Separation and Purification Technology 291 (2022) 120874

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Separation and Purification Technology

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

A novel integrated process of ceramic membrane filtration coupled with

peroxymonosulfate activation and adsorption for water treatment
Songxue Wang a, Qianqian Wu a, Boyin Yan a, Yuan Guo b, Wenxiang Xia a, *, Jincheng Li a,
Fuyi Cui c, Jiayu Tian d, *
a
School of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266520, China
b
State Key Laboratory of Eco-hydraulics in Northwest Arid Region, Xi’an University of Technology, Xi’an 710048, China
c
College of Urban Construction and Environmental Engineering, Chongqing University, Chongqing 400044, China
d
School of Civil Engineering and Transportation, Hebei University of Technology, Tianjin 300401, China

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

Keywords: Emerging contaminants have been widespread in water, while conventional membrane separation is difficult to
Ceramic membrane effectively remove these organic micropollutants. This study develops a novel integrated process of ceramic
Peroxymonosulfate activation membrane filtration combined with peroxymonosulfate (PMS) activation and adsorption for organic pollutants
Granular active carbon
removal by loading Co coated granular active carbon (Co@GAC) into the membrane channels. The removal and
Adsorption
Integrated process
stability performance of the strategy was systematically investigated. Excellent removal efficiency of bisphenol A
(BPA) in the Co@GAC-membrane/PMS system was attained owing to the activated PMS and enhanced
adsorption by the Co@GAC in the membrane channels. Based on the scavenger tests and electron paramagnetic
resonance (EPR) analyses, sulfate radicals (SO4•− ) and hydroxyl radicals (•OH) were identified as the major
reactive species responsible for the degradation of BPA in the system, and the redox circles of Co(III)/Co(II) on
the Co@GAC were primarily responsible for PMS activation. Moreover, the Co@GAC-membrane/PMS system
exhibited excellent universality for various organic pollutants and stability for repetitive use. This study provides
a new insight into the design and development of the integrated process of membrane filtration coupled with
advanced oxidation processes (AOPs) and adsorption for water treatment.

1. Introduction and ongoing cost reduction of membrane preparation [9,10]. However,

In recent years, with the rapid development of industry and wide
applications of new technologies, more and more emerging organic
pollutants, such as pharmaceuticals and personal care products (PPCPs),
environmental endocrine disruptors (EDCs), persistent organic pollut­
ants (POPs), enter the water through various ways with human activities
[1,2]. Despite of the low concentration of these organic contaminants in
water, the majority of them are difficult to breakdown, which can exist
in water environment for a long time and continuously migrate and
transform among various environmental media, thus posing potential
ecological environmental risks [3–5]. Simultaneously, emerging organic
contaminants can eventually reach the human body through the food
chain, drinking water, and other routes, creating a serious health risk
[6–8]. Membrane separation technology has been widely developed and
utilized in the field of drinking water and wastewater treatment because
of its benefits of compact footprint, simple operation and management,
the conventional microfiltration/ultrafiltration membrane is difficult to
efficiently remove the above refractory organic pollutants by intercep­
tion of membrane pores due to their large molecular weight cutoff,
which has become a major barrier to the widespread application of
membrane separation technology [11,12]. Therefore, it has become one
of the tough challenges for membrane water treatment that how to
economically and efficiently remove refractory organic pollutants from
water and improve effluent quality during membrane separation.
Advanced oxidation processes (AOPs) are the key technologies to
solve the problems of water pollution and drinking water safety
[8,13,14]. It can be predicted that the coupling of AOPs and membrane
separation technology will provide a new approach of high efficiency,
low consumption, and easy operation and management for the removal
of refractory organic pollutants in water [15–17]. Recently, a large
number of research results have proved that AOPs coupled with mem­
brane filtration can not only effectively degrade refractory organic

* Corresponding authors at: School of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266520, China (W. Xia) (J. Tian).
E-mail addresses: xia-wx@qut.edu.cn (W. Xia), tjy800112@163.com (J. Tian).

