Separation and Purification Technology 303 (2022) 122177

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Separation and Purification Technology

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

Singlet oxygen-dominated activation of peroxymonosulfate by 3D

hierarchical MnO2 nanostructures for degradation of organic pollutants in
water: Surface defect and catalytic mechanism
Yichuan Wang , Dezhi Chen *, Zhi-Xia Zhang , Tianlin Zhou , Jian-Ping Zou *
Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, School of Environmental and Chemical Engineering, Nanchang Hangkong
University, Nanchang 330063, China

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

Keywords: Manganese dioxide (MnO2) is attracting significant attention in the activation of persulfate for the degradation of
Manganese oxide organic pollutants in water. But the factor determining the catalytic efficiency of MnO2, and the evolution of
Peroxymonosulfate activation reactive oxygen species (ROS) remain equivocal and elusive. Herein, three-dimensional (3D) hierarchical MnO2
Non-radical pathway
nanostructures are synthesized via the calcination of hydrothermal product and used to active perox­
Degradation of organic pollutant
Wastewater treatment
ymonosulfate (PMS) for degradation of acid orange 7 (AO7) in water. The results show that the calcination
temperature can tune the morphology of 3D hierarchical MnO2 nanostructures from flower to urchin-like as well
as phase transformation from δ-MnO2 to α-MnO2. Owing to the presence of more surface defects and surface
adsorbed oxygen species, the urchin-like α-MnO2 nanostructures prepared at 500 ◦ C (MnO2-500) deliver the best
catalytic activity in activation of PMS, and 98.3 % of AO7 is degraded in 300 s. Additionally, the MnO2-500
shows wide pH applicability (3.5–9.6). Quenching tests and electron paramagnetic resonance spectra reveal that
the catalytic oxidation of AO7 in the MnO2-500/PMS system is mainly mediated by the non-radical pathway, and
the dominated ROS is 1 O2 . Besides, electrochemical experiment confirms the presence of electron transfer in the
catalytic process. Density functional theory calculations indicate that the C–N and C–S groups of AO7 with high
electron density are easily attacked by electrophilic ROS, which is further confirmed by liquid chromatography-
mass spectrometry. Finally, MnO2-500 exhibits gradually enhanced catalytic activity with the increased cycle
number due to the increased surface defects and the surface adsorbed oxygen. This study provides new insight
into the PMS activation by MnO2-based catalyst for the remediation of organic pollutants in water.

1. Introduction
With the rapid industrialization, many organic pollutants such as azo
dyes, pesticide residues, and antibiotics, are dumped into the water,
causing serious threats to the water quality, ecosystem, and public
health impacts [1,2]. Acid orange 7 (AO7) is a common azo dye used in
paper, printing, and other chemical industries. AO7 is highly toxic and
can cause cancerization of tissues and organs [3]. Because of its rela­
tively high stability and biological toxicity, it is challenging to treat AO7
efficiently by biodegradation and conventional physicochemical pro­
cesses, such as adsorption, membrane separation, oxidation, and so on
[4].
Advanced oxidation processes (AOPs), mainly including Fenton and
Fenton-like by generating powerful ROS of hydroxyl radicals (•OH), are
effective in removing refractory azo dyes in water due to their mild
operating conditions, high decolorization and mineralization efficiency
[5,6]. Recently, sulfate radicals (SO•− 4 )-based AOPs are gradually
attracting widespread attention [7–9]. Compared with •OH (E0 = 1.9 ~
2.7 V), SO•−
4 not only shows similar strong oxidation (E0 = 2.5 ~ 3.1 V)
but also possesses a longer half-life (30 ~ 40 μs) and better selectivity,
which is conducive to the degradation of the target pollutant [10,11].
Generally, SO•−4 radicals are obtained from the activation of persulfate,
including peroxymonosulfate (PMS) and peroxydisulfate (PDS), by
external substances or energy.
Manganese dioxide (MnO2) has demonstrated outstanding perfor­
mance and great potential in the activation of persulfate [12]. Saputra
et al. [13], first reported that α-MnO2 nanowires can activate PMS to
degrade phenol in aqueous solutions, which is superior to β-MnO2

* Corresponding authors.
E-mail addresses: chendz@nchu.edu.cn (D. Chen), zjp_112@126.com (J.-P. Zou).

