Chemical Engineering Journal 453 (2023) 139969

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Chemical Engineering Journal

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

Rotary-angle 3D printing multilayer membrane dead-end filtration for

rapid and highly efficient water treatment
Yujun Ju a, 1, Jianwei Zhang b, 1, Qinyu Cai c, 1, Zhengze Zhang a, Yan Zhao a, Jianguo Cui d,
Ruien Hou d, Yi Wei c, Zhiqiang Liang b, *, Fengjuan Chen a, *
a
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Gansu, Lanzhou 730000, China
b
Institute of Functional Nano & Soft Materials Laboratory (FUNSOM), Jiangsu Key Laboratory for Carbon Based Functional Materials & Devices, Soochow University,
Jiangsu, Suzhou 215123, China
c
Key Laboratory of Western China’s Environmental Systems (Ministry of Education) and Engineering Research Center of Fine Particle Pollution Control Technology and
Equipment of Gansu Province, College of Earth and Environmental Sciences, Lanzhou University, Gansu, Lanzhou 730000, China
d
Baotou Research Institute of Rare Earths, Inner Mongolia, Baotou 014000, China

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

Keywords: Polluted water caused by antibiotics leads to serious risks to human health and ecosystem. Rapidly and efficiently
Rotary 3D printing treating antibiotic pollutions to make it safe is urgently needed for environmental protection and public health.
Water treatment Herein, we report that ZIF-67 derived nano-cube Co3O4 as model catalysts were immobilized in the rotary-angle
Antibiotic pollutant degradation
three-dimensional (3D) printed multilayer reduced graphene oxide/carbon nanotubes (Co3O4/R-rGO/CNTs)
membrane for the highly efficient degradation of antibiotic pollutants through sulfate radical-based advanced
oxidation process (SR-AOP). The macropores in the designed Co3O4/R-rGO/CNTs membrane are distributed in a
rotationally staggered arrangement, which increases the opportunity for contaminant contact with the catalyst.
The micro-cellular structures formed by the freeze-casting treatment in Co3O4/R-rGO/CNTs membrane provide
abundant anchor sites for catalysts as-well-as plentiful active sites for catalytic reactions. The degradation effi­
ciency of the designed membrane toward aureomycin hydrochloride (CTC) reached 99.3% at a flux rate of 636.9
L m− 2 h− 1, which is increased by 100% comparing with the traditional 3D printing membrane with vertical
macroporous arrays. This strategy put forward a new idea for the efficient degradation of antibiotic pollutants
and has great application prospects in the field of environmental remediation.

1. Introduction Sulfate radical-based advanced oxidation process (SR-AOP) is one of

the most effective and promising wastewater treatment technology
Achieving sustainable use of water is vital for life and most industrial because of which it can produce abundant of reactive oxygen species
processes. Wastewater from pharmaceutical, agricultural and industrial (ROS) to decompose organic pollutants unselectively [11–14]. Recently,
use contains potentially threat to the environment and human healthy metal–organic frameworks (MOFs) derived metal oxides have received
[1,2]. Particularly, large quantities of antibiotic pharmaceuticals are tremendous attention in the treatment of organic pollution in water
widely used every day worldwide [3,4]. After use, antibiotic pharma­ because of its distinct advantages in terms of adjustable structures,
ceutical metabolites are discharged directly into the environment, seri­ diverse morphologies, large specific surface areas and abundant active
ously threatening the safety of drinking water [5]. Traditional water sites [15]. More importantly, carbon nanoscale’s generated from the
treatment methods include biodegradation [6] and adsorption [7,8]. carbonization process of MOF subunits not only increase the adsorption
The adsorption can only separate pollutants, which are difficult to performance toward organic pollutants but also prevent metal ion
effective degradation refractory organic pollutants in water [9,10]. leakage into the treated water [16]. Unfortunately, MOFs-based nano-
Therefore, it is highly desired to develop efficient, safe, and cost- catalysts are always in powdered configurations, which are tend to
effective techniques to degrade organic pollutants in water. agglomerate and difficult to be separated from the wastewater treatment

* Corresponding authors.
E-mail addresses: zqliang@suda.edu.cn (Z. Liang), chenfj@lzu.edu.cn (F. Chen).
1
These authors contributed equally.