https://doi.org/10.1016/j.seppur.2022.120874
Received 23 January 2022; Received in revised form 28 February 2022; Accepted 17 March 2022
Available online 21 March 2022
1383-5866/© 2022 Elsevier B.V. All rights reserved.
S. Wang et al.
pollutants in water to improve effluent quality, but also help to alleviate
membrane fouling [18,19]. For example, Wang et al. [20] reported that
a high-performance membrane coupling with photo-Fenton by doping
CuFe2O4 in the PVDF membrane was developed and dramatically
enhanced the separation efficiency and permeate flux. Lee et al. [21]
developed a novel hybrid catalytic ozonation-membrane filtration pro­
cess with the CeOx and MnOx impregnated ceramic membranes to
degrade the emerging micropollutants and showed prominent perfor­
mance. However, photocatalysis is vulnerable to water quality, weather
and other conditions, and the ozone-based technology requires addi­
tional equipment and energy input, resulting in increased operational
and administrative costs. Peroxymonosulfate (PMS) activation, as one of
the novel developing AOPs, has attracted great attention from domestic
and foreign researchers in recent years [22,23]. In the processes of
persulfate activation by different catalysts, some active substances with
significant oxidation capacity can be produced, such as sulfate radical
(SO4•− ), hydroxyl radical (•OH), singlet oxygen, and so on, which has
huge development potential in the field of removing refractory organic
pollutants in water [24–26]. However, it is difficult for organic mem­
brane materials to make long-term operation in a strongly oxidizing
environment due to their properties [21,27]. This defect limits the
further development and large-scale application of the system of PMS
activation coupling with membrane filtration in the field of water
treatment. Compared with organic membrane, ceramic membrane ex­
hibits high mechanical strength and superior chemical stability, and
thus it can withstand high intensity chemical oxidation, providing a
broader space for the construction of PMS and ceramic membrane
filtration coupling system [28,29]. Currently, most researchers devel­
oped the catalytic membrane by loading catalysts directly onto the
ceramic membranes to achieve AOPs and decompose organic pollutants
during the filtration process [13,30,31]. Although this method could
achieve filtration and degradation at the same time, it brought a critical
issue that loading the catalyst onto the membrane changed the pore
structure of the membrane, thereby reducing the flux in the filtration
process and increasing the cost of operation, which would be detri­
mental to practical applications. Moreover, it is difficult for PMS to fully
contact and react with the catalyst supported on the membrane because
of the short contact time between PMS and catalytic membrane during
the filtration process, which may lead to unsatisfactory degradation of
organic pollutants in water.
Porous carbon is not only a widely used adsorbent material, but also
a good catalyst carrier. Loading the catalyst onto porous carbon material
can achieve the dual functions of efficient activation of PMS and
adsorption of organic pollutants [32–34]. By observing the macroscopic
structure of ceramic membrane, it can be found that the commonly used
tubular membrane and flat-sheet membrane have large channels struc­
ture for water collection. Inspired from this, a novel integrated process
of ceramic membrane filtration combined with PMS activation and
adsorption was creatively designed by filling the channels of the ceramic
membrane with activated carbon catalysts, which not only could avoid
the destruction of membrane pore structure but also effectively improve
the degradation of organic pollutants. In this study, the integrated sys­
tem was developed and applied in water treatment. The removal per­
formance of aqueous organic compounds and the effects of operation
parameters on removal efficiencies in this system were evaluated. The
roles of active species in the degradation process were investigated via a
series of experiments and instrument characterization. Furthermore, the
influence of actual water matrix on the removal performance and the
stability and reusability of the integrated system were also assessed.
2. Materials and methods
2.1. Materials and reagents
Peroxymonosulfate (PMS, KHSO5⋅0.5KHSO4⋅0.5K2SO4) was ob­
tained from Shanghai Macklin Biochemistry Technology Co. Ltd.
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Separation and Purification Technology 291 (2022) 120874
(China). Granular active carbon (GAC, coconut shell, iodine value: 700
~ 1200 mg/g) was purchased from Xinzhiyuan Activated Carbon Co.,
Ltd. (China). Bisphenol A (BPA), 4-chlorophenol (4-CP), sulfadiazine
(SDZ), and methylene blue (MB) were obtained from Aladdin Industrial
Corporation (China). Cobalt nitrate hexahydrate (Co(NO3)2⋅6H2O),
methanol (MeOH), tert-butyl alcohol (TBA), phenol, and rhodamine B
were purchased from Sinopharm Chemical Reagent Co., Ltd. (China). All
solutions were prepared using deionized (DI) water, and natural surface
water samples were collected from Dingjiahe Reservoir (Qingdao,