https://doi.org/10.1016/j.seppur.2022.122177
Received 28 July 2022; Received in revised form 7 September 2022; Accepted 17 September 2022
Available online 23 September 2022
1383-5866/© 2022 Elsevier B.V. All rights reserved.
Y. Wang et al.
nanorods and γ-MnO2 nanofibers [14]. Zhu et al. [15] discovered that
one-dimension α-MnO2 and β-MnO2 nanomaterials demonstrated much
high activity in the activation of PDS among the various manganese
oxides for selective degradation of organic contaminants, and 1 O2 was
the primary ROS. Zhou et al. [16], found that α-MnO2 exhibited much
better catalytic performance in activating PMS for the degradation of 4-
nitrophenol in water than δ-MnO2, and SO•− 4 and •OH were the main
active radicals. Khan et al. [17]. reported that ε-MnO2 could activate
PMS more efficiently than α-MnO2, β-MnO2, and δ-MnO2, and the
1
generated ROS were SO•− 4 , •OH, O2 , and O2 . Lyu et al.[18] found that
•−
ε-MnO2 can effectively enhance the catalytic performance of β-FeOOH in
PMS activation due to the synergistic effect Fe3+/Fe2+ and Mn4+/Mn3+
as well as the generated FeOH+ and MnOH2+. The above results indicate
that the crystalline phase of MnO2 nanomaterials can influence their
catalytic activity for the activation of persulfate. Besides, it was reported
that the morphology of MnO2 nanomaterials also plays essential roles in
activating persulfate. Wang et al. [19] found that α-MnO2 nanowires
exhibited higher activity than the α-MnO2 nanorods and nanotubes
because of the higher specific surface area and larger amount of hy­
droxyl radical generation. In addition, α-MnO2 nanowires could effi­
ciently activate persulfate for 2,4-dichlorophenol (DCP) oxidation, and
SO•−4 and •OH radicals were the dominated ROS in the α-MnO2/per­
sulfate system [20]. Furthermore, Compared with these non-
hierarchical nanostructures, three-dimensional (3D) hierarchical archi­
tectures are of much interest in heterogeneous catalysis because of their
high performance and easy separation [21–23]. Deng et al.[24] verified
that the highly catalytic activity of α-MnO2 nanoflowers in activating
PMS mainly relied on their high specific surface area and high crystal­
linity. 3D-hierarchically structured corolla-like δ-MnO2 assembled by
nanosheets showed higher activity for activating PMS in the degradation
of phenol than the urchin-shaped α-MnO2 with sub-blocks of nanorods,
and SO•− 4 played a major role in phenol oxidation [21]. Although so
many meaningful results have been achieved, the activation of persul­
fate by MnO2 with different 3D hierarchical nanostructures prepared
under different calcination temperature for the degradation of pollut­
ants have not been described, and the intrinsic mechanisms are required
to be further studied.
In this paper, 3D hierarchical MnO2 nanostructures with different
morphologies and phases were prepared by a simple calcination of hy­
drothermal products, and their catalytic activities in activating PMS for
the AO7 degradation were evaluated. In addition, the influence of
calcination temperature on the catalytic efficiency of 3D hierarchical
MnO2 nanostructures for activating PMS was investigated. The influence
of experimental parameters, including initial pH, PMS dosage, MnO2
dosage, reaction temperature, coexisting inorganic ions, and organic
matters, on the degradation of AO7 in the MnO2/PMS system was
explored. Finally, the degradation pathway of AO7 and its intermediates
in the MnO2/PMS system were proposed, and the metal leaching and the
cycle stability of catalysts were evaluated to prove the application po­
tential of the MnO2/PMS system in the actual wastewater treatment.
2. Materials and methods
2.1. Materials
All reagents (see Text S1) were analytical and used without further
purification. Deionized water (18 MΩ cm) was used in the experiment.
2.2. Preparation of 3D hierarchical MnO2 nanostructures
In the synthesis process, 6 mol of KMnO4 and 1 mol of MnSO4 were
dissolved in 70 mL of deionized water and the obtained solution was
transferred to a 100 mL Teflon-lined stainless steel autoclave. The
autoclave reactor was sealed and placed in an oven at 120 ◦ C for 12 h
and then naturally cooled to room temperature. The product was
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Separation and Purification Technology 303 (2022) 122177
collected by vacuum filtration and washed six times with deionized
water and then dried at 60 ◦ C. The dried product was heat-treated at
different temperatures for 2 h in air with a heating rate of 5 ◦ C/min. The
obtained 3D hierarchical MnO2 nanostructures at 300, 400, 500, 600,
700 ◦ C were labeled as MnO2-300, MnO2-400, MnO2-500, MnO2-600,
and MnO2-700, respectively.
2.3. Characterization
The as-prepared MnO2 samples were characterized using thermog­
ravimetric/differential thermal analyzer (TG/DTA), scanning electron
microscope (SEM), transmission electron microscopy (TEM), X-ray
powder diffractometer (XRD), Fourier-transform infrared spectrometer
(FTIR), Raman spectrometer, EPR spectrometer, surface area & pore size
analyzer, X-ray photoelectron spectrometer (XPS). Details of charac­
terization are shown in Text S2.
2.4. Catalytic degradation of AO7
In a typical degradation process, 50 mg of MnO2 catalyst was added
to a 250 mL brown beaker containing 100 mL of AO7 solution with the
initial concentration (C0) of 50 mg/L with continuous stirring at 400
rpm. After uniform dispersion of the catalyst, PMS was put in the reac­
tion solution to trigger the AO7 degradation. At the set time interval, 2.5
mL of the reaction solution was collected and separated using a pipette
equipping with 0.22 μm filter membrane, 0.5 mL of methanol was used
to terminate the degradation reaction. All experiments were carried out
in triplicate. Liquid chromatography (LC) and LC-mass spectrometry
(LC-MS) were used to detect the AO7 concentration and the in­
termediates (Detail in Text S3), respectively. The radicals in the MnO2/
PMS system were determined by EPR spectrum (Detail in Text S4). TOC-
L CPH/CPN analyzer (Shimadzu) was used to analyze the total organic
carbon (TOC) during the degradation of AO7 in water. Finally, to
evaluate the reproducibility of the catalyst, the used MnO2 was collected
and washed using water and methanol alternately-three times, and then
dried at 80 ◦ C. The leached metal ions were detected using a Bremen
Hanna-Kunath-Sir.11, 28,199 inductively coupled plasma mass spec­
trometer (ICP-MS).
3. Results and discussion
3.1. Characterization
3.1.1. SEM