https://doi.org/10.1016/j.cej.2022.139969
Received 20 August 2022; Received in revised form 12 October 2022; Accepted 18 October 2022
Available online 26 October 2022
1385-8947/© 2022 Elsevier B.V. All rights reserved.
Y. Ju et al. Chemical Engineering Journal 453 (2023) 139969

system [17], leading to poor reusability and secondary contamination. membrane for highly efficient activation PMS and effective degradation
Alternatively, membrane filtration integrated with MOFs-based of pollutants in water. The magnified image shows that Co3O4/R-rGO/
nano-catalysts has been explored as a fantastic candidate for practical CNTs features interlaced macropores, increasing the contact opportunity
polluted water treatment due to its low cost, low energy consumption, between pollutants and catalysts. Meanwhile, the existence of micro-
and easy operation [18–20]. To date, various membrane, such as cellular structure in the membrane increases the specific surface area,
ceramic [21], polymeric [22,23], or carbonic membranes [24,25], have offering abundant anchoring sites for Co3O4 and providing plentiful
been designed by blending or coating strategies to load nano-catalysts. catalytic active sites. Benefiting from the nano-cube Co3O4 and rGO in
However, most membranes suffer from poor mass transportation, low the Co3O4/R-rGO/CNTs membrane, PMS is activated through radical
activation performance toward PMS, and low organic pollutant degra­ and non-radical pathways to generate plenty of ROS, which can effi­
dation efficiency because of the dense microstructure, macro mass ciently decompose organic pollutants in wastewater (Fig. 1c). Therefore,
transfer channel, poor catalyst loadings, or insufficient contact between we combined rotary-angle 3D printing technology with SR-AOP for the
pollutants and catalysts [26]. Therefore, it is urgent to explore a novel highly efficient and rapid degradation of antibiotic pollutants in
membrane to realize the rapid and efficient degradation of antibiotic wastewater, which resulted in a novel, efficient, and promising strategy
pollutions in water. However, manufacturing such a membrane with for environmental remediation.
designed porous structures at different scales remains as a significant
challenge. 2. Experimental section
The fast-growing three-dimensional (3D) printing technology offers
a promising strategy to integrate various membrane materials into 2.1. Chemicals and materials
designed 3D structures [27–29]. In particular, 3D-printed reduced gra­
phene oxide (rGO)-based membranes featuring hierarchical porous Cobaltous nitrate hexahydrate ((Co (NO3)2⋅6H2O), 99%), 5,5-
structures have attracted great attention in the field of water treatment. dimethyl-1-pyrroline N-oxide (DMPO, 98%), 2,2,6,6-tetramethyl-1-
The micro-cellular structure is formed during the freeze-drying process, piperidinyloxy (TEMP, 98%), peroxymonosulfate (2KHSO5⋅KH­
offering a larger specific surface area to load more catalysts [30–32]. SO4⋅K2SO4), sulfamethoxazole (SMX, 98%), and levofloxacin (LEV,
The vertically aligned macro-channels in traditional 3D-printing rGO/ 98%) were purchased from Macklin. The graphite flakes (XF049, 50
CNTs (T-rGO/CNTs) improves water flux (Fig. 1a). However, the mesh) and multiwalled carbon nanotubes (CNTs) were purchased from
degradation efficiency is not satisfactory, due to the fact that polluted XFNANO Inc. and Tanfeng Tech Inc., respectively. Fuming nitric acid
water is inclined to transport through these vertical channels and cannot (HNO3, 98%) and concentrated sulfuric acid (H2SO4, 98%) were pur­
well contact the catalysts loaded on the T-rGO/CNTs membrane. chased from China Sun Specialty Products Co. Potassium permanganate
Therefore, desiging and manufacturing a membrane with hierarchical (KMnO4) and phosphorus pentoxide (P2O5) were purchased from Sino­
porous structures combining rapid water flux and high water treatment pharm Chemical Reagent Co., ltd. Ascorbic acid (AA) for GO reduction
efficiency is highly desirable. was purchased from Sigma Aldrich. 2-Methylimidazole, bisphenol A
Towards these aims, we design a rotary-angle 3D printing multilayer (BPA, 99%), and hydrogen peroxide (H2O2, 30%) were supplied by
reduced graphene oxide/carbon nanotubes (R-rGO/CNTs) membrane Aladdin. Cetyltrimethylammonium bromide (CTAB) was obtained from
with hierarchical porous structures for effective degradation of anti­ Shanghai Zhongqin Chemical Reagent Co. Chlortetracycline hydro­
biotic pollutants in wastewater by activating PMS. Note that the cross- chloride (CTC, 90%), tetracycline (TC), furfuryl alcohol (FFA, 98%),
linked CNTs were incorporated between the rGO sheets to enhance norfloxacin (NOR, 98%), potassium persulfate (K2S2O8) and benzoqui­
the mechanical strength of printed 3D structures [30]. The R-rGO/CNTs none (BQ, 97%) were obtained from Energy Chemical Reagent Co.
membrane consists of ten layers, in which each layer was printed by Methanol (MeOH) and tert-butylalcohol (TBA, 99%) were supplied by
rotary different angles to form staggered and interconnected macro­ Lianlong Tianjin Pharmaceutical Chemical Co.
scopic pore structure (Fig. 1b). Nano-cube Co3O4 particles generated
from ZIF-67 as a model catalyst were decorated on the R-rGO/CNTs

Fig. 1. a) Schematic diagram of the traditional 3D printing

membrane for the removal of pollution. The formation of a
larger number of vertically arranged macropores in the tradi­
tional 3D printing membrane. b) Schematic diagram of the ro­
tary -angle 3D printing membrane with a hierarchical porous
structure for highly effective water treatment. The rotary 3D
printing membrane generates interlaced macropores. c) Co3O4/
R-rGO/CNTs activating PMS generates ROS for highly efficient
degradation pollution.

