that the degradation efficiency of phenol gradually
increased from 79.1% to 96.6% when the CoO loadings in CTM
increased was from 2.21% (5%CTM) to 5.39% (10%CTM), which could
be ascribed to the increased active sites from CoO, boosting the PMS
activation and offering more heterojunction sites for charge transfer.
However, there was a slight decline in the degradation efficiency of
phenol with the CoO content further increasing to 11.42% (20%CTM).
This is probably because the excessive addition of Co species resulted in
the agglomeration of CoO nanoparticles, the coverage of TiO2 and
fragmentized MXene nanosheets (Fig. S3), resulting in the suppression
of catalytic activity. 10%CTM was therefore chosen as the optimized
catalyst for the subsequent studies.
A further evaluation for the catalytic performance of the 10%CTM
was conducted by varying the operating parameters including 10%CTM
dosage, PMS dosage, phenol concentration, initial pH and coexisting
anions. Fig. 5b shows that the degradation efficiency of phenol exhibited
M. Ding et al. Journal of Hazardous Materials 420 (2021) 126686

positive correlation with the dosage of 10%CTM catalyst. This is mainly
because that the increased catalyst amount improved the availability of
redox-active centers for photon adsorption and PMS activation, which in
turn benefiting the generation of reactive radical species and conse­
quently the catalytic activity.
Generally, the PMS concentration would directly influence the
amount of generated •OH and SO•− 4 species. As depicted in Fig. 5c, the
degradation efficiency of phenol gradually accelerated with the PMS
concentration increasing from 0.1 g L− 1 to 0.5 g L− 1, while decreased
when the PMS concentration was further increased to 0.8 g L− 1. This
phenomenon could be explained by three reasons: (i) the appropriate
PMS could act as the charge acceptor to enhance the catalytic process,
(ii) the photogenerated electrons and Co(II) active sites are not sufficient
to activate the excessive PMS and (iii) the excessive PMS would react
with the SO•− 4 radicals to generate the SO5 species with weaker
•−
oxidative ability, reducing the removal efficiency (Eq. (1)) (Golshan
et al., 2018). Fig. 5d illustrates the effect of phenol concentration on the
degradation efficiency. As expected, the degradation efficiency of
phenol decreased from 99.8% to 96.6%, 76.3% and 56.7% at 15 min
when the phenol concentration was increased from 10 to 20, 50 and
100 mg L− 1, respectively. Higher amount of phenol would increase
coverage of active sites on the catalyst surface and hinder the penetra­
tion of visible light, thus inhibiting the generation of radical species for
the elimination of the phenol.
SO•− − •− 2− +
4 + HSO5 → SO5 + SO4 + H /OH
−
(1)
Fig. 5e shows the influence of the initial pH of the solution on phenol
degradation. It was found that the 10%CTM/PMS/Vis system main­
tained a good catalytic performance over a wide pH range from 3 to 11
and the removal efficiency of phenol improved with the increasing pH.
In acidic conditions, the interaction between H+ and HSO−5 become