Fig. 1 shows the typical SEM images of as-prepared MnO2 hierar­
chical structures. Pristine MnO2 exhibits the hydrangea-like structures
(Fig. 1a), assembled by nanosheets (Fig. 1b). After heat-treatment at 300
and 400 ◦ C, the obtained MnO2-300 (Fig. 1c-d) and MnO2-400 (Fig. 1e-f)
remain the hydrangea-like structures, but the thickness of nanosheet
units is increased. When the temperature of heat-treatment increased to
500 ◦ C, the hydrangea-like structures are transformed into urchin-like
structures composed by nanorods (Fig. 1g-h), implying the presence of
crystal transformation between 400 and 500 ◦ C. From SEM images of
Fig. 1i-j at 600 ◦ C, we can observe that these nanorods in urchin-like
structures become thin and long. When the temperature increased to
700 ◦ C, the size of urchin-like structures decreases and the length of
nanorod units gets shorter and parts of nanorods detach from the hier­
archical architecture (Fig. 1k-l), which may be due to the structure
collapse at high temperature.
3.1.2. XRD
XRD patterns were used to determine the crystalline phase of as-
prepared MnO2 samples. As shown in Fig. 2a, we can see three main
XRD peaks in the pristine MnO2 at 2θ = 12.35, 24.70 and 37.22◦ , which
match well with the (1 0 0), (0 0 2) and (0 0 3) crystal plane of
K0.46Mn1.54Mn0.46O4(H2O)1.4 (JCPDF No. 80–1098) namely δ-MnO2,
Y. Wang et al.
Fig. 1. SEM images of a-b) pristine MnO2, c-d) MnO2-300, e-f) MnO2-400, g-h) MnO2-500, i-j) MnO2-600, k-l) MnO2-700.
respectively. The shift to low angel for the three XRD peaks is common in
the layered δ-MnO2 because of the intercalation of water molecules and
K ions. The obtained MnO2-300 displays the same characterization
peaks as the pristine MnO2. Meanwhile, the increased 2θ to 24.82◦ for
the (0 0 2) peak indicates the decrease of interplanar spacing in MnO2
caused by the removal of intercalated water molecules, which was
confirmed by TG curves shown in Fig. S1. With the increase of calci­
nation temperature, apart from the characterization peaks for δ-MnO2,
we can observe new diffraction peaks at 2θ = 12.60, 18.04, 28.76,
37.47, 41.79, 49.67, 56.14, 59.99, and 65.10◦ in MnO2-400, corre­
sponding to the (1 1 0), (2 0 0), (3 1 0), (2 1 1), (3 0 1), (4 1 1), (6 0 0),
(5 2 1) and (0 0 2) crystal plane of α-MnO2 (JPCDS No. 44–0141),
respectively. It indicates that part of the metastable δ-MnO2 was trans­
formed into thermostable α-MnO2 at 400 ◦ C, which can be confirmed by
TG/DTA results (Fig. S1). More water molecules were removed from the
crystal structure of MnO2-400. When the temperature was increased to
500 ◦ C and more, it can be seen only α-MnO2 diffraction peaks, agreeing
well with the morphological evolution observed in SEM images (Fig. 1).
In addition, the enhanced diffraction peak intensity demonstrates that
the crystallinity of α-MnO2 increased gradually with the increase of
calcination temperature.
3.1.3. FTIR
Fig. 2b shows the FTIR spectra of as-prepared MnO2 samples. The
bands between 400 and 800 cm− 1 correspond to the Mn–O vibrations of
MnO6 octahedra in MnO2 [25,26]. With the increase of calcination
temperature, the bands centered at 472, 590 and 717 cm− 1 appear and
become gradually sharp, indicating the presence of phase trans­
formation from δ-MnO2 to α-MnO2 [25,27] and the increased degree of
crystallinity for α-MnO2. The bands located at 1637 and 3440 cm− 1 can
be attributed to the O–H stretching and bending vibrations of water,
respectively [28]. The band at 1051 cm− 1 corresponds to the bending
vibrations of OH in Mn-OH. The strong band at 1384 cm− 1 for MnO2
nanostructures, prepared at 400 ◦ C and more-higher calcination tem­
2 ) adsorbed on
perature, belongs to the bending of peroxide species (O•−
the lattice surface of MnO2 [29,30]. When the heat-treatment temper­
ature increased to 600 ◦ C and more, the band at 1117 cm− 1 appears and
can be attributed to the bending vibrations of OH in Mn-OH [31]. The
FTIR results suggest that the phase transformation from δ-MnO2 to
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Separation and Purification Technology 303 (2022) 122177
α-MnO2 is conducive to the oxygen species adsorbed on the surface of
MnO2, and the infrared activity of OH combined with Mn atoms in­
creases with the increase of calcination temperature.
3.1.4. Raman and EPR
Fig. 2c demonstrates the Raman spectra of the as-prepared MnO2
nanostructures after calcination. Raman spectroscopy is sensitive for
probing the short-range environment of oxygen coordination around
transition metal cations in oxide lattices [32]. The band at 642 cm− 1
corresponds to the symmetric stretching vibration of Mn-O bond in
MnO6 groups [33]. Generally, the intensity of Raman band at 642 cm− 1
is used to evaluate the state of Mn-O bond. More high intensity repre­
sents the more perfect Mn-O bond. MnO2-500 shows a barely visible
band at 642 cm− 1, suggesting its weakest Mn-O bond in MnO6 groups in
all the heat-treated samples. The weak Mn-O bond implies the presence
of structure defects on the surface of MnO2. Therefore, the room-
temperature solid-state EPR spectroscopy was used to determine the
oxygen vacancy of all the heat-treated MnO2 samples. As shown in
Fig. 2d, the signal at g = 2.002 indicates the presence of oxygen va­
cancies on the surface of the as-prepared MnO2 samples. The stronger
signal for MnO2-500 suggests its more oxygen vacancies than other
MnO2 samples.
3.1.5. XPS
To further determine the valence state of Mn and the chemical
environment of O on the surface of the as-calcined MnO2 samples, XPS
spectra were obtained and displayed in Fig. 3. In the XPS survey spectra
shown in Fig. 3a, Mn, O and K signals can be observed in all the heat-
treated MnO2 samples. K is originated from the KMnO4. The Mn
average oxidation state (AOS) on the surface of MnO2 plays a vital role in
the activation of PMS. The AOS was obtained by the Mn 3 s multiple
splitting spectra method based on the following equation: AOS = 8.95 –
1.13 × ΔE, where ΔE is the energy difference between the main peak
and its satellite in Mn 3 s [34]. According to the Mn 3 s XPS spectra
presented in Fig. 3b, the calculated Mn surface AOS (Table S1) of MnO2-
300, MnO2-400, MnO2-500, MnO2-600, and MnO2-700 is 3.74, 3.7,
3.63, 3.82, and 3.87, respectively. Previous literature reported that the
low AOS is beneficial to obtaining high catalytic activity for crystalline
MnO2 [34,35]. The valence state of Mn on the surface of the as-calcined
Y. Wang et al.
Fig. 2. a) XRD pattens, b) FTIR, c) Raman and d) EPR spectra of as-prepared MnO2 samples.