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Y. Ju et al. Chemical Engineering Journal 453 (2023) 139969

2.2. Characterization membrane. Finally, the R-rGO/CNTs membrane was calcined in a tube
furnace at 300 ℃ for 60 min in an Ar atmosphere with a ramping rate of
Scanning electron microscopy (SEM, Apreo S, test voltage: 30 kV, 1 ℃ min− 1.
measurement model: SE, current: 3.2 nA) and transmission electron
microscopy (TEM, Tecnai F30, test voltage: 300 kV) were adopted to 2.4. Catalytic performance test
obtain the surface morphologies of the synthesized samples. The struc­
tural of materials were characterized via X-ray diffraction (XRD, D/Max- Aureomycin hydrochloride (CTC) was chosen as a model pollutant
2400). The functional groups on the surface of the samples were (10 ppm) to evaluate the catalytic performance of the Co3O4/R-rGO/
analyzed by X-ray photoelectron spectroscopy (XPS, Shimadzu Axis CNTs membrane. First, an all-in-one filter was designed and assembled
Supra). The presence of ROS in the degradation system was further by integrating of the Co3O4/R-rGO/CNTs membrane (diameter 2 cm,
proven by electron spin resonance (ESR, ER200DSRC10/12) spectra. thickness 1 cm) in a plastic kettle. Secondly, CTC contaminant (10 ppm)
The rheological properties of rGO/CNTs inks were analyzed by stress- and PMS (0.5 g/L) were added into the syringe. The catalytic reaction
controlled rheometer (Kinexus pro, Malvern). conditions are as follow: the concentration of CTC 10 ppm; PMS 0.5 g/L;
pH = 7; water flux: 636.9 L m− 2 h− 1.The different flow rates were set to
2.3. Synthesis of catalytic membrane assess the catalytic-filtration performance of the Co3O4/R-rGO/CNTs
membrane. The water flux was controlled by regulating the flow rate of
2.3.1. Acidification of CNTs injection pump during the contaminant degradation process. The CTC
The acidification treatment of CNTs was carried out according to the concentration in the water before and after treatment with the Co3O4/R-
following process: First, 1 g of CNTs, 11 mL HNO3 and 33 mL H2SO4 rGO/CNTs membrane was determined by UV–visible adsorption
were mixture and stirred at 90 ◦ C for 2.5 h to reflux. Secondly, the spectroscopy.
mixture solution was cooled to room temperature, which was diluted
with distilled water and pumped in a membrane extractor until the 2.5. Real wastewater treatment
pumped liquid was neutral. Finally, the obtained solution was concen­
trated was then concentrated by vacuum filtration to obtain acidified Yellow River water was obtained from the Yellow River in Lanzhou,
CNTs suspension. Gansu Province. Sea water was obtained from the South China Sea. The
water samples were filtered to remove the solid particulate before use.
2.3.2. rGO/CNTs ink preparation CTC pollutants were added into Yellow River water and sea water to
The rGO/CNTs ink was prepared according to the methods reported simulate real wastewater. The concentration of CTC in Yellow River
in the literature [30]. Briefly, the acidified CNTs were mixed into the water and sea water was 10 mg/L.
partially reduced GO solution under vigorous stirring to obtain a ho­
mogeneous dispersion. After that, the mixed solution was then
2.6. Computational fluid dynamics (CFD) simulations
concentrated by vacuum filtration into a 3D printable ink.
The computational fluid dynamics (CFD) simulations model was
2.3.3. 3D printing of the R-rGO/CNTs membrane
established based on the SEM analysis. A cylindrical computational
The R-rGO/CNTs membrane was performed on a homemade printer,
domain was determined with a radius of 100 mm and height of 100 mm.
including an industrial robotic dispenser (Fisnar F5200n), a ValveMate
The top and bottom boundary conditions of the cylindrical computa­
9000, and a controller with a computer. Before printing the rGO/CNTs
tional domain are set as the velocity inlet and pressure outlet, respec­
membrane, the rGO/CNTs ink was loaded into a syringe barrel fitted
tively. Water flows through the top at a rate of 200 mL h− 1 and flows out
with a pneumatic piston and a stainless-steel nozzle with a diameter of
from the bottom after contacting the membrane. Additionally, we as­
510 µm. The printing pressure and nozzle moving speed were set in the
sume that the computational domain is immersed in a water environ­
range of 80–120 kPa and 10–20 mm s− 1, respectively. Then, the target
ment at all times during the filtration process. Based on these conditions,
3D patterns were printed in ambient air with no need for any additional
we assume that the fluid flow during this simulation is stable, incom­
in situ curing treatment. In particular, by adjusting the printing pro­
pressible, laminar, and governed by the continuity and Navier-Stokes
gram, the printing angle of each layer in the rGO/CNTs grid can be
Eqs. (1) and (2):
precisely controlled, thus enabling the preparation of rGO/CNTs mem­
branes with a unique rotary-angle structure. ∇⋅u = 0 (1)
The printed samples were subjected to a quick freezing-cast treat­
ment in a liquid nitrogen bath and then freeze-dried to remove water. ρ(∇⋅u)u = − ∇⋅(pI) + ∇⋅(μ∇u) (2)
Finally, the dried samples were further annealed at 300 ◦ C for 2 h.
where u is the flow velocity vector, I is the identity tensor, p is the
2.3.4. Synthesis of nano-cube Co3O4 pressure, ρ and μ are the density and dynamic viscosity of water,
ZIF-67-derived Co3O4 was obtained according to previous literature respectively.
[33]. First, Co(NO3)2⋅6H2O (0.292 g) and CTAB (0.004 g) were dissolved
in 10 mL of deionized water. The above solution was then rapidly 2.7. Density functional theory (DFT) calculation
injected into 70 mL of deionized water containing 2-methyimidazole
(4.54 g) and stirred for 40 min. Secondly, the product was collected The density functional theory (DFT) calculations were conducted by
by centrifugation and washed. Finally, the as-prepared ZIF-67 was the Vienna ab initio Simulation Package (VASP 5.4.4). The calculation
annealed at 200 ℃ for 30 min with a heating rate of 1 ℃ min− 1 in air, models of Co-PMS, O–H–PMS, C–C–PMS, and C– – O-PMS were con­
further annealed at 300 ℃ for 30 min, and cooled to room temperature structed via Avogadro 2.0. The VASP was applied to optimize the
naturally. models. A structure model with a size of 17.43*12.09*16.27 Å was built.