China) which was pre-filtered through a 0.45 μm membrane. All the
water samples were controlled under neutral condition (pH = 7.0 ± 0.2)
prior to the experiments and room temperature was kept during the
entire operating period. Flat-sheet ceramic membrane fabricated from
our laboratory was employed in this study and the composition and
characteristic parameters of the membrane are listed in Table 1.
2.2. Fabrication of Co@GAC and Co@GAC-membrane module
The GAC was sonicated in DI water and washed several times to
remove impurities from the GAC surface, and then the GAC was dried in
an oven at 70 ◦ C for 6 h. After drying, the fine particles were removed by
sieving, and the particle size of GAC was controlled to be 2 ~ 4 mm for
reserve. 5 g of Co(NO3)2⋅6H2O was dissolved in 100 mL of DI water, and
then GAC (10 g) was added to this solution and soaked for 24 h. After
draining excess solution and drying in an oven at 80 ◦ C for 12 h, the
soaked GAC were calcined in a muffle furnace at 600 ◦ C for 3 h to obtain
the Co coated GAC (Co@GAC). The loading content of Co catalyst in
Co@GAC was determined by measuring the weight of the GAC before
and after fabrication. The Co@GAC-membrane module was composed of
a piece of flat-sheet ceramic membrane with a length of 7.5 cm by taken
with a cutting machine, 5 g of Co@GAC, polypropylene punching mesh
(72 mm × 7.5 mm) with pore size of 1 mm which can prevent Co@GAC
from flowing out of the channels during the operation of filtration, and
bottom seal and upper outlet polyamide mold. The fabrication process of
the Co@GAC-membrane module was presented in Fig. 1. The effective
membrane area of the prepared Co@GAC-membrane module was ~92
cm2.
2.3. Characterization of Co@GAC
The morphologies and energy dispersive spectrometry (EDS)
element mapping of Co@GAC samples were investigated by a field
emission scanning electron microscopy (FE-SEM) (SIGMA300, Zeiss,
Germany). The material composition and crystal phase of the Co@GAC
samples were characterized by an X-ray diffractometry (XRD) (Smartlab
9 kW, Rigaku, Japan). A photoelectron spectrometer (ESCALAB 250Xi,
Thermo Scientific, USA) equipped with a monochromatic Al K excitation
source was used to undertake X-ray photoelectron spectroscopy (XPS)
investigations. The Brunauer-Emmett-Teller (BET) surface area of the
samples was determined on a Micromeritics ASAP 2020 analyzer.
2.4. Experimental procedures and analysis
The membrane filtration and degradation tests were conducted using
Table 1
Properties of the flat-sheet ceramic membrane.
Description Virgin membrane
Major material Al2O3, TiO2, SiO2
Width (mm) 72
Thickness (mm) 6
Channels (mm) 15 (4 × 4)
Channel wall thickness (mm) 1
Average pore size (nm) 300
Porosity (%) 42
Pure water flux (LMH/bar) 1.28 × 103
S. Wang et al.
Fig. 1. Fabrication process of the Co@GAC-membrane module.
a submerged ceramic membrane filtration setup in our lab and the
schematic representation was shown in Fig. S1. During the operation,
the permeate flux of the filtration system was kept constant using a
peristaltic suction pump and the trans-membrane pressure (TMP) was
recorded by a pressure transducer. In the filtration and degradation
experiments, the targeted pollutant was dissolved in a feed tank with 1.2
L of DI water. The membrane module was installed in the feed tank and
PMS was added to the feed water. The pump was started and then begin
timing when the outlet end emerges from permeate. At each time in­
terval, 1 mL of the permeate sample was collected and filtered through
0.22 μm filter. At the same time, the sample was quenched with 0.2 mL
of pure methanol. The concentrations of organic pollutants were
detected by a high-performance liquid chromatography (HPLC) (LC-
20AT, Shimadzu, Japan) equipped with C18 column (250 mm × 4.6
mm, 5 µm) and UV absorbance detector (Shimadzu SPD-20A). The
detailed determination conditions are listed in Table S1. The generated
reactive oxygen species in the system were identified by Electron spin
resonance (ESR) spectroscopy (Bruker A300 spectrometer, Germany).
Fig. 2. SEM images of GAC (a, b) and Co@GAC (c, d).
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Separation and Purification Technology 291 (2022) 120874
The total organic carbon (TOC) concentration of the permeate and feed
were measured with a TOC analyzer (Multi N/C 2100S, AnalytikJena,
Germany). The leaching concentration of metal ions in aqueous solution
was analyzed by an inductively coupled plasma optical emission spec­
trometry (ICP-OES) (Optima 5300DV, Perkin Elmer, USA).
3. Results and discussion
3.1. Characterization of Co@GAC
As presented in Fig. 2, SEM was employed to characterize the
morphology of GAC and Co@GAC. Fig. 2a and b show the surface mi­
crostructures of GAC at low and high magnification. The surface of GAC
was uneven with massive structures and abundant pores. Compared to
GAC, the surface of Co@GAC was uniformly coated with a thin flaky
substance that formed more pore structures (Fig. 2c and d). Fig. S2
shows the EDS mapping of Co@GAC suggesting that the thin flaky
substance may be cobalt oxide and shows a relatively uniform coating.
S. Wang et al. Separation and Purification Technology 291 (2022) 120874

