Environ. Eng. Res.

2023; 28(5): 220606 pISSN 1226-1025

https://doi.org/10.4491/eer.2022.606 eISSN 2005-968X

Research

Study on Treatment of Basic Yellow 28 dye Wastewater by

Micro-nano Bubble Ozone Catalytic Oxidation
Jie Wei1, Hongwei Sha1, , Ruonan Wang1,2
1
Department of Environmental Engineering, School of Municipal and Environmental Engineering, Shenyang Jianzhu University, Shenyang, Liaoning
Province, 110168, China
2
Liaoning COSCO Architectural Design Corporation, Shenyang, Liaoning Province, 110021, China

Received October 20, 2022, Revised December 12, 2022 Accepted January 12, 2023

ABSTRACT
Mn loaded AC (Mn/AC), Cu loaded AC (Cu/AC), and Fe loaded AC (Fe/AC) catalysts were prepared by the impregnation-calcination
method, which can be used to degrade Basic Yellow 28 dyes in simulated printing and dyeing wastewater for catalytic ozonation.
The catalyst preparation and reaction conditions were optimized with the degradation efficiency of chemical oxygen demand (COD)
and the absorbance of some organic compounds under 254 nm UV light (UV254) as indicators. The surface structure, specific surface
area, and active component distribution of the catalysts were analyzed by scanning electron microscopy (SEM), nitrogen adsorption,
and X-ray diffraction (XRD) characterization. Results indicated that Mn was the best active component, and a catalyst dosage of 3.5
g/L, an initial pH of 9.4, and an initial temperature of 31.7°C were the best reaction parameters to degrade Basic Yellow 28 dyes. After
five recycling experiments, the catalysts could retain a relatively stable catalytic effect. Furthermore, this study can be informative for
the sustainable development of future catalysts.

Keywords: Catalyst, Cationic dye wastewater, Micro-nano bubbles, Ozonation

†
This is an Open Access article distributed under the terms Corresponding author
of the Creative Commons Attribution Non-Commercial License E-mail: 13904052793@163.com
(http://creativecommons.org/licenses/by-nc/3.0/) which per-
Tel: +86-13904052793
mits unrestricted non-commercial use, distribution, and reproduction in any
medium, provided the original work is properly cited. Fax:
ORCID: 0000-0002-4085-0339
Copyright © 2023 Korean Society of Environmental Engineers

1
Jie Wei et al.
Graphical Abstract
1. Introduction
Ozone oxidation is a typical advanced oxidation method. The
ozone-activated advanced oxidation process often generates ∙OH,
O-2 and 1O2 [1, 2]. Although O3 has a high reduction potential
(E=2.07V) [1], oxidation by ozone alone is highly selective and
it only attacks the nucleophilic sites of the aromatic ring due
to ozone’s dipolar, electrophilic, and nucleophilic nature [1, 3].
In recent years, the heterogeneous catalytic ozonation has been
proposed to overcome these problems. The use of catalysts in
this technology can increase the generation of ∙OH during the
ozonation process [2]. This technology can minimize the loss of
active components of the catalyst and ensure higher stability and
no secondary pollution for the catalyst [4]. O3 can produce ∙OH
with a redox potential of 2.80 V in the presence of catalysts. ∙OH
is an ion with a strong oxidizing property and is effective in degrad-
ing organic matters [5].
Activated carbon, molecular sieves, zeolites, and Al2O3 have
been used as supporters for catalytic ozonation [4]. Activated carbon
has become one of the most widely used supporters in catalytic
ozonation due to its easy availability, large surface area, high stabil-
ity, and good adsorption performance [6, 7]. Several metal oxides
have been investigated as the active components for ozonation
such as Mn, Fe and Cu [8-10]. Mn and Fe exist in multiple valence
states, which offer excellent catalytic properties [11-13]. Cu is
also a common and effective precursor in catalytic applications
[14, 15]. During the catalytic ozonation process, catalysts can accel-
erate the generation of free active radicals by ozone and enhance
the kinetics of pollutant conversion by ozone [16-18]. Many pre-
2
vious studies have indicated that compared with ozonation alone,
metal oxides supported on activated carbon can enhance the pollu-
tant removal efficiency [19-22].
Furthermore, the commercial application of ozone has been
limited due to its small specific surface area, low dissolved ozone
concentration and low partial pressure [23]. A gas-liquid mixing
pump can be used to disperse ozone into numerous micro-nano
bubbles (MNBs) to enhance the mass transfer rate of ozone [23,
24]. Unlike the conventional fine-bubble aeration, the micro-nano
bubble-aerated systems (MNBAs) possess more advantages such
as higher O3 stability, higher gas-liquid mass transfer efficiency,
and larger specific surface areas [25]. MNBs can increase the mass
transfer efficiency of ozone significantly and thus enhance the
treatment efficiency [26, 27]. In addition, the bubbles generated
by MNBAs could remain stable in water over a period of days
or months owing to the high zeta potential [28, 29], and then
promote the proliferation of reactive oxygen species (ROS), such
as hydroxyl radicals (∙OH), and superoxide radical anion ( ),
through ozone decomposition [30, 31]. Studies have shown that
the O3/MBAs process removes organic matters at a higher efficiency
than ozonation alone, which can be ascribed to accelerated decom-
position of ozone and enhanced generation of hydroxyl radicals
during the collapse of ozone microbubbles [32, 33]. Therefore,
the MNBA technology can be widely used in catalytic ozonation.
However, very few studies have focused on the combination of
the MNBA technology and heterogeneous catalytic ozonation along
with the use of metal-loaded activated carbon as catalysts [34].
In this work, we combined O3/MNBA technology and catalysts
to degrade Basic Yellow 28 dye which are typical cationic dyes