MnO2 samples was further analyzed by Mn 2p spectra (Fig. 3c). Mn 2p3/
2 can be fitted into three peaks around 640.4, 641.5, and 643.2 eV,
corresponding to Mn3+ and Mn4+ [36]. The content of Mn3+ and Mn4+
on the surface of all the as-prepared MnO2 samples was calculated from
the peak area, and the ratio of Mn3+/Mn4+ is displayed in Table S1.
Generally, the high ratio of Mn3+/Mn4+ is good for the catalytic activity
of MnO2 because the electron transfer between Mn3+ and Mn4+ can
promote the PMS activation for generating ROS [17,37]. Moreover,
oxygen species on the surface of MnO2 can affect its catalytic perfor­
mance in activating PMS. Fig. 3d demonstrates the O 1 s narrow scan
spectra, which can be deconvoluted into two peaks centered at 529.6
and around 532 eV, corresponding to surface lattice oxygen (OL) and
surface adsorbed oxygen or surface hydroxy species (OA). The center of
OA peaks is shifted from 531.9 eV of MnO2-300 to 532.3 eV of MnO2-
500, suggesting the change of OA. According to the XPS and the FTIR,
we hold that the shift is mainly attributed to the adsorbed oxygen (O•−2 )
formatted at the calcination temperature of 400 ◦ C and more. It indicates
that the phase transformation from δ-MnO2 to α-MnO2 is conducive to
the formation of O•− 2 on the surface of MnO2 samples. The previous
works had found that the increased OA showed a positive effect on the
activation of PMS by MnO2 [34,38–40].
3.1.6. TEM
TEM images (Fig. 4) of the as-calcined MnO2-400 and MnO2-500
were selected to observe the microstructure of the as-prepared MnO2
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Separation and Purification Technology 303 (2022) 122177
samples. Fig. 4a shows that the hydrangea-like MnO2 structures in the
as-prepared MnO2-400 are assembled by nanosheets, which are curled
and stacked together (Fig. 4b). HRTEM image of Fig. 4c displays mul­
tiple groups of lattice fringes, including ordered and disordered lattice
fringes. Two kinds of lattice fringes with the lattice spacing of 2.53 and
2.39 Å match well with the (2 0 0) plane of δ-MnO2 and (2 1 1) plane of
α-MnO2, respectively. It indicates that the MnO2-400 contains both
metastable δ-MnO2 and thermally stable α-MnO2, matching with the
XRD results shown in Fig. 2a. The high-angle annular dark-field scan­
ning transmission electron microscopy (HAADF-STEM) and energy
dispersive X-ray spectroscopy (EDX) results in Fig. 4d demonstrate that
the presence of O, Mn, and K elements. Fig. 4e displays the TEM image of
MnO2-500, indicating the urchin-like structure constructed by MnO2
nanorods. The HRTEM image in Fig. 4f shows the highly ordered lattice
structure of MnO2 nanorods, and the corresponding selected area elec­
tron diffraction pattern (SAED) (inset of Fig. 4f) confirms that the MnO2
nanorod is a single crystal. The clearly ordered lattice fringes (Fig. 4g)
with the plane spacing of 6.99 Å are assigned to the (1 1 0) plane of
α-MnO2. The HADDF-STEM and EDX results in Fig. 4h exhibit the
presence of O, Mn, and K elements.
3.1.7. N2 adsorption/desorption isotherm
Fig. S2a shows the nitrogen adsorption/desorption isotherms of all
the as-prepared MnO2 samples. The typical type IV isotherms suggest the
presence of IUPAC-graded slit-like pores. The obtained isotherms and
Y. Wang et al.
Fig. 3. XPS spectra of all heat-treated MnO2 sample. a) survey, b) Mn 3 s, c) Mn 2p, d) O 1 s.
hysteresis loop are almost overlapping, indicating no obvious difference
in the specific surface area (SBET) and pore volume (VBJH) of all the as-
prepared MnO2 samples before and after calcination, though the
morphology of MnO2 units change significantly from nanosheets to
nanorods. Table S2 presents the calculated SBET and VBJH. Fig. S2b
demonstrates a similar pore size distribution for all MnO2 samples and
the presence of mesopores is conducive to the transfer of mass [41].
3.2. Catalytic performance of MnO2
3.2.1. Effect of calcination temperature
Fig. 5a shows the effect of calcination temperature on the catalytic
degradation of AO7. AO7 is stable and almost no self-degradation in
aqueous solution. When MnO2-500 was put alone into AO7 aqueous
solution, negligible degradation of AO7 indicates that both the adsorp­
tion capacity and the degradation efficiency of AO7 is low in the pres­
ence of MnO2-500. Furthermore, only 12.6 % of AO7 is degraded under
the dosing of PMS alone. However, the degradation of AO7 is fast in the
MnO2/PMS system, and the degradation efficiency of AO7 is from 56.0
% to 98.3 % in 300 s, suggesting that the oxidant PMS can be effectively
activated by the as-prepared MnO2 samples. Fig. 5b shows the corre­
sponding pseudo-first-order kinetic rate constant for the MnO2/PMS
system, and the obtained α-MnO2 samples at 500, 600 and 700 ◦ C show
5
Separation and Purification Technology 303 (2022) 122177
much higher catalytic activity than the pristine δ-MnO2, δ-MnO2 at
300 ◦ C and the δ-MnO2 plus α-MnO2 at 400 ◦ C. In addition, the MnO2-
500 demonstrates the highest catalytic activity in all as-prepared sam­
ples, suggesting that the suitable calcination temperature is essential for
the catalytic activity of the as-prepared MnO2 to activate PMS. To reveal
the effect of calcination temperature on the catalytic activity, the rela­
tionship between AO7 degradation rate constants and structure char­
acteristics of the as-prepared MnO2 samples are plotted. Generally, the
higher SBET of catalyst provide more active sites for the activation of
PMS [24]. Fig. 5c displays that the high SBET of the as-prepared MnO2
samples is advantageous to the AO7 degradation in the MnO2/PMS
system except for the MnO2-300 because of its crystalline phase of
δ-MnO2 and low crystallinity [13,16]. However, the low correlation
value (R2 = 0.66) indicates the SBET is not the main reason for control­
ling the catalytic performance of MnO2. In addition, the surface defect is
a key to the catalytic activity of MnO2 because the surface defects are
usually used as reaction sites, and higher defect density is conducive to
the PMS adsorption on the surface of MnO2 [42]. Fig. 5d shows the
correlation between degradation rate of AO7 and the intensity of the
Raman band at 642 cm− 1, which represents the state of the Mn-O bond
on the surface of MnO2. From MnO2-300 to MnO2-700, we can see that
the MnO2 sample with a weaker Mn-O bond exhibit a higher degradation
rate of AO7 no matter what δ-MnO2 or α-MnO2. It means that the weak
Y. Wang et al. Separation and Purification Technology 303 (2022) 122177