Further, the crystalline structure of the thin flaky substance generated

on the Co@GAC surface was determined by XRD. As shown in Fig. 3a,
the reflection peaks of Co@GAC at 19.0◦ , 31.3◦ , 36.9◦ , 44.8◦ , 55.6◦ ,
59.3◦ , and 65.2◦ corresponding to (1 1 1), (2 2 0), (3 1 1), (4 0 0), (4 2 2),
(5 1 1), and (4 4 0) were well indexed to tricobalt tetraoxide (Co3O4)
(PDF#78–1970) demonstrating that the thin flaky material that was
successfully coated on the GAC was principally composed of Co3O4. In
addition, the specific surface area of the samples was investigated in
Fig. 3b. The specific surface area of Co@GAC (671.83 m2/g) was higher
than that of GAC (516.40 m2/g). The coated Co3O4 with a thin sheet
structure would improve the performance of catalytic activation due to
its higher specific surface area.

3.2. Co@GAC-membrane permeate and BPA removal performance

To investigate the influence of loading Co@GAC into the membrane

channels on the membrane permeate property, the trans-membrane
pressure (TMP) of the virgin membrane and Co@GAC-membrane was
recorded at the different constant fluxes of 20 L/m2⋅h (LMH), 35 LMH,
and 50 LMH in the submersed membrane system. As shown in Fig. 4, at Fig. 4. TMP of virgin membrane and Co@GAC-membrane at the different
the constant flux of 20 LMH, the TMP of virgin membrane and Co@GAC- constant fluxes (20 LMH, 35 LMH, and 50 LMH).
membrane were 1.8 kPa and 1.9 kPa, respectively, after running for 60
min. When the operating flux was increased to 35 LMH, the difference of
filtration systems, the BPA removal efficiency of the GAC-membrane/
the TMP of virgin membrane and Co@GAC-membrane was only 0.1 kPa
PMS system was approximately 50.5%, while the Co@GAC-
after 60 min. Until the flux went up to 50 LMH, slight change was
membrane/PMS system achieved 92.8% BPA degradation. The result
observed that the TMP of the Co@GAC-membrane was only 0.3 kPa
indicated that Co@GAC loaded into the ceramic membrane channels
higher than that of the virgin membrane. As a result, there was little
was responsible for the increased catalytic activity for PMS activation
effect on membrane permeate property for loading Co@GAC into the
and BPA degradation. In order to intuitively display the high degrada­
membrane channels because of the relatively low operation flux for
tion efficiency of Co@GAC-membrane/PMS system, rhodamine B was
submerged membrane filtration system in practical application.
used as the target contaminant in the experiment. As shown in Fig. 5b
In this study, BPA was chosen as the target contaminant to evaluate
and c, the permeate water of the Co@GAC-membrane was still colored,
the removal efficacy in the membrane filtration systems under various
however, the Co@GAC-membrane/PMS system was able to immediately
experimental conditions. Fig. 5a displays that BPA adsorption was
produce colorless permeate water, implying that contaminated water
negligible by the virgin membrane, and about 5.0% of BPA was
can achieve efficient treatment immediately after flowing through the
degraded when only PMS was present in the system. The average BPA
system.
removal efficiency was 7.3% in the virgin membrane/PMS system
indicating that virgin membrane shows almost no catalytic activity for
PMS activation. Co@GAC-membrane presented a higher adsorption 3.3. Influence of experimental conditions
than the GAC-membrane. Co@GAC-membrane produced about 59.1%
BPA reduction in concentration and the BPA removal of GAC-membrane The removal efficiency of BPA in the Co@GAC-membrane/PMS
was about 38.4%, due to the loading of Co3O4 on GAC surface enhancing system under different conditions was investigated experimentally. As
the Co@GAC surface area. It is consistent with the result of BET for shown in Fig. 6a, the effect of BPA concentration on BPA removal was
Co@GAC and GAC (Fig. 3b). When PMS was added into the membrane examined in the system. When the BPA concentration increased from 2