significant and could hinder the catalysis process (Lim et al., 2018). At
the same time, the consumption of free radicals including •OH and SO•− 4
by excess H+ (Eqs. (2 and 3)) could also be responsible for the declined
degradation efficiency (Wang et al., 2017). When under the alkaline
condition, OH− could participate in the PMS activation process, accel­
erating the generation of reactive radical species (Chen et al., 2020).
•OH + H+ + e− → H2O (2)
SO•− +H +e → + −
HSO•− (3)
4 4
To evaluate the stability of 10% CTM catalyst in the simultaneous
PMS/visible light system, recycle tests were performed for the phenol
degradation. As displayed in Fig. 6a, the removal efficiency of phenol,
can still maintain 87.3% after five successive cycles, highlighting that
the 10% CTM catalyst has a good stability in the combined catalytic
process. During the catalysis process, the concentration of leached co­
balt ions was detected to be 0.52 μg/L (Fig. S9), which was well below
the maximum permissible concentration (1 mg L− 1) on the basis of the
Chinese National Standard (GB 25467-2010) (Li et al., 2018a, 2018b).
The slight decline in the catalytic activity of 10%CTM during the recycle
test was probably attributed to the coverage of active sites by the organic
compounds. Moreover, the XRD spectra in Fig. 6b demonstrate that the
intensity of the diffraction peaks of CoO slightly declined after the
recycle test. This could be due to the partial conversion of the CoO
component and the adsorption of intermediate products on the material
surface.
3.3. Proposed catalysis mechanism
In order to identify the active radicals in the 10%CTM/PMS/Vis
system, a series of EPR experiments using DMPO and TEMP as spin-
trapping reagents were carried out. As depicted in Fig. 7, the distinct
DMPO- •OH and DMPO- SO•− 4 signals were observed in the dark con­
dition with the existence of PMS, which was derived from the PMS
activation by CoO nanoparticles. After the visible light irradiation, the
intensity of DMPO signals gradually strengthened with the increasing of
illumination time, suggesting that visible light could accelerate the PMS
activation for the generation of •OH and SO•− 4 radicals. Moreover, no
characteristic peaks of TEMP-1O2 and DMPO-O•− 2 were detected in the
10%CTM/PMS system. The corresponding signals were only observed
after the illumination and increased over time, which demonstrates that
1
both O•− 2 and O2 signals were produced during the photocatalysis
process.
Radical quenching experiments were further performed to evaluate
the contribution of the involved reactive species in the 10%CTM/PMS/
Vis system. In this work, five scavengers including MeOH, TBA, p-BQ,
EDTA-2Na and NaN3 were applied to capture the •OH, SO•− 4 , O2 , h ,
•− +
1
and O2, respectively, owing to the corresponding rapid reaction rate
(Lim et al., 2018; Gong et al., 2018). Specially, MeOH was used as the
quenching agent for both ⋅OH and SO•- 4 while TBA was scavenger of ⋅OH.
It is clear from Fig. 8 that all scavengers exhibited inhibition perfor­