with benzene ring and unsaturated structure and are widely used
in industry [35]. Then we optimized the reaction conditions in
order to provide a reference for the efficient application of the
catalysts. We also investigated the stability of the catalysts during
the reaction process.
2. Experimental
2.1. Materials
The Mn(NO3)2, Cu(NO3)2, Fe(NO3)2, and activated carbon used
for the preparation of catalysts were purchased from Shenyang
Shenglongfu Experimental Equipment Co., Ltd. and Shenyang
Dongxing Reagent Factory; the Basic Yellow 28 dyes used for
the preparation of experimentally simulated wastewater were ob-
tained from Hangzhou Advance Technology Co. Ltd. Additional
information on other chemicals and reagents is shown in Table
S1. All chemicals and reagents were analytically pure. The water
used throughout the whole work was deionized.
2.2. Preparation of Catalysts
The catalysts were prepared by the impregnation-calcination
method. First, 6-8 mesh granular activated carbon was washed
with pure water 2-3 times. Next, a certain amount of pretreated
granular activated carbon was dipped into the impregnation
solution. After being stirred for 6 h at room temperature, the impreg-
nated activated carbon was first steamed dried in a water bath
at 80 ℃ and then dried in an oven at 120 ℃. Finally, the dried
activated carbon was roasted in a muffle furnace at a specific
temperature for a while to obtain the catalysts.
2.3. Characterization of Catalysts
The surface crystal structure of the catalysts was analyzed by
an X-ray diffractometer (XRD-7000, Shimadzu, Japan) using Cu
K α radiation. Scanning electron microscopy (SEM) images of the
catalysts were obtained through a high-energy electron beam using
a cold field emission scanning electron microscope (S-4800,
HITACHI, Japan). The pore structure and specific surface area
of the catalysts were measured by a Brunauer-Emmett-Teller (BET)
physical adsorption instrument (Autosorb-IQ, Conta, USA).
Nitrogen was used as the test gas for adsorption. The samples
were dried and degassed under vacuum at 300 °C before testing.
2.4. Catalytic Ozonation Experiment
Pressurized dissolved gas was used to produce MNBs. The ex-
perimental setup of catalytic ozonation is schematically illustrated
in Fig. S1. An O3 generator (Shijiazhuang Ouneng General
Technology Co., Ltd.) was used to generate O3. A gas-liquid mixing
pump (model 20QY-1, power 0.55 kW–7.5kW, gas-liquid volume
ratio: 11%) mixed the sucked wastewater and O3, pressed the
mixture into a dissolved gas tank through a connecting pipe and
then into a reactor through an aeration disk. This process generated
MNBs 20-30 μm in diameter [36]. The experimental reactor was
a plastic tank with an effective working volume of 20 L. The
catalysts were fixed in the middle of the reactor. At 15-min intervals,
3
Environmental Engineering Research 28(5) 220606
a water sample was taken from the sampling port at the bottom
of the reactor. During the experiment, the residual O3 was quenched
by 10 % KI.
2.5. Analytical Methods
The pH of the wastewater was determined by a composite glass
electrode (SX711, San-Xin Instrumentation Factory, Shanghai).
The COD of the wastewater was measured using the rapid closed
catalytic digestion method. The concentration of O3 in the solution
was measured using the sodium indigo disulfonate (IDS) spec-
trophotometry method. The point of zero charge (pHpzc) of the
catalysts was determined by the salt titration method [37]. The
content of the metal in the solution was measured by ICP-MS.
A UV-visible spectrophotometer (UV-5500, Yuan Analysis
Instrument Co., Ltd., Shanghai) was used to determine the absorb-
ance of water samples at 440 nm, which is the maximum absorption
wavelength of the Basic Yellow 28 dyes. UV254 is a parameter
representing the amount of carbon source in wastewater, which
directly reflects the ability of ozone to mineralize organic pollutants.
3. Results and Discussion
3.1. Comparation of Different Aeration Systems
The experiment was intended to discuss the performance of
O3-Micro-nano Bubbles (O3-MNBs) and O3-Ordinary Bubbles
(O3-OBs) concretely. The ozone inlet flowrate and concentration
were set at 3 L/min and 10.3 mg/L, respectively, to serve as the
reaction conditions in the subsequent experiments.
The effects of O3-MNBs and O3-OBs on the liquid phase ozone
concentration and ozone mass transfer coefficient were
investigated. We assumed that the dissolution of ozone in water
can be described by a mass transfer coefficient equation of gas
in solution (based on Eqs (1)-(2)) [38]:
(1)
(2)
where , and are the ozone mass transfer coefficient, ozone
saturated concentration, and bulk concentration in water,
respectively. The results are shown in Fig. 1a and b. Clearly, the
O3-MNBs exhibited a higher liquid phase ozone concentration
and a higher ozone mass transfer efficiency than the O3-OBs.
According to Young–Laplace equation, MNBs have a higher internal
pressure than ordinary bubbles, leading to the dissolution of more
ozone in water [28, 39]. As described in a previous study, more
ozone can be dissolved into water through the bubble interface
because of the larger total surface area of the MNBs [40]. The
ozone mass transfer coefficient of the O3-MNBs was 1.77 times
higher than that of the O3-OBs, which agreed with the conclusion
in the literature [41, 42]. Studies have shown that the gas-liquid
transfer efficiency of ozone was effectively improved due to the
self-pressurization effect of MNBs [40, 43]. It can be concluded
from Fig. 1c that the efficiency of COD removal by O3/MNBAs
Jie Wei et al.