Fig. 3. XRD spectra (a) and N2 adsorption–desorption isotherms (b) of GAC and Co@GAC.

4
S. Wang et al.
Fig. 5. (a) BPA removal in different systems ([BPA]0 = 10 mg/L, [PMS]0 = 0.2
mM, Flux = 35 LMH) and (b,c) dye removal by Co@GAC-membrane and
Co@GAC-membrane/PMS systems ([dye]0 = 10 mg/L, [PMS]0 = 0.2 mM, Flux
= 35 LMH).
mg/L to 5 mg/L, there was little change in the BPA removal rate that was
both about 99%. As the BPA concentration increased to 20 mg/L, the
BPA removal efficiency dropped gradually. The removal efficiencies of
93.1% and 75.3% were achieved with the initial BPA concentrations of
10 and 20 mg/L, respectively. The result indicated that the system ex­
hibits super performance of BPA removal when the BPA concentration
was below 10 mg/L. Fig. 6b displays the effect of PMS dosage on the BPA
removal in the system. As the PMS dosage increased from 0.1 mM to 0.5
mM, BPA removal was continually enhanced, because more PMS were
activated by Co@GAC in the membrane. However, the BPA removal
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Separation and Purification Technology 291 (2022) 120874
efficiency increased slightly from 97.6 to 99.6%, as the PMS dosage
further increased from 0.5 to 1.0 mM due to the limited loading of
Co@GAC in the membrane channels. In addition, the influence of the
permeate flux on the BPA removal in the system was carried out and the
result is presented in Fig. 6c. The BPA removal efficiency declined from
96.2% to 77.0% with the increase of permeate flux from 20 LMH to 70
LMH. High permeate flux decreased the residence time of solution in the
membrane, leading to the reduction of interaction probability between
PMS and Co@GAC in the membrane channels. Furthermore, the
normalized effects of the experimental conditions were calculated on the
basis of the above experiments (the details were provided in Text S1 and
Table S2-4), as illustrated in Fig. 6d. It can be seen more intuitively that
the high concentration of BPA was detrimental to the removal perfor­
mance, which was not suitable for this system. Increasing the dosage of
PMS in a certain range could significantly improve the BPA removal and
a relatively low operation flux was conducive to the removal
performance.
3.4. Mechanism analysis of degradation for Co@GAC-membrane/PMS
system
According to Fig. 5a, the contribution of action in major regions of
the system was estimated for BPA removal at that condition and illus­
trated in Table 2 (the degradation of PMS alone, adsorption of virgin
membrane and degradation of virgin membrane/PMS were ignored due
to their low contribution). It shows that the adsorption and catalytic
performance were both improved when Co3O4 was coated on GAC. The
reason for improved adsorption performance of Co@GAC-membrane is
that the coated Co3O4 with thin flaky substance performed a larger
specific surface area on the surface, which has been mentioned by
analysis of SEM and BET results in Section 3.1. Therefore, the major
mechanism of BPA removal by Co@GAC-membrane/PMS will be dis­
cussed in the following part.
Firstly, a series of radical quenching experiments were carried out to
investigate the roles of active species in the oxidation process. MeOH
and TBA were used as free radical scavengers to distinguish SO4•− and
•
OH in the Co@GAC-membrane/PMS system. MeOH is a typical scav­
enger for SO4•− (k = 2.5 × 107 M− 1s− 1) and •OH (k = 9.7 × 108 M− 1s− 1),
and TBA is widely considered as a selective radical scavenger for •OH
with the rate constant of 3.6 ~ 7.6 × 108 M− 1s− 1. As shown in Fig. 7a,
when 50 mM TBA was added to the Co@GAC membrane/PMS system,
the BPA removal efficiency decreased from 95.5% to 82.5%. As more
TBA (100 mM) was added, the removal efficiency of BPA further drop­
ped to 77.0%, illustrating that •OH was generated in the Co@GAC
membrane/PMS system. The inhibition of BPA removal was more sig­
nificant that the BPA removal efficiency decreased from 95.5% to 68.1%
when 50 mM MeOH was added to the system. The BPA removal rate fell
from 68.1% to 61.6% as MeOH concentration increased from 50 mM to
100 mM, which is nearly the same as the BPA adsorption of Co@GAC,
suggesting that SO4•− was also generated in the catalytic oxidation. The
above results indicate that both SO4•− and •OH were the dominant
species and responsible for the BPA degradation in the Co@GAC-
membrane/PMS system. Moreover, the quenching experiments were
conducted in the Co@GAC/PMS system to eliminate the influence of
membrane system, because the activation of PMS by Co@GAC in the
membrane channels is the primary cause of BPA degradation. As illus­
trated in Fig. S3a, after 30 min of adding excess TBA to the Co@GAC/
PMS system, the BPA removal efficiency decreased from 97.7% to
71.5%. And after the addition of excess MeOH to the system, the BPA
removal rate significantly dropped to 34.3%. Similarly, Co3O4 powder
obtained under the same conditions was used for the radical quenching
experiment and the result is presented in Fig. S3b. When external MeOH
and TBA were added to the Co3O4/PMS system, the degradation effi­
ciency of BPA declined from 82.6% to 44.2% and 64.6%, respectively.
The above results further provided evidence for the involvement of both
SO4•− and •OH were the dominant species in the Co@GAC-membrane/
S. Wang et al. Separation and Purification Technology 291 (2022) 120874