Considering the natural environment and practical application, it is mance for the removal efficiency of phenol and followed the order of
necessary to evaluate the interference of inorganic anions. Fig. 5f MeOH > p-BQ > NaN3 > EDTA-2Na > (TBA), revealing that •OH,
1
demonstrates that the introduction of inorganic anions apparently SO•−4 , O2 , h , and O2 all contributed to the degradation of phenol.
•− +

retarded the degradation efficiency of phenol, following the order of
HCO−3 > NO−3 > Cl− > SO2− 4 . This result was mainly derived from the
scavenging effect of anions for the photo-generated holes and free rad­
Remarkably, the presence of MeOH, p-BQ and NaN3 showed more sig­
nificant influence on phenol degradation with smaller reaction rate
1
constants, indicating that SO•− 4 , O2 and O2 are the predominant
•−

icals (such as •OH and SO•− 4 ), as described in Eqs. (4–11) (Jorfi et al., reactive species in the oxidation process.
2017; Wang et al., 2016), which would lead to the production of radical The light-harvesting capability is one of the crucial factors governing
species with a lower oxidation ability. Moreover, it is clear that SO2− 4 the combined catalysis process. The UV–visible diffuse reflectance
also exhibited some minor inhibition on the phenol degradation, which spectroscopy was conducted to investigate the light absorption proper­
is still ambiguous to explain and deserves further research. ties of the catalysts and the results are shown in Fig. 9a. Pure MXene
showed the highest light absorption from 230 to 800 nm owing to its
Cl− + SO•− 2−
4 → SO4 + •Cl (4) characteristic of black color, while no obvious absorption edge was
Cl •−
+ OH → ClOH •−
(5) observed, revealing the metallic nature of MXene. By contrast, TM
exhibited the distinct absorption edge at 449 nm mainly due to the
−
Cl + h → •Cl +
(6) formation of TiO2. With the addition of CoO, 10% CTM showed
improved optical adsorption throughout the measured UV–vis region
NO−3 + SO•− → SO2− + •NO3 (7)
4 4
with the absorption edges at 575 nm, which would benefit the utiliza­
NO−3 + •OH → •NO3 + OH− (8) tion of visible light for the photocatalytic reaction. According to the
empirical equation (Chen et al., 2020), the band gap energy (Eg) of TM
NO−3 +
+ h → •NO3 (9) and 10% CTM catalyst was calculated to be 2.76 eV and 2.15 eV,
HCO−3 + SO•− → SO2− +
+H + CO•− (10) respectively. The narrower band gap of 10% CTM is probably derived
4 4 3
from the synergistic effect between CoO and TM through significant
HCO−3 + •OH → CO•−
3 + H2O (11) interfacial coupling interaction. It has been reported that the band gap
energy of commercial TiO2 is about 3.1 eV (Wang et al., 2013), which is

7
M. Ding et al. Journal of Hazardous Materials 420 (2021) 126686

Fig. 6. (a) Recycle test of 10% CTM/PMS/Vis system for the degradation of phenol. (b) XRD pattern of 10% CTM before and after recycle test.

1
Fig. 7. EPR spectra of 10%CTM/PMS/Vis system for (a) DMPO- •OH and DMPO- SO•−
4 , (b) DMPO- O2 and (c) TEMP- O2.
•−

Fig. 8. (a) Degradation efficiency of phenol and (b) the values of degradation kinetics constants of phenol with the presence of different scavengers. Conditions:
[phenol] = 20 mg L− 1, [PMS] = 0.2 g L− 1, [catalyst] = 0.2 g L− 1, [MeOH] = [TBA] = 2 M, [p-BQ] = [EDTA-2Na] = [NaN3] = 12 mM, initial pH 7,
λ > 420 nm, and T = 25 ◦ C.

higher than that of TM. This is probably ascribed to the “bridge” effect of
the carbon layer, significantly boosting the interfacial electron transfer.
In addition, the band gap of CoO was evaluated to be 2.2 eV (Fig. S10),
which is in accordance with the previous reports (Mao et al., 2017).
Heterojunction offers a special channel for the transport of photo-
generated charge carriers in hybrids, which could be identified by the
interfacial interaction of each composition and the surface chemical
state. The Fermi level of pure MXene (− 0.04 eV vs. NHE) was lower than
the conduction band (CB) of the TiO2 (− 0.25 eV vs. NHE) (Low et al.,
2018), suggesting that the photogenerated electrons from TiO2 could be
easily captured by MXene. As the photocatalyst could be in-situ excited
by the X-ray irradiation, the XPS spectrum was used to further confirm
the migration of electrons (Fig. S11). Compared with pure MXene, a
relative negative shift of C1s state in the binding energy of TM was
observed, which manifests that the photogenerated electrons were
moved from TiO2 to MXene nanosheets, leading the formation of
Schottky junction between TiO2 and MXene.
To gain deep insight into the coupling interaction between TM and
CoO, ultraviolet photoelectron spectroscopy (UPS) was further applied
to evaluate the energy band structures of these two materials. As shown
in Fig. 9b, the valence band (VB) energy (Ev) of TM and CoO was esti­
mated to be − 8.18 eV and − 5.52 eV by subtracting the width of the He
I UPS spectra from the excitation energy (21.22 eV) (Wang et al., 2013;
Shi et al., 2017). Based on the formula of Eg = Ev − Ec, the corre­
spondingly conduction band (CB) energy (Ec) was thus evaluated to be
− 5.42 eV and − 3.32 eV for TM and CoO, respectively, equivalent to