O3-Micro Nano
a O3-Ordinary B b O3-Micro Nano Bubble
2.5 1
O3-Ordinary Bubble
Liquid phase ozone concentration/mg·L-1

2.0
0

1.5 y=-0.437x+0.992

ln(Cs-Ct)
-1 R2=0.980

1.0
-2 y=-0.761x+1.053

0.5 R2=0.988
-3

0.0
-4
0 2 4 6 8 10 12 0 2 4 6 8 10
t/min t/min
c

Fig. 1. Effect of different aeration processes (ozone dosage at 2 L/min, pH at 7.1, reaction temperature at 25 , and continuous aeration time
at 10 min).

was approximately 3.1 and 1.7 times higher than that by MNBAs
alone and by ozonation alone, respectively. This could be attributed
to the fact that O3/MNBAs produced a higher concentration of
∙OH in solution, which corresponded to a higher COD removal
rate. Nam et al. demonstrated that microbubble ozonation per-
formed particularly well in benzo pyrene degradation due to the
higher ∙OH concentration [44]. Therefore, the O3/MNBA technology
was applied in this work.
3.2. Comparation of Different Catalyst Systems
Different roasting temperatures (400 ℃, 500 ℃, and 600 ℃), roast-
ing times (2 h, 3 h, and 4 h), and impregnation solution concen-
trations (0.5 mol/L, 1.0 mol/L, and 2.0 mol/L) were set to optimize
the preparation conditions of the catalysts. To degrade 20 L of
simulated dye wastewater with a concentration of 100 mg/L, 2
L/min ozone dosage, 10.47 mg/L ozone concentration, and 1 g/L
catalyst dosage or activated carbon were used as the reaction
conditions.
As shown in Table 1, the optimal preparation conditions for
Mn/GAC, Cu/GAC, and Fe/GAC were 500 ℃, 500 ℃, and 400
℃ roasting times, 3 h, 4 h, and 4 h roasting times, and 0.5 mol/L,
0.5 mol/L, and 1.0 mol/L impregnation solution concentrations,
respectively. According to the COD removal results, the Mn/GAC
catalyst showed a better treatment performance than the other
two catalysts.
3.3. Characterization of Catalysts
The three catalysts with the best removal performance were charac-
terized and analyzed to observe the surface morphology and crystal
structure. The SEM images of the unmodified activated carbon
and the catalysts are provided in Fig. S2a, b, c, and d. Unlike
the unmodified activated carbon (Fig. S2a), the surface of the
Mn-nitrate-modified activated carbon (Fig. S2b) was covered by
lamellar particles, which may be the typical morphology of MnO2
as reported in the literature [45, 46]. From Table S2, it can be
known that the activated carbon showed a decrease in its specific

4
 Environmental Engineering Research 28(5) 220606

surface area, pore volume, and pore size after being loaded with
three metals. In addition, the pore structure may change and re-
combine after calcination [47]. This helps to ensure the successful
loading of metal oxides on the surface and in the pore channels
of the activated carbon [48]. It is worth noting that the activated
carbon modified by iron nitrate showed a sharp decrease in its
specific surface area, pore volume, and pore size. This could be
attributed to the fact that the iron oxide particles were mainly
distributed on the surface of the supporters in the form of metal
clusters (Fig. S2d) [47, 49]. After modification by manganese nitrate
and copper nitrate, the activated carbon did not show apparent
change in its specific surface area, but its COD removal rate changed
significantly.
Fig. 2 shows the effects of different reaction systems on the
COD removal efficiency. When activated carbon was used as an
adsorbent, the COD removal efficiency was only 2.4%. This sug-
gested that activated carbon offered very limited adsorption for
the removal of contaminants in the system. Compared with ozona-
tion alone, adding activated carbon to the ozonation system could
increase the efficiency of COD removal by 16.11 %, implying
that activated carbon could promote the transformation of aqueous
ozone into more[50]. The figure also provides a clear illustration
of the performance of Mn/AC, Cu/AC, and Fe/AC catalysts in the
removal of COD from dye wastewater. During the reaction process,
all these catalysts showed good performance in COD treatment,
with Mn/AC performing the best of all. Mn is a particular transition
metal oxide with valence states from +2 to +7, compared to Cu
or Fe with a maximum formal oxidation state of +4 or +3. This
advantage promotes the participation of manganese in the electron
transfer reaction with O3 during the catalytic cycle [51]. After
data analysis and catalyst characterization, Mn/AC was finally
selected as the optimal catalyst.
The XRD patterns of activated carbon and Mn/AC are presented
in Fig. S3. The unmodified activated carbon exhibited characteristic
diffraction peaks of SiO2 and CaCO3, which indicated that the
activated carbon contained a small amount of SiO2 and CaCO3
impurities [52]. After modification by manganese nitrate, character-

Fig. 2. COD removal rates of different catalysts

5
Jie Wei et al.
istic diffraction peaks at 12.80º, 18.10º, and 32.88º were observed,
which might be the crystalline phases of α-MnO2 [53]. The intensity
of the diffraction peaks of the activated carbon became weaker,
indicating that the diffraction peaks of the activated carbon de-
creased after loading of manganese onto the activated carbon.
It has also been demonstrated that MnO2 [54] has the best catalytic
treatment performance among the various valence states of man-
ganese oxides.
3.4. Optimization of Process Parameters
Given its good catalytic performance, Mn/AC was used in this
part of the experiment, and the operating conditions were optimized
by investigating the basic parameters (catalyst dosage, pH, and
reaction temperature).
3.4.1. Effect of catalyst dosage
Both Brønsted and Lewis acid sites are considered to be the active
centers for catalytic ozonation [55, 56]. Water molecules can be
adsorbed on manganese oxides to combine with Lewis acid sites,
and then dissociate into protonated surface hydroxyl groups. Lots
of research has shown that neutral hydroxyl groups and protonated
hydroxyl groups are the active sites for catalytic ozonation [57].
Hence, the catalyst dosage affects the number of active sites
indirectly. The effect of catalyst dosage in the range of 1 to 5
g/L on the COD and UV254 removal rates of the Mn/AC system
was investigated. The ozone dosage, pH, reaction temperature,
and continuous aeration time were set at 2 L/min, 7.1, 25 ℃,
and 120 min, respectively. As shown in Fig. 3, the COD and UV254
removal rates increased significantly when the catalyst dosage
increased from 1.0 g/L to 3.0 g/L. This suggested that the addition
of the catalyst enhanced the degradation efficiency of Basic Yellow
28 dyes. This may be explained as follows. As the catalyst dosage
increased, the total specific surface area and the number of active
sites of the catalyst were increased as well. This could facilitate
the reaction with O3 to promote the generation of ∙OH [58, 59],
thus improving the COD and UV254 removal rates. From the stabi-
lized COD and UV254 removal rates, it can be deduced that excessive
a b
Fig. 3. Effect of different catalyst dosages on (a) COD removal rate and (b) UV254 removal rate (ozone dosage at 2 L/min, pH at 7.1, reaction
temperature at 25 , and continuous aeration time at 120 min).
6
catalyst dosage hindered the generation of ∙OH, which converted
into without catalytic ability. Besides, as the number of O3 mole-
cules per unit volume of the solution was fixed, increasing the
catalyst dosage failed to make the O3 in the bubbles come into
sufficient contact with the active sites on the catalyst surface [41,
60]. It can also be seen that the COD and UV254 removal rates
were not linear related with the increase of catalyst dosage, but
there existed a critical value [60]. Therefore, from the perspectives
of both cost efficiency and treatment performance, 3.0 g/L was
used as the optimal catalyst dosage in the subsequent experiments.
3.4.2. Effect of initial pH of solution
The performance of heterogeneous catalytic oxidation is greatly
affected by environmental factors, and as reported in the literature,
it is particularly affected by the pH of the solution. On the one
hand, the pH of the solution affects the oxidation mode and the
decomposition rate of O3 [57]. For instance, based on Eqs.(3)-(8)
[61], in the solution will decompose O3. Nevertheless, ex-
cessive will inhibit the generation of ∙OH.
(3)
(4)
(5)
(6)
(7)
(8)
On the other hand, the pH of the solution affects the charged
state of the catalyst surface, which can be expressed by the metal
oxide proton balance equations [62] (Eqs.(9)-(10)).
(9)
 Environmental Engineering Research 28(5) 220606