2.3.5. Fabrication of Co3O4/R-rGO/CNTs membrane 3. Results and discussion

First, 5 g/L Co3O4 was dissolved in 10 mL ethanol solution, and the
catalyst was better dispersed by ultrasound for 30 min. Then, the R-rGO/ 3.1. Characterization of the Co3O4/R-rGO/CNTs membrane
CNTs (radius: 1 cm, thickness: 1 cm) membrane was impregnated
several times in Co3O4 solution to obtain Co3O4/R-rGO/CNTs Extrusion-based rotary 3D printing technology was employed to

3
Y. Ju et al. Chemical Engineering Journal 453 (2023) 139969

construct multilayer interlaced scaffolds with hierarchical porous mangnified SEM image shows the morphology of micron-sized cellualr
structures for highly efficient water treatment. An aqueous ink was structures in the R-rGO/CNTs membrane (Fig. 2e).
utilized for rotary 3D printing, which consists of partially reduced gra­ Nano-cube Co3O4 generated from ZIF-67 is widely utilized for SR-
phene oxide (rGO) and pre-dispersed carbon nanotubes (CNTs). The AOP through activation of PMS for efficient degradation of organic
printable ink should hold obvious shear-thinning behavior, high initial pollutants. Therefore, ZIF-67 derived nano-cube Co3O4 was chosen as a
storage modulus (G′ ), as well as adequate yield stress (τy) [34]. The model catalyst, which was decorated on the surface of R-rGO/CNTs
prepared rGO/CNTs ink exhibits excellent self-supporting ability, as membrane by the impregnation method. The actual load of Co3O4
demonstrated by its poor fluidity and solid-like appearance (Fig. S1). (15.79 wt%) was characterized by an inductive coupled plasma emission
Rheology measurements indicate that the rGO/CNTs ink features sig­ spectrometer (ICP). Co3O4 with a nano-cube morphology, rGO, and
nificant shear-thinning behavior, which indicates that rGO/CNTs ink is a CNTs can be seen in the transmission electron microscope (TEM) image,
non-Newtonian fluid. The rGO/CNTs inks can be smoothly extruded demonstrating that Co3O4 was successfully loaded in the R-rGO/CNTs
through the nozzle without clogging under appropriate printing pres­ membrane (Fig. 2f). High-angle annular dark field scanning TEM
sure (Fig. S2). Moreover, the very high G’ plateaus (~7 × 105 Pa) of the (HAADF-STEM) and elemental mapping images confirm that the ele­
rGO/CNTs ink imply that the newly extruded ink filaments have ments Co, O, and C are uniformly distributed in Co3O4 (Fig. 2g). The
excellent shape retention capacity and self-supporting behavior during presence of element C in Co3O4 is attributed to the thermal decompo­
the 3D printing process (Fig. S3) [35]. In addition, the G’ plateau is sition of the ligand of ZIF-67. The high-resolution transmission electron
significantly higher than the loss modulus (G“) plateau (~6 × 104 Pa), microscopy (HRTEM) image exhibits lattice fringes of Co3O4 (Fig. 2h).
which ensures that the printed 3D membrane maintains structural The interplanar distance of Co3O4 was 0.29 nm, which corresponds to
integrity without collapsing. the (2 2 0) planes of Co3O4 [36,37]. In addition, to evaluate the me­
As illustrated in Fig. 2a, each layer of the R-rGO/CNTs scaffold was chanical properties of the R-rGO/CNTs membrane, a stress–strain test
printed at a certain rotary angle. The entire membrane consists of 10 was carried out. The maximum compressive stress and compressive
layers with a thickness of 1 cm. The optical image of the R-rGO/CNTs strain of the R-rGO/CNTs membrane are approximately 29 kPa and
membrane is depicted in Fig. 2b, and numerous interlaced macroscopic 90%, respectively (Fig. 2i). These results suggested that the excellent
pores can be seen in the whole membrane. The printed schematic of the compressibility of R-rGO/CNTs membranes is caused by the 3D printed
R-rGO/CNTs membrane is shown in Fig. S4. The SEM image of the R- macroscopic pore and micro-cellular structure [31].
rGO/CNTs membrane top view displays a hierarchical porous structure, The crystal structure of different samples was analyzed using X-ray
including 3D printed interconnected macroscopic pores array, and diffraction (XRD). The diffraction peaks of Co3O4/R-rGO/CNTs conform
micro-cellualr structure formed under the extrusion of ice crystals to Co3O4 (JCPDS Card No: 43–1003) and rGO (JCPDS Card No:
(Fig. 2c). Cross sectional SEM image of the R-rGO/CNTs membrane 75–0444) (Fig. S5), which confirms that Co3O4/R-rGO/CNTs success­
presents the interlaced macropores, which is attributed to the rotary- fully formed. X-ray photoelectron spectroscopy (XPS) and Raman were
angle multilayer rGO/CNTs scaffold structure (Fig. 2d). The utilized to determine the surface chemical characteristics of samples.

Fig. 2. a) Schematic diagram of the rotary angle of each layer of R-rGO/CNTs scaffolds. b) Optical image of the Co3O4/R-rGO/CNTs membrane. c-e) SEM images of
Co3O4/R-rGO/CNTs membrane. f) TEM image of Co3O4/R-rGO/CNTs. g) HAADF STEM image and its corresponding elemental mapping of Co3O4. h) HRTEM image
of Co3O4. i) Stress–strain curves of the R-rGO/CNTs membrane.

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Y. Ju et al. Chemical Engineering Journal 453 (2023) 139969