Fig. 6. (a) Effect of BPA concentration on BPA removal ([PMS]0 = 0.2 mM, Flux = 35 LMH), (b) effect of PMS dosage on BPA removal ([BPA]0 = 10 mg/L, Flux = 35
LMH), (c) effect of permeate flux on BPA removal ([BPA]0 = 10 mg/L, [PMS]0 = 0.2 mM) and (d) normalized effects of different concentrations on BPA removal.

and •OH in the Co@GAC-membrane/PMS system. These reaction steps

Table 2
can be described as Eq. (1)-Eq. (4), which have been accepted by most
Contribution of action in major regions of the system for BPA removal.
researchers [3,34–36].
Action of different GAC GAC/ Co@GAC Co@GAC/
regions adsorption PMS adsorption PMS GAC-Co(III) + HSO5− → GAC-Co(II) + SO5•− + H+ (1)
BPA removal 38.4% 12.1% 59.1% 33.7%
GAC-Co(II) + HSO5− → GAC-Co(III) + SO4 •−
+ OH −
(2)
Percentage 76.0% 24.0% 63.7% 36.3%
contribution
SO4 •−
+ H2O → SO42− •
+ OH + H +
(3)
•− •
SO4 + OH + BPA → intermediates → CO2 + H2O (4)
PMS system and the radicals were produced via the activation of PMS by
Co3O4. Furthermore, EPR spectroscopy was used to detect the reactive
radicals from the Co@GAC/PMS system using the spin-trapping agent
DMPO. Fig. 7b shows that the characteristic peaks of DMPO-SO4•− and
DMPO-•OH adducts were both detected, further confirming that SO4•− 3.5. Universality and stability
and •OH were generated in the system. Fig. 7c and d present the Co
species of the fresh and used Co@GAC by XPS analysis to understand the Various organic pollutants including 4-chlorophenol (4-CP), phenol,
catalytic effect on the generation of SO4•− and •OH in the Co@GAC- sulfadiazine (SDZ), and methylene blue (MB) were used in the system to
membrane/PMS system. The two peaks located at around 779.6 eV evaluate the removal performance of Co@GAC-membrane. Fig. 8a
and 780.7 eV were assigned to the Co(III) 2p3/2 and Co(II) 2p3/2, shows that 92.6% of 4-CP, 92.9% of phenol, 94.6% of SDZ, and 88.8% of
respectively, and the accompanying 2p1/2 spin–orbit component for Co MB were removed by the Co@GAC-membrane/PMS system during the
(III) and Co(II) appear at 795.0 eV and 796.2 eV, respectively. The filtration processes, exhibiting satisfactory universality of the integrated
different relative proportion of Co(III) and Co(II) before and after the process. Moreover, as shown in the inset of Fig. 8a, the Co@GAC-
reaction indicated that the redox circles of Co(III)/Co(II) on the membrane/PMS system also realized a relatively high TOC removal
Co@GAC were mainly responsible for PMS activation to generate SO4•− rate (40%~50%) for these various organic pollutants. The effect of
actual water matrix on BPA removal in the Co@GAC-membrane/PMS