a b

Fig. 4. Effect of different initial pH values of the solution on (a) COD removal rate and (b) UV254 removal rate (ozone dosage at 2 L/min, catalyst
dosage at 3.0 g/L, reaction temperature at 25 , and continuous aeration time at 120 min).

(10)

We investigated how the initial pH values 5.0, 7.1, 9.4, and

10.8 affect the COD and UV254 removal rates of the Mn/AC/O3
system. The ozone dosage, catalyst dosage, reaction temperature,
and continuous aeration time were set at 2 L/min, 3.0 g/L, 25
℃, and 120 min, respectively. As shown in Fig. 4, when the pH
of the solution increased in the range of 5.0 to 9.4, it could increase
the rate of COD removal from dye wastewater. Therefore, it could
be concluded that the increase of the pH in this range could increase
the concentration of in the solution, which promoted the generation
of ∙OH. After 120 min of continuous aeration, when the initial
pH was 9.4, the removal efficiencies of COD and UV254 reached
73.6% and 79.3%, respectively, compared with the initial pH of
5.0, COD and UV254 removal rates soared about 12.9% and 9.8%,
respectively. First of all, the pH at the potential of zero-point
Fig. 5. Effect of different initial pH values of the solution (ozone dosage
charge (pHpzc) of the catalyst was found to be approximately 6.54
at 2 L/min, catalyst dosage at 3.0 g/L, reaction temperature at
lower than the pH of 9.4 in the solution. In this case, the catalyst
25 , and continuous aeration time at 120 min).
surface was negatively charged and showed good catalytic perform-
ance [63]. This was conducive to the adsorption of the Basic Yellow
It could affect both the decomposition rate of O3 and the charged
28 dyes with a positive charge. As reported in the literature,
state of the catalyst surface. Moreover, it could also affect the
MnOx/SBA-15 can adsorb organic matters to combine with the
surface properties of metal oxides covered by surface hydroxyl
hydroxyl groups on the catalyst surface to facilitate further oxi-
groups [67, 68]. The COD and UV254 degradation efficiencies ob-
dization and decomposition by ∙OH in the solution [64]. It can
tained under alkaline conditions were much higher than under
be seen from Fig. 5, the catalysts were more stable under alkaline
acidic conditions. Given these findings, the initial pH of 9.4 was
conditions and retained more manganese. The manganese caused
used in the subsequent experiments.
the formation of oxygen vacancies, which adsorbed more pollutants
to accelerate the ozonation process [65, 66]. Apart from this, ∙OH 3.4.3. Effect of initial temperature of solution
could also facilitate the decomposition of O3 to produce more We investigated how the initial solution temperatures 12.5℃, 23.
∙OH. However, it is worth noting that when the pH exceeded 2℃, and 31.7℃ affect the COD and UV254 removal rates of the
9.4, the COD and UV254 removal rates declined sharply. This could Mn/AC/O3 system. The subsequent experiment was carried out
be attributed to that excessive OH- consumed the ∙OH (Eq(8)) and under the optimum reaction conditions. From Fig. 6, it can be
competed with the catalyst to adsorb O3, which inhibited the activ- observed that COD and UV254 degradation efficiencies increased
ity of the catalyst and thus affected the COD and UV254 removal slowly with the increase of reaction temperature. The reaction
rates. The above-mentioned results demonstrated that the pH of temperature affected the catalytic ozonation process from two per-
the solution had a significant effect on the removal performance. spectives: the activation energy of the reaction and the solubility

7
Jie Wei et al.

a b

Fig. 6. Effect of different initial temperatures of the solution on (a) COD removal rate and (b) UV254 removal rate (ozone dosage at 2 L/min,
catalyst dosage at 3.0 g/L, pH at 7.1, and continuous aeration time at 120 min).