The Raman spectra are depicted in Fig. S6. R-rGO/CNTs reveals two volume of the R-rGO/CNTs membrane [42]. The pore size distribution of
typical peaks ascribed to the D-band and G-band [38]. The peaks of all samples is mainly located in the mesopore (Fig. S10b). These results
nano-cube Co3O4 at 194 cm− 1, 483 cm− 1, and 622 cm− 1 correspond to suggested that the designed Co3O4/R-rGO/CNTs membrane serves as a
the F2g mode vibration. The peaks located at 522 cm− 1 and 693 cm− 1 promising candidate for efficient water treatment, which can be ascribed
correspond to Eg and A1g mode vibrations, respectively [39]. Compared to the Co3O4/R-rGO/CNTs membrane has excellent mechanical prop­
with pure Co3O4 and R-rGO/CNTs, the characteristic peaks of Co3O4/R- erties, good stability and sustainability in the water treatment process.
rGO/CNTs shifted to a lower wavenumber, suggesting that there existed
a strong interaction between R-rGO/CNTs and Co3O4. XPS measure­
ments were conducted to gain in-depth insights into the surface element 3.2. Comparison between R-rGO/CNTs and T-rGO/CNTs
compositions and valence states of the samples. Comparing the XPS
spectra of Co3O4/R-rGO/CNTs with those of R-rGO/CNTs and Co3O4, To investigate the influence of the interlaced macropores resulting
the characteristic peaks of Co 2p, O 2p, and C 1 s of the composite from the rotary 3D printing on the water treatment efficiency. We
matched well with those of pure R-rGO/CNTs and Co3O4 (Fig. S7–9). compared the water treatment performance of R-rGO/CNTs with that of
The XPS results show that Co3O4/R-rGO/CNTs was successfully pre­ T-rGO/CNTs under the same reaction conditions. The cross-section
pared, and interactions existed between R-rGO/CNTs and Co3O4 schematic images of R-rGO/CNTs and T-rGO/CNTs are shown in
[40,41]. Moreover, the Brunauer-Emmett-Teller surface area and pore Fig. 3a and b. Rotary 3D printing creates numerous interlaced macro­
size distribution of the samples were measured by N2 adsorp­ pores in the whole membrane, which promotes sufficient contact be­
tion–desorption isotherm measurements at 77 K. The specific surface tween pollutants and the catalyst. In contrast, T-rGO/CNTs membranes
areas of R-rGO/CNTs, Co3O4, and Co3O4/R-rGO/CNTs were 141.92 m2 form vertically arranged macropores in the membrane. Aureomycin
g− 1, 64.96 m2 g− 1, and 108.03 m2 g− 1, respectively (Fig. S10a). These hydrochloride (CTC) is a common antibiotic with strong antibacterial
results show that the specific surface area of R-rGO/CNTs decreased and anti-inflammatory effects that is widely applied in daily life. Trace
after loading Co3O4, which was attributed to the reduced mesopore amounts of antibiotics in water are difficult to degrade through tradi­
tional water treatment methods because of their high chemical stability.

a) b) c)

Degradation efficiency (%)

100

80

60

40

20

0
Co3O4/R-rGO/CNTs Co3O4/T-rGO/CNTs
R-rGO/CNTs T-rGO/CNTs
d) e)

f) g)

Fig. 3. Schematic of the cross section of the a) R-rGO/CNTs membrane and b) T-rGO/CNTs membrane. c) Comparison of the degradation efficiency of Co3O4/R-rGO/
CNTs and Co3O4/T-rGO/CNTs. d) The fluid velocity contours of R-rGO/CNTs along the Z-axis. e) The fluid velocity contours of T-rGO/CNTs along the Z-axis. f)
Streamline chart of R-rGO/CNTs along the Z-axis. g) Streamline chart of T-rGO/CNTs along the Z-axis.

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Y. Ju et al. Chemical Engineering Journal 453 (2023) 139969