6
S. Wang et al. Separation and Purification Technology 291 (2022) 120874

Fig. 7. (a) Effects of the radical scavengers in the PMS/Co@GAC-membrane system ([BPA]0 = 5 mg/L, [PMS]0 = 0.1 mM, Flux = 35 LMH), (b) EPR spectra of the
reaction in the presence of DMPO and high-resolution XPS spectra of Co 2p before (c) and after (d) catalytic reaction.

Fig. 8. (a) Versatile removal of organic pollutants by Co@GAC-membrane/PMS system and the inset shows the TOC removal efficiency, (b) effort of water quality on
BPA removal in the Co@GAC-membrane/PMS system ([Organic pollutant]0 = 10 mg/L, [PMS]0 = 0.2 mM, Flux = 35 LMH).

7
S. Wang et al.
system was also conducted using the water sample from Dingjiahe
Reservoir in Qingdao, China. As displayed in Fig. 8b, the BPA removal
efficiency in the systems using real water and DI water were both higher
than 93.0%, suggesting that the integrated process possesses a promising
potential for practical applications.
The stability and reusability of the Co@GAC-membrane were tested
by six cycles and the results are shown in Fig. 9. As shown in Fig. 9a, BPA
removal rates in the system still maintained at about 90 % after six
repeated runs. Co leaching concentration was less than 0.06 mg/L and
decreased with the increase of experimental cycles. In addition, crys­
talline structures of the fresh and used Co@GAC were monitored by XRD
diffraction pattern and shown in. Fig. 9b. In comparison to the fresh
sample, there was no discernible difference in the crystalline structure of
the used Co@GAC. Further, Fig. 9c and d confirmed that huge amounts
of catalyst were maintained on the Co@GAC surface after repeated
usage. The above results indicated that the integrated process exhibited
excellent reusability and possessed sustainable operation with high
performance.
4. Conclusions
A novel integrated process of ceramic membrane filtration combined
with PMS activation and adsorption by loading Co@GAC into the
membrane channels for organic pollutants removal was developed in
this work. The performance of organic pollutants removal and stability
of the strategy were systematically investigated.
Fig. 9. (a) BPA removal and metal ions leaching in the reusability test ([BPA]0 = 10 mg/L, [PMS]0 = 0.2 mM, Flux = 35 LMH), (b) XRD spectra of Co@GAC before
and after use and (c, d) SEM images of Co@GAC before and after use.
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Separation and Purification Technology 291 (2022) 120874
(1) Compared with pristine membrane and GAC-membrane,
Co@GAC-membrane exhibited higher BPA removal efficiency
in the presence of PMS due to the enhanced adsorption and PMS
activation of Co@GAC in the membrane channels.
(2) The operation flux of the Co@GAC-membrane/PMS system
played a key role in the removal of organic pollutant at lower
concentrations. The generated SO4•- and •OH in the Co@GAC-
membrane/PMS system were the main reactive species respon­
sible for BPA degradation according to the radical quenching tests
and EPR characterization.
(3) The Co@GAC-membrane/PMS system showed satisfactory
removal performance of various organic pollutants, even a su­
perior removal efficiency of BPA in actual water. Furthermore,
relatively high BPA removal rates in the system were still main­
tained and low Co leaching concentration was achieved during
multiple cycle experiments.
CRediT authorship contribution statement
Songxue Wang: Conceptualization, Methodology, Formal analysis,
Writing – original draft, Funding acquisition. Qianqian Wu: Visualiza­
tion, Writing – original draft. Boyin Yan: Investigation, Data curation.
Yuan Guo: Writing – review & editing. Wenxiang Xia: Validation,
Investigation. Jincheng Li: Methodology. Fuyi Cui: Conceptualization.
Jiayu Tian: Resources.
S. Wang et al.
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.
Acknowledgments
This work was supported by the National Natural Science Foundation
of China (No. 52100010) and the Natural Science Foundation of Shan­
dong Province (No. ZR2021QE185).
Appendix A. Supporting Information
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.seppur.2022.120874.
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