8
M. Ding et al.
Fig. 9. (a) UV–vis diffuse reflectance spectrum of MXene, TM and 10%CTM. (b) UPS spectra and (c) the energy level diagrams of TM and CoO. (d) High-resolution
XPS spectrum of Co2p in 10%CTM/PMS/Vis and 10%CTM/PMS system.
0.72 V and − 1.12 V versus normal hydrogen electrode (NHE). In
principle, the position and compatibility of the conduction band and
valence band levels of catalysts are essential for the formation of het­
erojunction and redox reaction. The energy level diagrams of TM and
CoO is demonstrated in Fig. 9c. It is reasonable to deduce that photo­
generated electrons in the CB of the TM would easily migrate to the VB
of the CoO and combine with the holes to form the direct Z-scheme
heterojunction, contributing to the effective separation of charge carries
and strong oxidation and reduction potentials. In this case, abundant
reactive species including •OH, O•−
2 and SO4 could be produced due to
•−
their lower production potentials (•OH /OH- = +2.73 eV, O2/
2−
O•−
2 = − 0.33 eV and SO4 / SO4 = 2.5–3.1 V vs NHE, respectively)
•−
(Wang et al., 2020a, 2020b), which is in accordance with the results of
EPR. Remarkably, the CB level after band alignment is more negative
than the redox potential of Co(III)/Co(II) in weak acid solution (1.95 V
vs NHE), meeting the thermodynamic requirements for the reduction of
Co(III) by the interfacial charge transport from TM, which would
Fig. 10. (a) Transient photocurrent responses and (b) EIS Nyquist plots of different systems.
9
Journal of Hazardous Materials 420 (2021) 126686
effectively favor the recovery of Co(II) and restrict the passivation of
CoO. As revealed by the high-resolution XPS spectrum of Co2p after
catalytic reaction in Fig. 9d, the appearance of Co(III) in the 10%
CTM/PMS system demonstrates the Co(II) as the active site was partially
oxidized during the PMS activation process. It is obvious that the rela­
tive content of Co(II) in the 10%CTM/PMS/Vis system (36.8%) is higher
than that in 10%CTM/PMS system (32.4%), confirming the self-healing
effect of visible light irradiation for the continuous replenishment of Co
(II).
Transient photocurrent responses and electrochemical impedance
spectroscopy (EIS) were conducted to verify the separation and migra­
tion properties of photo-generated carriers in the CTM hybrid. By
contrast with the TM/Vis system, 10% CTM/Vis system exhibited
enhanced photocurrent density and maintained outstanding photo-
stability after five-cycle successive on-off operation (Fig. 10a), sug­
gesting that recombination of photo-generated charge carriers was
effectively restricted by the introduction of CoO. After adding PMS, a
M. Ding et al. Journal of Hazardous Materials 420 (2021) 126686

further significant improvement in the photocurrent density was ob­ photocatalytic reduction process (Eq. (19)). Along with these reactions,
tained, indicating that the PMS molecules were prone to serve as the the phenol in the solution would be degraded by the generated reactive
charge acceptor to undergo the activation and benefit the separation species into smaller intermediates, CO2 and H2O.
efficiency of photo-generated electrons and holes pairs. The arc radius
on the EIS Nyquist plot is related to the interfacial charge transport TM/CoO + hv → h+ + e− (12)
ability, wherein the smaller arc size corresponds to the lower charge O2 + e− → O•−
2 (13)
transfer resistance and fast charge migration property. As shown in
Fig. 10b, the EIS Nyquist plot of 10% CTM/PMS/Vis system showed the H2O + h+ → •OH + H+ (14)
smallest arc radius compared to other systems, confirming the acceler­
HSO−5 −
+e → SO•− + OH -
(15)
ated kinetics in the interfacial electron shuttling and highly efficient
4