Therefore, we chose CTC as a model pollutant to assess the water 3.3. Catalytic performance of the Co3O4/R-rGO/CNTs membrane.
treatment performance of Co3O4/R-rGO/CNTs and Co3O4/T-rGO/CNTs.
The experimental setup was prepared by assembling the Co3O4/R-rGO/ 3.3.1. Study of the degradation performance of the Co3O4/R-rGO/CNTs
CNTs membrane into a filter, which was utilized for the degradation of membrane
antibiotic pollutants (Fig. S11). The water flux is precisely controlled by A schematic diagram of the degradation of pollution by the Co3O4/R-
adjusting the flow rate of injection pump. The flux of the treatment is rGO/CNTs membrane is illustrated in Fig. 4a. The contaminants were
calculated with equation (3): degraded by the Co3O4/R-rGO/CNTs membrane. The degradation per­
formance of the Co3O4/R-rGO/CNTs membrane was explored by
V
W= (3) adjusting the water flux (Fig. 4b). The results showed that the degra­
S
dation efficiency of the Co3O4/R-rGO/CNTs membrane for the CTC
where V is the flow rate of the syringe pump (L h− 1), S is the effective pollutant reached 93.6% when the water flux was 1.27 × 103 L m− 2 h− 1.
area of the Co3O4/R-rGO/CNTs membrane (m2), and W is the treatment The absorption peak for CTC pollution (367 nm) completely disappeared
flux (L m− 2 h− 1). after the pollutants were degraded by the Co3O4/R-rGO/CNTs mem­
The calculation formula of degradation efficiency as following: Eq. brane (Fig. S12), which suggests that the CTC pollutant was decom­
(4): posed. In addition, the effect of thickness of membrane on removal
efficiency was explored. As depicted in Fig. S13, compared with the
C0 − C
Degradation efficiency (%) = 100 × ( ) (4) catalytic membrane with 10 layers, the removal efficiency of the cata­
C0 lytic membrane with 15 layers is hardly improved. Considering the
energy consumption of the membrane material, we chose 10 layers of
where C0 and C are the CTC concentrations before and after Co3O4/T-
catalytic membrane as our research object. When the catalytic mem­
rGO/CNTs membrane treatment, respectively.
brane is 5 layers, the degradation performance is relatively poor, which
The Co3O4/T-rGO/CNTs membrane displays a lower degradation
is mainly attributed to the insufficient contact between catalyst and
efficiency of 49.6% toward CTC, which is attributed to the majority of
pollutant. The influence of pH on the degradation efficiency of the
polluted water being transported through the 3D printed vertical
Co3O4/R-rGO/CNTs membrane is depicted in Fig. 4c. The results
arrayed channels. In contrast, the Co3O4/R-rGO/CNTs membrane ex­
demonstrate that the Co3O4/R-rGO/CNTs membrane displays an
hibits a high degradation efficiency of 99.3% for CTC pollution under
excellent degradation efficiency for CTC in the pH range of 3–7. When
the same reaction conditions (Fig. 3c). The outstanding water treatment
the pH value is higher than 7, the treatment efficiency dramatically
performance of the designed Co3O4/R-rGO/CNTs membrane can be
decreases, which can be explained by the following reasons: (1) abun­
attributed to the curved water flow channels in the rotary-angle struc­
dant SO2− 2−
5 and SO4 are generated from the activation process of PMS
ture. The staggered channel structure in the rotary-angle structure in­
[44], leading to poor degradation efficiency. (2) The surface of the
creases the length of the path that the effluent needs to pass through the
catalyst adsorbs excessive OH− , limiting the interaction between the
membrane, which in turn enhances the chance of contact between
catalyst and PMS. The long-term stability and cycle stability of the
catalyst and pollutant.
Co3O4/R-rGO/CNTs membrane determine whether it can be applied in
Additionally, we applied computational fluid dynamics (CFD) sim­
practical wastewater treatment. In order to prove that the Co3O4/R-
ulations to explore the transport model of polluted water flowing