Fig. 7. The stability of catalysts (ozone dosage at 2 L/min, catalyst dosage at 3.0 g/L, pH at 9.4, and continuous aeration time at 120 min).

of O3 in the solution. The gradually increased reaction temperature
could cause the catalysts to reduce the activation energy of the
reaction. This could accelerate the chemical reaction between the
catalysts, O3, and pollutants. This could also promote the decom-
position of O3 molecules in the dye wastewater, which in turn
accelerated the generation of ∙OH to degrade organic matters.
However, with the increase in the initial temperature of the dye
wastewater, the solubility of O3 in the wastewater would decrease
[69-71]. This could hinder the conversion of O3 from the gas phase
to the liquid phase and affect the concentration of O3 and ∙OH,
thus failing to facilitate the COD and UV254 degradation efficiencies.
It was also found that the removal rates varied little among the three
solution temperatures, indicating that the initial temperature of the
solution had little effect on the ozone-catalyzed oxidation system.
However, the experimental results suggested that the initial temper-
ature of the solution had a positive effect on the catalytic ozonation
for the degradation of Basic Yellow 28 dyes. In other words, the
increase in reaction temperature played a greater role in the increase
in reaction rate than in the decrease in the solubility of O3.
3.5. The Stability of Catalysts
To evaluate the stability of the Mn/AC catalyst, it was reused
five times under the same conditions. As shown in Fig. 7, as
the catalyst was used for an increased number of times, the COD
and UV254 removal efficiency decreased, but to a small extent.
After the catalyst was used for the fifth time, the leaching percentage
of Mn was only 1.4%, which could have little effect on the activity
of the catalyst. These results demonstrated that the Mn/AC catalyst
remained stable and effective during the reaction process.
4. Conclusion
In this study, three catalysts were prepared by the impregnation-