separation of photo-generated electron-hole pairs, which was in good SO•−

4 + OH → -
SO2−
4 + •OH (16)
agreement with the result of transient photocurrent. Data were fitted
according to an equivalent electrical circuit with two constant-phase O•−
2 + •OH → O2 + OH 1 -
(17)
elements, where the high frequency region is related to surface Co(II) + HSO−5 → Co(III) + SO•− −
(18)
4 + OH
porosity (CPE1-Rp) and the low frequency region reflects the charge
transfer process at the catalyst/electrolyte interface (CPE2-Rct). The
−
Co(III) + e → Co(II) (19)
fitted values of Rct in 10% CTM/PMS/Vis system was 1695 ohm, which
is lower than that of the other system (10% CTM/Vis for 3709 ohm, TM/
PMS/Vis for 2410 ohm and Mxene/PMS/Vis for 12,319 ohm), suggest­
ing the rapid charge transfer in 10% CTM/PMS/Vis system. 4. Conclusions
On the basis of the above analysis, a possible mechanism for the
stable synergistic effect of photocatalysis and PMS activation in the In summary, a hierarchical CoO@TiO2/MXene hybrid consisting of
CTM/PMS/Vis system was proposed and depicted in Fig. 11. Upon the well-designed Schottky junction and Z scheme heterojunction was pre­
visible light illumination, the electrons excited in the VB of TiO2 firstly pared using a facile sonication-hydrothermal treatment method. By
transported to the conductive MXene through the carbon layer binder, virtue of the improved light harvesting ability, effective interfacial
forming the Schottky junction in the TM composite. Then, photo- carrier separation, rapid recovery of active site and large surface area,
induced electron-hole pairs were generated in both TM composite and the CTM hybrid exhibited superior and continuous reactivity for the
CoO (Eq. (12)). Owing to the proper position and superior suitability of synergistic photocatalysis and PMS activation process. over 96% phenol
the band structure, the electrons in the CB of the TM would recombine degradation was achieved in the 10%CTM/PMS/Vis system within
with the holes in the VB of the CoO to form the direct Z-scheme heter­ 15 min. Based on radical quenching experiment and EPR analysis, it is
1
ojunction, thus leading to the enhanced photocatalytic activity. The concluded that ⋅OH, SO•−4 , O2 , h , and O2 are involved in the oxidation
•− +
1
photogenerated electrons in the CB of CoO were inclined to be trapped process, while SO4 , O2 and O2 are the predominant reactive species
•− •−

by O2 to generate O•− for the phenol degradation. This work would pave an alternative path
2 (Eq. (13)), while the holes in the VB of TM could
directly oxidize organic contaminants or combine with the adsorbed for the rational design of efficient heterostructured catalysts for envi­
H2O to form •OH (Eq. (14)). In the presence of PMS, the photo- ronmental remediation.
generated electrons would further react with PMS molecules, facili­
tating the separation of charge carriers and the production of SO•− 4
CRediT authorship contribution statement
radicals and •OH (Eqs. (15 and 16)). The subsequent reaction between
O•− 1
2 and •OH could generate O2 (Eq. (17)). Besides, PMS also could be
Ding Mingmei: Methodology, Data curation, Writing – original
activated by Co(II) active sites in CoO to form SO•−
4 (Eq. (18)). It is worth
draft. Wang Ao: Conceptualization, Methodology, Software. Xu Hang:
noting that Co(II) could be immediately regenerated by the Supervision, Funding acquisition. Chen Wei: Software, Validation. Lin
Tao: Software, Validation. Shen Zhen: Software, Validation. Liu

Fig. 11. Proposal of catalytic degradation mechanism in CTM/PMS/Vis system.

10
M. Ding et al.
Huihong: Visualization, Investigation. Lu Chunhui: Software, Valida­
tion. Xie Zongli: Writing – reviewing & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was supported by National Key Research and Develop­
ment Project of China (2016YFC0400803), the National Natural Science
Foundation of China (No. 51738013 and No. 51978239), the 111 Project
under grant number B20044 and a project funded by the Priority Aca­
demic Program Development of Jiangsu Higher Education Institutions
(PAPD).
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.jhazmat.2021.126686.
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