rGO/CNTs membrane still has a good removal efficiency on the low
through R-rGO/CNTs or T-rGO/CNTs membranes [43]. Water flow was
concentration of CTC pollutants. As shown in Fig. S14, the Co3O4/R-
kept laminar throughout the simulation. However, due to the interlaced
rGO/CNTs membrane shows outstanding degradation efficiency for low
macropores formed by rotary 3D printing, the flow pattern of polluted
concentration of CTC pollutants (1 ppm), which demonstrates that the
water of in membrane will be disturbed to a certain extent. The
Co3O4/R-rGO/CNTs membrane can remove different concentrations of
diffusion-convection process between the fluid and the membrane is
CTC pollutants and has certain universality. The long-term stability of
promoted, which improves the reaction time of pollutants on the cata­
the Co3O4/R-rGO/CNTs membrane was evaluated by continuous
lyst surface. The fluid velocity contours along the Z-axis of the R-rGO/
running for 12 h. As shown in Fig. 4d, the degradation efficiency was
CNTs membrane are shown in Fig. 3d. The calculated results demon­
maintained at approximately 94.7% after 12 h of continuous running. In
strated that the intricately arranged and interlaced pore structure of the
addition, after repeated use 5 times, the degradation performance of the
R-rGO/CNTs membrane led to intermittent changes in the flow direc­
Co3O4/R-rGO/CNTs membrane did not obviously decrease (Fig. S15).
tion, which dramatically “disturbed” the unidirectional fluid flow. The
These results demonstrate that the Co3O4/R-rGO/CNTs membrane ex­
existence of such a “disturbance” could help the pollution sufficiently
hibits good long-term stability and cycle stability, and had a certain
contact the catalyst and increase the degradation efficiency. The fluid
application prospect. The structure stability of the after-used Co3O4/R-
velocity contours of the Z-axis of the T-rGO/CNTs membrane are
rGO/CNTs membrane was studied via XRD. The XRD patterns after
depicted in Fig. 3e. An amount of vertically arranged macropores was
using Co3O4/R-rGO/CNTs match well with those before use, demon­
formed by the T-rGO/CNTs membrane, resulting in unidirectional flow
strating its good structural stability (Fig. S16). Additionally, inductive
of the fluid along vertical channels as well as poor water treatment ef­
coupled plasma emission spectrometer (ICP) was applied to test the
ficiency. Additionally, the streamline chart is shown in Fig. 3f and g.
amount of leaching of Co ions. As depicted in Fig. S17, after continuous
Compared with the T-rGO/CNTs membrane, the flow state of the R-rGO/
treatment of 1600 mL wastewater by Co3O4/R-rGO/CNTs membrane,
CNTs membrane is chaotic and tends to transition to turbulence. The
the concentration of Co ion in aqueous solution is less than 1 ppm [45],
turbulence state of the R-rGO/CNTs membrane will consume part of the
which proved that the leaching amount of Co ions does not cause harm
energy of the flow, thus reducing the kinetic energy of the fluid and
to the environment.
allowing pollution to sufficiently contact the catalyst. As a result, the
Except for CTC, we further investigated the degradation performance
interlaced macropores formed by rotary 3D printing not only disturb the
of the Co3O4/R-rGO/CNTs membrane for other common antibiotic
unidirectional flow of polluted water but also improve the contact op­
pollutants in water, such as tetracycline (TC), levofloxacin (LEV), nor­
portunity between pollutants and catalyst, leading to rapidly and highly
floxacin (NOR), and sulfamethoxazole (SMX). The chemical structure
efficient water treatment.
and physical–chemical properties of the chosen antibiotics are demon­
strated in Fig. S18 and Table S1. The detection methods of different
antibiotics are shown in Table S2. The degradation efficiency of the
Co3O4/R-rGO/CNTs membrane toward TC, LEV, NOR, and SMX reached
95.6%, 95.4%, 91.9%, and 97.4%, respectively. These results indicate