8

calcination method under optimized conditions. The Mn/AC cata-
lyst obtained under the optimal conditions (500 ℃ roasting temper-
ature, 3h roasting time, and 0.5 mol/L impregnation solution con-
centration) achieved the best COD removal efficiency. The charac-
terization of the catalysts revealed that the Mn/AC catalyst had
better surface characteristics and pore structure than the other
two. Our investigation showed that different reaction conditions,
i.e., catalyst dosage, initial pH of the solution, and initial temper-
ature of solution, had different effects on the treatment performance
of Basic Yellow 28 dye wastewater. During the reaction process,
it was demonstrated that the increasing catalyst dosage could en-
hance the active sites in the system. For a good balance between
the removal rates of COD and UV254, 3.0 g/L was determined as
the optimal catalyst dosage. An appropriate alkalinity could not
only promote the decomposition of O3 but also improve the surface
characteristics of the catalysts. Accordingly, the initial pH 9.4
was beneficial to promoting catalytic ozonation. Besides, the rising
reaction temperature played a positive role in catalytic ozonation.
A possible area of future research would be to investigate methods
to improve the COD and UV254 degradation efficiencies by loading
multiple active components onto the supporter. Furthermore, it
is also important to go beyond laboratory models to explore the
practical functionality and applicability of the catalysts.
Acknowledgements
We acknowledge the financial support provided by the Major
Science and Technology Project on Water Pollution Control and
Treatment (2018ZX0760100401) and the Liaoning Provincial
Department of Education Project (lnjc202011).
Conflict-of-Interest Statement
The authors declare no competing interests.
Author Contributions
W.R.N. (student) conducted the experiments. S.H.W. (student)
conducted the experiments, wrote and revised the manuscript.
W.J. (associate professor) revised the manuscript.
Reference
1. Liu HB, Gao Y, Wang J, Pan JW, Gao BY, Yue QY. Catalytic
ozonation performance and mechanism of Mn-CeOx@γ
-Al2O3/O3 in the treatment of sulfate-containing hypersaline
antibiotic wastewater. Sci. Total Environ. 2022;807:150867.
https://doi.org/10.1016/j.scitotenv.2021.150867.
2. Wang JL, Wang SZ. Reactive species in advanced oxidation
processes: Formation, identification and reaction mechanism.
Chem. Eng. J. 2020;401:126158. https://doi.org/10.1016/j.cej.
2020.126158.
9
Environmental Engineering Research 28(5) 220606
3. Stock NL, Peller J, Vinodgopal K, Kamat PV. Combinative sonol-
ysis and photocatalysis for textile dye degradation. Environ.
Sci. Technol. 2000;34:1747-1750. https://doi.org/10.1021/
es991231c.
4. Jiang HB, Zhang R, Hao JL, et al. Design, preparation, character-
ization, and application of MnxCu1-xOy/γ-Al2O3 catalysts in ozo-
nation to achieve simultaneous organic carbon and nitrogen
removal in pyridine wastewater. Sci. Total Environ. 2021;
774:145189. https://doi.org/10.1016/j.scitotenv.2021.145189.
5. Martins RC, Quinta-Ferreira RM. Remediation of phenolic
wastewaters by advanced oxidation processes (AOPs) at am-
bient conditions: comparative studies. Chem. Eng. Sci. 2011;
66:3243-3250. https://doi.org/10.1016/j.ces.2011.02.023
6. Ahmadi M, Kakavandi B, Jaafarzadeh N, Babaei AA. Catalytic
ozonation of high saline petrochemical wastewater using
PAC@FeIIFe2IIIO4: optimization, mechanisms and biodegrad-
ability studies. Sep. Purif. Technol. 2017;177:293-303. https://
doi.org/10.1016/j.seppur.2017.01.008.
7. Rekhate CV, Srivastava J. Recent advances in ozone-based ad-
vanced oxidation processes for treatment of wastewater-A
review. Chem. Eng. J. Adv. 2020;3:100031. https://doi.org/
10.1016/j.ceja.2020.100031.
8. Cheng J, Xie YR, Wei Y, et al. Degradation of tetracycline
hydrochloride in aqueous via combined dielectric barrier dis-
charge plasma and Fe-Mn doped AC. Chemosphere. 2022;286:
131841. https://doi.org/10.1016/j.chemosphere.2021.131841.
9. Hu EL, Wu XB, Shang SM, Tao XM, Jiang SX, Gan L. Catalytic
ozonation of simulated textile dyeing wastewater using meso-
porous carbon aerogel supported copper oxide catalyst. J. Clean
Prod. 2016;112:4710-4718. https:/doi.org/10.1016/j.jclepro.
2015.06.127.
10. Nawrocki J. Catalytic ozonation in water: controversies and
questions. Discussion paper. Appl. Catal. B. 2013;142:465-471.
https://doi.org/10.1016/j.apcatb.2013.05.061.
11. Wu ZW, Zhang GQ, Zhang RY, Yang FL. Insights into mecha-
nism of catalytic ozonation over practicable mesoporous
Mn-CeOx/γ-Al2O3 catalysts. Ind. Eng. Chem. Res. 2018;57:
1943-1953. https:/doi.org/10.1021/acs.iecr.7b04516.
12. Sui MH, Liu J, Sheng L. Mesoporous material supported man-
ganese oxides (MnOx/MCM-41) catalytic ozonation of nitro-
benzene in water. Appl. Catal. B. 2011;106:195-203. https://do-
i.org/10.1016/j.apcatb.2011.05.025.
13. Tian SQ, Qi JY, Wang YP, Liu YL, Wang L, Ma J. Heterogeneous
catalytic ozonation of atrazine with Mn-loaded and Fe-loaded
biochar. Water Res. 2021;193:116860. https://doi.org/10.1016/j.
watres.2021.116860.
14. de Oliveira SB, Barbosa DP, de Melo Monteiro AP, Rabelo
D, do Carmo Rangel M. Evaluation of copper supported on
polymeric spherical activated carbon in the ethylbenzene
dehydrogenation. Catal. Today. 2008;133:92-98. https://do-
i.org/10.1016/j.cattod.2007.12.040.
15. Pimentel M, Oturan N, Dezotti M, Oturan MA. Phenol degrada-
tion by advanced electrochemical oxidation process elec-
tro-Fenton using a carbon felt cathode. Appl. Catal. B. 2008;
83:140-149. https://doi.org/10.1016/j.apcatb.2008.02.011.
16. Huang YX, Cui CC, Zhang DF, Li L, Pan D. Heterogeneous
catalytic ozonation of dibutyl phthalate in aqueous solution
Jie Wei et al.
in the presence of iron-loaded activated carbon. Chemosphere.
2015;119:295-301. https://doi.org/10.1016/j.chemosphere.2014.
06.060.
17. Abdedayem A, Guiza M, Ouederni A. Copper supported on