Fig. 4. TEM, HRTEM, HADDF-STEM and EDX mapping images of a-d) MnO2-400, e-f) MnO2-500.

Fig. 5. a) Effect of calcination temperature on the degradation of AO7 (Reaction condition: [catalyst] = 0.5 g/L, [PMS] = 1.2 g/L, [AO7] = 50 mg/L, T = 30 ◦ C,
initial pH = 5.60); b) the corresponding pseudo-first order kinetic rate constant; AO7 degradation rate constant versus c) SBET, d) intensity of band at 642 cm− 1, e)
intensity of Ov, f) AOS, g) content of surface Mn3+, and h) content of surface OA.

Mn-O bond is beneficial for the high catalytic activity of MnO2 [37,43].
Meanwhile, the weak Mn-O band suggests the presence of oxygen va­
cancies (Ov) and Mn3+. Fig. 5e and Fig. 5f demonstrate that the presence
of Ov and Mn3+ is good for the activation of PMS, respectively, and the
high density of both Ov and Mn3+ can boost the AO7 degradation in the
MnO2/PMS system. Subsequently, the influence of Ov and Mn3+ on the
degradation rate of AO7 is further confirmed by the AOS of the as-
calcined MnO2 samples shown in Fig. 5g, which is consistent with pre­
vious results that the low AOS of MnO2 was conducive to activating PMS
[37,44]. Besides, the surface adsorbed oxygen species (OA) are impor­
tant for the catalytic activity of MnO2 [45]. Fig. 5h shows a positive
linear relationship between the degradation rate of AO7 and the OA
concentration of catalysts, suggesting that the OA on the surface of as-
calcined MnO2 samples, including both adsorbed oxygen and surface
hydroxy species, can improve the activation of PMS. Furthermore, the
correlation value (R2 = 0.78) indicates that the OA plays a crucial role in
the PMS activation of the heat-treated MnO2 samples. Finally, the
leaching of Mn was determined by ICP-MS, Table S3 presents the
leaching of Mn in these MnO2/PMS systems, the extremely low con­
centration of Mn ions indicates that as-calcined MnO2 samples are stable
and the influence of leached Mn ions on the degradation of AO7 can be
almost negligible. The highest leaching concentration of Mn ions is 167
μg/L for MnO2-700, which is much lower than the requirements (2 mg/
L) of the Effluent Standards (GB8978-1996) in China.