porous activated carbon obtained by wetness impregnation:
effect of preparation conditions on the ozonation catalyst's
characteristics. C. R. Chim. 2015;18:100-109. https://doi.org/10.
1016/j.crci.2014.07.011.
18. Rao YF, Luo HJ, Wei CH, Luo LF. Catalytic ozonation of phenol
and oxalic acid with copper-loaded activated carbon. J. Cent.
South Univ. 2010;17:300-306. https://doi.org/10.1007/s11771-
010-0046-y.
19. Ma J, Sui MH, Chen ZL, Wang LN. Degradation of refractory
organic pollutants by catalytic ozonation—activated carbon
and Mn-loaded activated carbon as catalysts. Ozone Sci. Eng.
2004;26:3-10. https://doi.org/10.1080/01919510490426027.
20. Wu GP, Jeong TS, Won CH, Cui LZ. Comparison of catalytic
ozonation of phenol by activated carbon and manganese- sup-
ported activated carbon prepared from brewing yeast. Korean
J. Chem. Eng. 2010;27:168-173. https://doi.org/10.1007/s11814-
009-0337-x.
21. Huang F, Luo MH, Cui LZ, Wu GP. Catalytic ozonation of
methylene blue in aqueous solution by loading transition metal
(Co/Cu/Fe/Mn) on carbon. Korean J. Chem. Eng. 2015;32:
268-273. https://doi.org/10.1007/s11814-014-0238-5.
22. Chen CM, Chen HS, Guo X, Guo SH, Yan GX. Advanced ozone
treatment of heavy oil refining wastewater by activated carbon
supported iron oxide. J. Ind. Eng. Chem. 2014;20:2782-2791.
https://doi.org/10.1016/j.jiec.2013.11.007.
23. Quan XJ, Luo D, Wu J, Li RH, Cheng W, Ge SP. Ozonation
of acid red 18 wastewater using O3/Ca(OH)2 system in a micro
bubble gas-liquid reactor. J. Environ. Chem. Eng. 2017;5:
283-291. https://doi.org/10.1016/j.jece.2016.12.007.
24. Khuntia S, Majumder SK, Ghosh P. Catalytic ozonation of dye
in a microbubble system: hydroxyl radical contribution and
effect of salt. J. Environ. Chem. Eng. 2016;4:2250-2258. https://
doi.org/10.1016/j.jece.2016.04.005.
25. Rojviroon O, Rojviroon T. Photocatalytic process augmented
with micro/nano bubble aeration for enhanced degradation
of synthetic dyes in wastewater. Water Resour. Ind. 2022;27:
100169. https://doi.org/10.1016/j.wri.2021.100169.
26. Khuntia S, Majumder SK, Ghosh P. Removal of ammonia from
water by ozone microbubbles. Ind. Eng. Chem. Res. 2013;52:
318-326. https://doi.org/10.1021/ie302212p.
27. Hu LM, Xia ZR. Application of ozone micro-nano-bubbles to
groundwater remediation. J. Hazard. Mater. 2018;342:446-453.
https://doi.org/10.1016/j.jhazmat.2017.08.030.
28. Wu JJ, Zhang KJ, Cen C, Wu XG, Mao RY, Zheng YY. Role
of bulk nanobubbles in removing organic pollutants in waste-
water treatment. AMB. Express. 2021;11: 1-13. https://doi.org/
10.1186/s13568-021-01254-0.
29. Agarwal A, Ng WJ, Liu Y. Principle and applications of micro-
bubble and nanobubble technology for water treatment.
Chemosphere. 2011;84:1175-1180. https://doi.org/10.1016/
j.chemosphere.2011.05.054.
30. Takahashi M, Chiba K, Li P. Free-radical generation from col-
lapsing microbubbles in the absence of a dynamic stimulus.
10
J. Phys. Chem. B. 2007;111:1343-1347. https://doi.org/10.1021/
jp0669254.
31. Liu S, Oshita S, Kawabata S, Makino Y, Yoshimoto T.
Identification of ROS produced by nanobubbles and their pos-
itive and negative effects on vegetable seed germination.
Langmuir. 2016;32:11295-11302. https://doi.org/10.1021/acs.
langmuir.6b01621.
32. Xia ZR, Hu LM. Treatment of organics contaminated wastewater
by ozone micro-nano-bubbles. Water. 2018;11:55. https://do-
i.org/10.3390/w11010055.
33. Zheng TL, Zhang T, Wang QH, et al. Advanced treatment
of acrylic fiber manufacturing wastewater with a combined
microbubble-ozonation/ultraviolet irradiation process. RSC
Adv. 2015;5:77601-77609. https://doi.org/10.1039/c5ra14575a.
34. Zhang J, Huang GQ, Liu C, Zhang RN, Chen XX, Zhang L.
Synergistic effect of microbubbles and activated carbon on
the ozonation treatment of synthetic dyeing wastewater. Sep.
Purif. Technol. 2018;201:10-18. https://doi.org/10.1016/j.seppur.
2018.02.003.
35. Lorimer JP, Mason TJ, Plattes M, Phull SS, Walton DJ.
Degradation of dye effluent. Pure Appl. Chem. 2001;73:1957-
1968. https://doi.org/10.1351/pac200173121957.
36. Nanyuan Pump Industry Corporation. Self-priming gas-liquid
mixing pump [Internet]. c2019. [cited 20 October 2022].
Available from: https://www.nyp-pump.cn/product/557.html.
37. Mustafa S, Dilara B, Nargis K, Naeem A, Shahida P. Surface
properties of the mixed oxides of iron and silica. Colloids.
Surf. A. Physicochem. Eng. Asp. 2002;205:273-282. https://do-
i.org/10.1016/s0927-7757(02)00025-0.
38. Garcia-Ochoa F, Gomez E. Bioreactor scale-up and oxygen trans-
fer rate in microbial processes: an overview. Biotechnol. Adv.
2009;27:153-176. https://doi.org/10.1016/j.biotechadv.2008.
10.006.
39. Xu Z, Mochida K, Naito T, Yasuda K. Effects of operational
conditions on 1, 4-dioxane degradation by combined use of
ultrasound and ozone microbubbles. Jpn. J. Appl. Phys. 2012;51:
07GD08. https://doi.org/10.1143/jjap.51.07gd08.
40. Li HZ, Hu LM, Song DJ, Lin F. Characteristics of micro-nano
bubbles and potential application in groundwater
bioremediation. Water Environ. Res. 2014;86:844-851. https://do-
i.org/10.2175/106143014x14062131177953.
41. Chu LM, Xing XH, Yu AF, Zhou YN, Sun XL, Jurcik B. Enhanced
ozonation of simulated dyestuff wastewater by microbubbles.
Chemosphere. 2007;68:1854-1860. https://doi.org/10.1016/j.
chemosphere.2007.03.014.
42. Liu S, Wang QH, Zhai XD, Huang QF, Huang PK. Improved
Pretreatment (Coagulation-Floatation and Ozonation) of
Younger Landfill Leachate by Microbubbles. Water Environ.
Res. 2010;82:657-665. https://doi.org/10.2175/106143010x126
09736966522.
43. Kim S, Kim H, Han M, Kim T. Generation of sub-micron (nano)
bubbles and characterization of their fundamental properties.
Environ. Eng. Res. 2019;24:382-388. https://doi.org/10.4491/eer.
2018.210.
44. Nam G, Mohamed MM, Jung J. Enhanced degradation of benzo
[a] pyrene and toxicity reduction by microbubble ozonation.
Environ. Technol. 2021;42:1853-1860. https://doi.org/10.1080/