6
Y. Wang et al.
3.2.2. Effect of experimental parameters
3.2.2.1. Effect of the catalyst dosage. The effect of catalyst dosage on the
degradation of AO7 in the MnO2-500/PMS system is presented in
Fig. 6a. The degradation efficiency of AO7 gradually increases from
91.87 % to 98.32 % as the increased concentration of MnO2-500 from
0.3 to 0.5 g/L in 300 s, indicating that increasing the dosage of MnO2-
500 can effectively improve the degradation efficiency of AO7 due to
more MnO2-500 can provide more active sites for the PMS activation.
However, at 0.7 g/L, almost the same degradation kinetics and degra­
dation efficiency of AO7 indicate that the excessive catalyst dosage does
not improve the degradation reaction because of the limited ROS.
3.2.2.2. Effect of PMS dosage. The effect of PMS dosage on the AO7
degradation is shown in Fig. 6b. With the increase of PMS concentration
from 1 to 1.2 g/L, the degradation efficiency of AO7 increases in the
MnO2-500/PMS system. It is mainly attributed to that more ROS are
generated with the increase of PMS dose [46]. However, when the PMS
concentration is 1.4 g/L, both the degradation rate and degradation
efficiency of AO7 decrease, which is mainly due to the self-scavenging
effect in the presence of excess PMS (Eqs. (1)–(5)) [47,48].
2−
S2 O8 + SO•−4 →SO2−4 + S2 O•−8
−
S2 O28 + • OH→OH− + S2 O•−8
SO•−4 + SO•−4 →2SO2−4
•OH + • OH→H2 O2
SO•−4 +• OH→HSO−4
1
+ O2
2 temperature, R (8.314 J/(mol⋅K)) is the universal gas constant, and A is
Fig. 6. Effect of key experimental parameters on the degradation of AO7 in the MnO2-500/PMS system. a) MnO2-500 dosage, b) PMS concentration, c) initial pH of
AO7 solution, d) reaction temperature, e) inorganic anions (10 mM), f) humic acid. Control condition: [catalyst] = 0.5 g/L, [PMS] = 1.2 g/L, [AO7] = 50 mg/L, T =
30 ◦ C, initial pH = 5.60.
Separation and Purification Technology 303 (2022) 122177
3.2.2.3. Effect of pH. As shown in Fig. 6c, the degradation efficiency of
AO7 in the MnO2-500/PMS system under the initial solution pH value
from 3.6 to 9.6 reach more than 90 % in 300 s, demonstrating the high
efficiency of the MnO2-500/PMS system in a wide pH range. Fig. S3
displays the Zeta potential of MnO2-500. As the increase of pH value, the
Zeta potential of MnO2-500 decrease, and the PZC of MnO2-500 is 3.08,
suggesting that the surface charge of MnO2-500 is positive under acidic
condition. The pKa1 of PMS and pKa2 of PMS are 0 and 9.442, respec­
tively [49]. Therefore, at pH 5.6–9.6, HSO−5 , which is the main active
species of PMS, is easily activated by MnO2-500 to produce SO•− 4 radi­
cals, leading to the rapid degradation rate of AO7 [50]. In addition, in
strongly acidic media, 1 O2 is produced in the system much less than in
other media. Moreover, SO•− 4 and •OH may react with H , thus reducing
+
the activity of the oxidant in acidic media [51,52]. At high alkali con­
centration with an initial pH of 11.6, the degradation efficiency is
significantly reduced to 70.26 %, probably due to the fact that the
adsorption of PMS on the surface of MnO2 is suppressed by excess alkali
[42].
3.2.2.4. Effect of reaction temperature. Fig. 6d shows the influence of
reaction temperature on the AO7 degradation in the MnO2-500/PMS
(1) system. It indicates that high reaction temperature is conductive to the
degradation of AO7. The relationship between the reaction rate constant
(2)
and reaction temperature was illustrated through the variant of the
Arrhenius Equation:
(3)
Ea
In k = − + In A (6)
(4) RT
where k (min− 1) is the reaction rate constant and Ea (J/mol) is the
(5) activation energy for the degradation of AO7, T (K) is the absolute
7
Y. Wang et al.
the frequency or pre-exponential factor.
The correlation between the rate constant and temperature is fitted
by Eq. (6), as shown in the inset of Fig. 6d. The calculated Ea of AO7
degradation in the MnO2-500/PMS system is 12.72 kJ/mol [14], which
is much lower than the reported systems, including Mn3O4/rGO/PMS
(49.5 kJ/mol) [53], MFe2O4/rGO/PMS (25.7 kJ/mol) [54], Fe3O4@C/
MnCo2O4/PMS (52.62 kJ/mol) [55], and MnOx/PDS (36.614–46.772
kJ/mol) [56]. It indicates that the MnO2-500/PMS system exhibits a
high reactivity in the degradation of AO7.
3.2.2.5. Effect of organic and inorganic anions. To explore the applica­
tion potential of catalyst in actual wastewater treatment, the effect of
these common anions (Cl-, SO2− 4 and NO3 ) and natural organic matter
−
(NOM) in actual water body on the MnO2-500/PMS system was evalu­
ated. As shown in Fig. 6e, the addition of 10 mM of Cl- exhibits an
enhancement on the degradation rate of AO7, which may be due to the
reaction of Cl- and SO•−
4 to form Cl (Eq. (7)). Moreover, the produced
•
reactive Cl can catalyze the propagation reactions to produce more
•
4 , resulting in improving the degradation performance [57].
SO•−
SO•−4 + Cl− →SO2−4 + Cl•
Fig. 7. Influence of various quenching agents on AO7 degradation. a) MeOH, b) TBA, c) p-BQ, d) L-His. Reaction condition: [catalyst] = 0.5 g/L, [PMS] = 1.2 g/L,
[AO7] = 50 mg/L, T = 30 ◦ C, initial pH = 5.60.
Separation and Purification Technology 303 (2022) 122177
The influence NO−3 on the degradation of AO7 is very slight. Besides,
the SO2− 2−
4 can react with SO4 and •OH to form S2 O8 , OH , and SO4
•− − •−
(Eqs. (8) and (9)), declining the degradation efficiency of AO7 [58].
SO2−4 + SO•−4 →S2 O2−8 + e− (8)
SO2−4 + • OH→OH− + SO•−4 (9)
Fig. 6f displays the effect of humic acid on the degradation of AO7 in
MnO2-500/PMS system. Generally, the adsorption competition between
humic acid and PMS as well as the adsorption and oxidation competition
between humic acid and target pollutant is not conducive to the
degradation of target pollutant in water [59]. Under the presence of
humic acid from 10 to 50 mg/L, no apparent change can be seen. At 100
mg/L humic acid, the degradation efficiency of AO7 is slightly reduced.
Fig. S4 shows the degradation of AO7 by the MnO2-500/PMS in two
kinds of natural water samples. Compared with deionized water, the
degradation kinetics and degradation efficiency of AO7 in tap water and
river water are slightly decreased because of the inhibitory effect caused
by the presence of inorganic anions and organic matter [60], indicating
that the MnO2-500/PMS system has potential in actual application of
(7)
wastewater treatment.
8
Y. Wang et al.