09593330.2019.1683077.
45. Saroyan H, Kyzas GZ, Deliyanni EA. Effective dye degradation
by graphene oxide supported manganese oxide. Processes.
2019;7:40. https://doi.org/10.3390/pr7010040.
46. Wang YX, Xie YB, Sun HQ, Xiao JD, Cao HB, Wang SB. 2D/2D
nano-hybrids of γ-MnO₂ on reduced graphene oxide for catalytic
ozonation and coupling peroxymonosulfate activation. J.
Hazard. Mater. 2016;301:56-64. https://doi.org/10.1016/j.
jhazmat.2015.08.031.
47. Lee CG, Javed H, Zhang DN, et al. Porous electrospun fibers
embedding TiO2 for adsorption and photocatalytic degradation
of water pollutants. Environ. Sci. Technol. 2018;52:4285-4293.
https://doi.org/10.1021/acs.est.7b06508.
48. Glaze WH, Kang JW, Chapin DH. The Chemistry of Water
Treatment Processes Involving Ozone, Hydrogen Peroxide and
Ultraviolet Radiation. Ozone Sci. Eng. 2008;9:335-352.
https://doi.org/10.1080/01919518708552148.
49. Mosallanejad S, Dlugogorski BZ, Kennedy EM, Stockenhuber
M. On the chemistry of iron oxide supported on γ-alumina
and silica catalysts. ACS omega. 2018;3:5362-5374. https://do-
i.org/10.1021/acsomega.8b00201.
50. Li LS, Zhu WP, Zhang PY, Zhang QY, Zhang ZL. AC/O3-BAC
processes for removing refractory and hazardous pollutants
in raw water. J. Hazard. Mater. 2006;135:129-133. https://do-
i.org/10.1016/j.jhazmat.2005.11.045.
51. Roshani B, McMaster I, Rezaei E, Soltan J. Catalytic ozonation
of benzotriazole over alumina supported transition metal oxide
catalysts in water. Sep. Purif. Technol. 2014;135:158-164.
https://doi.org/10.1016/j.seppur.2014.08.011.
52. Zheng QF, Wang ZM, Chen BG, Liu GF, Zhao J. Analysis of
XRD Spectral Structure and Carbonization of the Biochar
Preparation. Spectrosc. spect. anal. 2016;36:3355-3359.
https://doi.org/10.3964/j.issn.1000-0593(2016)10-3355-05.
53. Li PC, Hu CC, Lee TC, Chang WS, Wang TH. Synthesis and
characterization of carbon black/manganese oxide air cathodes
for zinc-air batteries. J. Power Sources. 2014;269:88-97.
https://doi.org/10.1016/j.jpowsour.2014.06.108.
54. Hinokuma S, Shimanoe H, Kawabata Y, Kiritoshi S, Araki
K, Machida M. Supported and unsupported manganese oxides
for catalytic ammonia combustion. Catal. Commun.
2018;105:48-51. https://doi.org/10.1016/j.catcom.2017.11.009.
55. Beltrán FJ, Rivas FJ, Montero-de-Espinosa R. Catalytic ozona-
tion of oxalic acid in an aqueous TiO2 slurry reactor. Appl.
Catal. B: Environ. 2002;39:221-231. https://doi.org/10.1016/
s0926-3373(02)00102-9.
56. Ernst M, Lurot F, Schrotter JC. Catalytic ozonation of refractory
organic model compounds in aqueous solution by aluminum
oxide. Appl. Catal. B: Environ. 2004;47:15-25. https://do-
i.org/10.1016/s0926-3373(03)00290-x.
57. Zhao L, Ma J, Sun ZZ, Zhai XD. Mechanism of influence of
initial pH on the degradation of nitrobenzene in aqueous sol-
ution by ceramic honeycomb catalytic ozonation. Environ. Sci.
Technol. 2008;42:4002-4007. https://doi.org/10.1021/es 702926q.
58. Bai ZY, Yang Q, Wang JL. Fe3O4/multi-walled carbon nanotubes
11
Environmental Engineering Research 28(5) 220606
as an efficient catalyst for catalytic ozonation of p-hydrox-
ybenzoic acid. Int. J. Environ. Sci. Technol. 2016;13:483-492.
https://doi.org/10.1007/s13762-015-0881-3.
59. Liu XH, Li HP, Fang Y, Yang ZG. Heterogeneous catalytic ozona-
tion of sulfamethazine in aqueous solution using maghe-
mite-supported manganese oxides. Sep. Purif. Technol.
2021;274:118945. https://doi.org/10.1016/j.seppur.2021.118945.
60. Song JS, Ma NW, Chen WQ, Chen JM, Dai QZ. Insights into
mechanism of catalytic ozonation of cinnamyl alcohol over
core-shell Fe3O4@ SiO2@ La2O3 catalyst. Sep. Purif. Technol.
2022;282:119969. https://doi.org/10.1016/j.seppur.2021.119969.
61. Radhakrishnan R, Oyama ST, Chen JG, Asakura K. Electron
transfer effects in ozone decomposition on supported man-
ganese oxide. J. Phys. Chem. B. 2001;105:4245-4253. https://do-
i.org/10.1021/jp003246z.
62. Zhao L, Sun ZZ, Ma J, Liu HL. Enhancement mechanism of
heterogeneous catalytic ozonation by cordierite-supported cop-
per for the degradation of nitrobenzene in aqueous solution.
Environ. Sci. 2009;43:2047-2053. https://doi.org/10.1021/es803125h.
63. Psaltou S, Kaprara E, Triantafyllidis K, Mitrakas M, Zouboulis
A. Heterogeneous catalytic ozonation: The significant con-
tribution of PZC value and wettability of the catalysts. J. Environ.
Chem. Eng. 2021;9:106173. https://doi.org/10.1016/j.jece.2021.106173.
64. Sun QQ, Li LS, Yan HH, Hong XT, Hui KS, Pan ZQ. Influence
of the surface hydroxyl groups of MnOx/SBA-15 on heteroge-
neous catalytic ozonation of oxalic acid. Chem. Eng. J.
2014;242:348-356. https://doi.org/10.1016/j.cej.2013.12.097.
65. Li JR, Chen JS, Yu YK, He C. Fe-Mn-Ce/ceramic powder compo-
site catalyst for highly volatile elemental mercury removal
in simulated coal-fired flue gas. J. Ind. Eng. Chem. 2015;25:
352-358. https://doi.org/10.1016/j.jiec.2014.11.015.
66. Zhang JW, Guo Q, Wu WL, et al. Preparation of Fe-MnOx/AC
by high gravity method for heterogeneous catalytic ozonation
of phenolic wastewater. Chem. Eng. Sci. 2022;255:117667.
https://doi.org/10.1016/j.ces.2022.117667.
67. Ma J, Sui MH, Zhang T, Guan CY. Effect of pH on MnOx/GAC
catalyzed ozonation for degradation of nitrobenzene. Water
Res. 2005;39:779-786. https://doi.org/10.1016/j.watres.2004.
11.020.
68. Liu RX, Tang HX. Oxidative decolorization of direct light red
F3B dye at natural manganese mineral surface. Water Res.
2000;34:4029-4035. https://doi.org/10.1016/s0043-1354(00)00166-4.
69. Zhao L, Ma J, Sun ZZ, Zhai XD. Catalytic ozonation for the
degradation of nitrobenzene in aqueous solution by ceramic
honeycomb-supported manganese. Appl. Catal. B: Environ.
2008;83:256-264. https://doi.org/10.1016/j.apcatb.2008.02.009.
70. Nöthe T, Fahlenkamp H, Sonntag CV. Ozonation of wastewater:
rate of ozone consumption and hydroxyl radical yield. Environ.
Sci. Technol. 2009;43: 5990-5995. https://doi.org/10.1021/
es900825f.
71. Rischbieter E, Stein H, Schumpe A. Ozone solubilities in water
and aqueous salt solutions. J. Chem. Eng. Data. 2000;45:
338-340. https://doi.org/10.1021/je990263c.