3.3. Mechanism of AO7 catalytic degradation by the MnO2-500/PMS
system
To investigate the mechanism of AO7 degradation in the MnO2-500/
PMS system, the ROS during the reaction were identified by quenching
experiments. Methanol is usually considered as an effective scavenger of
4 and •OH, while tert-butyl alcohol (TBA) is only effective for •OH
SO•−
[61]. Fig. 7a shows that the inhibition effect of methanol on the
degradation reaction of AO7 is weak even the concentration of methanol
increased to 1000 mM, suggesting that SO•− 4 or •OH is not the dominant
ROS in the degradation of AO7 by the MnO2-500/PMS system. Fig. 7b
demonstrates that the inhibitory effect of TBA is slightly stronger than
that of methanol, probably because TBA is more hydrophobic than
methanol, thus preventing the free radicals generated near the catalyst
surface by AO7 [62]. With the increase of TBA from 10 mM to 1000 mM,
the slightly reduced degradation rate and almost invisible difference in
the degradation efficiency of AO7 further indicate that the presence of •
OH is not the dominant ROS in the degradation of AO7 by MnO2-500/
PMS system. With the introduction of different doses of p-benzoquinone
(p-BQ) (5, 10, and 20 mM), no inhibition in the degradation of AO7
reveals that the concentration of O•− 2 radicals is very low or its contri­
bution is very little to the degradation reaction in the MnO2-500/PMS
system (Fig. 7c). L-histidine (L-His) was used as a specific probe for the
generation of 1 O2 . As shown in Fig. 7d, the inhibition for the degrada­
tion of AO7 is greater with increasing L-His concentration, indicating
that 1 O2 is generated and possibly dominate the degradation reaction of
AO7 in the MnO2-500/PMS system.
EPR spectra were obtained to further analyze the involvement of
these ROS in the reaction solution. Fig. 8a shows the signals of DMPO-
4 and DMPO-•OH during the degradation of AO7 by the MnO2-500/
SO•−
PMS system. It indicates that the presence of SO•−
4 and •OH species, but
the signals with moderate intensity for the DMPO- SO•− 4 and DMPO-•OH
suggests that the SO•−4 and •OH species are not the dominant ROS in the
MnO2-500/PMS system. Fig. 8b displays the EPR spectra of DMPO-O•− 2 ,
weak signals after the introduction of PMS are observed due to the
autolytic decomposition of PMS [63,64], which suggests that the
contribution of O•− 2 can be ignored in the degradation reaction of AO7
by MnO2-500/PMS system. Fig. 8c demonstrates the signals of TEMP-
1
O2 at different reaction times in the degradation of AO7 by MnO2-500/
PMS system. The observed strong peaks of 1 O2 further reveal that the
generated 1 O2 dominates the degradation of AO7 in the MnO2-500/PMS
system, which matches well with the quenching experiment (Fig. 7) and
previous literature report [63,65,66].
Based on the above results, the quenching agents could not
completely inhibit the degradation reaction of AO7, indicating the
presence of another degradation path. MnO2 was reported to undergo
valence changes during degradation and used as a catalyst for electron
transfer to achieve high valence oxidation properties [67]. Therefore,
1
Fig. 8. EPR spectra of a) •OH and SO•−
4 , b) O2 and c) TEMP- O2 at different reaction times in the degradation of AO7 by MnO2-500/PMS system.
•−
9
Separation and Purification Technology 303 (2022) 122177
the electron transfer process on the surface of MnO2-500 was further
validated electrochemically (Text S5). Cyclic voltammetry (CV) curves
(Fig. S5a) demonstrate that the current increases when PMS and AO7
was dosed into the reaction system. According to the linear sweep vol­
tammetry (LSV) curves in Fig. S5b, when PMS and AO7 existed at the
same time, the oxidation current increases significantly, further proving
that the charge transfer in the degradation of AO7 is accelerated.
Furthermore, Fig. S5c shows the i-t curve in which displays that the
current slightly increases after the input of PMS at 200 s and AO7 at 400
s. It implies that the electron reaction and electron transfer ability are
better in the presence of both PMS and AO7, suggesting that the current
flows from the AO7 molecule to the catalyst surface [68]. The conduc­
tivity of catalyst plays an important role in the catalytic process of
producing active 1 O2 [69]. Electrochemical impedance spectroscopy
(EIS) experiment was performed to analyze the conductivity of catalyst.
Fig. S5d displays the obtained EIS Nyquist plots of MnO2-500 and pure
glassy carbon electrode (GCE). In the high frequency range, the half
circles indicate the charge transfer resistance (Rct). In the low frequency
range, the linear branches correspond to the diffusion process of the
reactants. It is clear that the MnO2-500 shows low Rct and good diffu­
sivity, suggesting its good electrical conductivity and good electron
transfer rate as well as easy diffusion of reactants [70]. Thus, the
development of non-radical catalytic pathways has been greatly
facilitated.
According to the above analysis, the possible catalytic mechanism for
the AO7 degradation in the MnO2-500/PMS system is shown in Scheme
1. The defective structure and vacancies of the MnO2-500 catalyst can
generate more electronic contact sites, which is conducive to improving
the catalytic activity. PMS can be activated by the mutual trans­
formation between Mn3+ and Mn4+ on the surface MnO2. Mn3+ provides
electrons for reducing PMS to generate SO•− 4 and is converted to higher
valence states. Meanwhile, Mn4+ accepts electrons from PMS to develop
3+
SO•−5 with lower activity and is reduced to Mn . The reaction processes
are shown in Eqs. 10–11 [71]. Owing to its high reactivity, O•− 2 radicals
can rapidly react with H+ to produce the hydroperoxyl radical (HO2 •)
according to Eq. (12) [72]. Then, the produced HO2 • is recombined with
1 4+
2 to generate O2 (Eq. (13)) [73,74]. In addition, Mn
O•− species on the
surface of the MnO2 catalyst can oxide O2 to product 1 O2 (Eq. (14)),
•−
which is thermodynamically feasible (E0(Mn4+ /Mn3+ ) = 0.95 VNHE and
E0O•−2 = –0.34 VNHE ). The redox cycles between Mn3+ and Mn4+ occur on
the surface of the MnO2 catalyst and facilitated electron transfer,
resulting in the formation of ROS during MnO2-500/PMS oxidation
[17].
Mn3+ + HSO−5 →Mn4+ + SO•−4 + OH− (10)
Mn4+ + HSO−5 →Mn3+ + SO•−5 + H+ (11)
Y. Wang et al. Separation and Purification Technology 303 (2022) 122177

Scheme 1. The proposed reaction mechanism for the MnO2-500/PMS system.

O•−2 + H+ →HO2 • (12) 3.4. AO7 degradation pathway in the MnO2-500/PMS system

O•−2 + HO2 • →1 O2 + HO2 (13) The electron density of atoms in the AO7 molecule was calculated by
density functional theory (DFT). As shown in Fig. S6, the C–N and C–S
[ ] [ ]
Mn4+ − OSO3 − OH + 3O•−2 → Mn3+ − OH + SO2−4 + 31 O2 (14) groups of AO7 possess high electron densities, implying that these
functional groups are easily attacked by electrophilic ROS. Furthermore,
the intermediate products during the AO7 degradation in the MnO2-

Scheme 2. Possible intermediates and degradation pathways of AO7 in the MnO2-500/PMS system.

10
Y. Wang et al.
500/PMS system were analyzed by LC-MS. According to the spectra
shown in Fig. S7 and the previous DFT result, the possible degradation
pathways of AO7 in the MnO2-500/PMS systems are proposed and
shown in Scheme 2. The initial AO7 molecule (m/z = 329) is mainly
degraded at the azo double bond. In pathway I, the ROS attacks the two
C–N bonds in the azo dye concurrently, resulting in the decomposition
of AO7 into p-phenol sulfonic acid (m/z = 175), 1, 2-naphthoquinone
(m/z = 159), and N2. 1, 2-naphthoquinone is transformed into the
product (m/z = 175), which is further oxidated to the hydroxylated
product (m/z = 191) and the ring-opening product (m/z = 193). In
pathway II, the sulfonic group of AO7 is removed and transformed into
the product (m/z = 265), which is further decomposition to p-diphenol,
1, 2-naphthoquinone, and N2 because the two C–N bonds are simulta­
neously attacked by ROS. The following degradation path is consistent
with the pathway I. These intermediates are degraded into small mole­
cules of carboxylic acids such as HCOOH, CH3COOH, etc., which are
further oxidized to generate carbon dioxide, water, and other inorganic
ions. Fig. S8 presents that 40 % TOC is removed, supporting the above
results.
3.5. Stability and recyclability of the catalyst
The catalyst was used repeatedly to evaluate its stability and recy­
clability in activating PMS for degradation of AO7. Fig. S9a demon­
strates the catalytic degradation curves of AO7 by the MnO2-500/PMS
system, and the corresponding degradation rate constant kobs of AO7
was calculated using the pseudo-first-order kinetic model and shown in
Fig. S9b, which indicates that the degradation rate of AO7 is increased
with the increase of cycle number in the MnO2-500/PMS system. To
analyze the enhanced catalytic activity of MnO2-500 after cycle, the XPS
spectra for the used catalyst after 2, 5 and 9 cycles are presented in
Fig. S9c. With the increase of cycle, the content of lattice oxygen on the
surface of MnO2-500 decreases but the surface adsorbed oxygen in­
creases, which suggests that the decreased lattice oxygen is transformed
to surface adsorbed oxygen for improving the contact between PMS and
catalyst and promoting the PMS activation. In addition, the increased
density of Mn3+ (Fig. S9d) and the decreased AOS (Table S1) for the used
MnO2-500 after cycle further verify the above results. Moreover, the Mn
ion leaching of the MnO2-500 catalyst during each cycle was determined
by ICP-MS. As shown in Table S4, the maximum leaching concentration
of Mn ions is 199 μg/L at the 2nd and 4th cycle, which is lower than the
requirements (2 mg/L) of the Effluent Standards (GB8978-1996). The
gradually reduced leaching concentration of Mn ions with the increase
of cycle indicates the excellent potential of the MnO2-500 in the actual
application for wastewater treatment.
4. Conclusion
In conclusion, 3D hierarchical MnO2 nanostructures with different
morphologies and phases were prepared through the calcination of hy­
drothermal product and used as heterogeneous catalysts for PMS acti­
vation. The heat-treatment temperature can control the catalytic activity
of as-calcined MnO2 nanostructures. Because of the more surface defects
and OA, the urchin-like α-MnO2 nanostructures (MnO2-500) delivers a
greater catalytic performance in activating PMS than other MnO2 sam­
ples. The quenching experiment and EPR spectra indicate that the non-
radical path dominate the catalytic degradation of AO7 in the MnO2-
500/PMS system. Furthermore, the intermediate products in the
degradation of AO7 were identified, and the possible degradation
pathway was proposed. More importantly, the MnO2-500 demonstrates
superior recyclability because of the gradually increased OA and surface
defects. Besides, the as-prepared 3D hierarchical MnO2 nanostructures
possessed a very low leaching amount. These impressive results provide
a new insight into the activation of PMS by MnO2-based catalyst for
wastewater treatment.
11
Separation and Purification Technology 303 (2022) 122177
CRediT authorship contribution statement
Yichuan Wang: Data curation, Writing – original draft. Dezhi Chen:
Conceptualization, Supervision, Funding acquisition, Writing – review
& editing. Zhi-Xia Zhang: Validation. Tianlin Zhou: Data curation.
Jian-Ping Zou: Supervision, Project administration.
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.
Data availability
No data was used for the research described in the article.
Acknowledgements
This work was supported by the National Natural Science Foundation
(51720105001, 51968049) of China, the Natural Science Foundation
(20192ACB21031, 20192BCB23012) of Jiangxi Province, China.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.seppur.2022.122177.
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