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Y. Ju et al. Chemical Engineering Journal 453 (2023) 139969

a) b) c)

Degradation efficiency (%)

100

Degradation efficiency (%)

100
Polluted water
80 80

60 60

40 40

20 20

0
0
0.0 0.3 0.6 0.9 1.2 2 4 6 8 10
Co3O4/R-rGO/CNTs 3
Flux (10 L∙m ∙h ) -2 -1
pH
membrane d) e) 100

Degradation efficiency (%)

100

Degradation efficiency (%)

80
80

60 60

40 40

20 20

Clean water 0
0
2 4 6 8 10 12 TC LEV NOR SMX
Continuous run (h)
f) 100
g) h)
TOC removal efficiency (%)

Degradation efficiency (%)

Degradation efficiency (%)

100 100
80
80 90
60
60 80

40 40 70

20 20 60

0 0 50
SMX TC LEV NOR TCT DI w S
Y 0 100 200 300 400 500 600
ater ellow riv ea water Flux (L m-2 h-1)
er

Fig. 4. The degradation efficiency of the Co3O4/R-rGO/CNTs membrane. a) Schematic diagram of water treatment by Co3O4/R-rGO/CNTs membrane. b) Degra­
dation efficiency under different water fluxes. c) Degradation efficiency at different pH values. d) Long-term stability. e) Degradation efficiency of different antibiotic
pollutants. f) TOC removal efficiency of different antibiotic pollutants. g) Degradation efficiency at different water sources. h) Comparisons of the degradation ef­
ficiency of Co3O4/R-rGO/CNTs with other materials. Reaction conditions: CTC, 10 ppm; PMS, 0.5 g/L; pH = 7; water flux: 636.9 L m− 2 h− 1.

that the Co3O4/R-rGO/CNTs membrane also has a fantastic degradation excellent water treatment performance as well as high water flux. The
efficiency for different kinds of antibiotic pollutants (Fig. 4e). Moreover, outstanding degradation efficiency of the Co3O4/R-rGO/CNTs mem­
the degree of mineralization of pollutants in the reaction system was brane for pollutants is ascribed to the following reasons: (1) the inter­
investigated, and the change in the concentration of total organic carbon laced macropores of the Co3O4/R-rGO/CNTs membrane enable
(TOC) was monitored during the degradation process. As illustrated sufficient contact between pollutants and the catalyst; (2) the existence
in Fig. 4f, the TOC removal efficiency toward SMX, TC, LEV, NOR, and of micro-cellular structure increases the loading amount of the catalyst
CTC by the Co3O4/R-rGO/CNTs membrane reached 78.7%, 63.0%, and provides abundant active sites; (3) the hierarchical porous structure
69.4%, 79.6%, and 43.5%, respectively. This result demonstrates that of the catalytic membrane can effectively enrich pollutants, while R-
the Co3O4/R-rGO/CNTs membrane exhibited an excellent mineraliza­ rGO/CNTs and Co3O4 synergistically activate PMS for degradation
tion performance for antibiotic contaminants. We also studied the pollutants; and (4) the large specific surface areas of nano-cube Co3O4
removal efficiency of the Co3O4/R-rGO/CNTs membrane for CTC derived from ZIF-67 exhibit high catalytic activity.
pollution in different water resources, such as Yellow River water and
sea water. The results suggest that the degradation efficiency of CTC in 3.3.2. The possible degradation pathway and toxicity assessment of CTC
Yellow River water and sea water was slightly lower than that of DI pollution
water (Fig. 4g), which was ascribed to the existence of other organic High-performance liquid chromatography-mass spectrometry
pollutants in real water samples that would consume part of the ROS (HPLC-MS) was carried out to explore the intermediates generated from
generated from PMS (Table S3) [46]. To compare the Co3O4/R-rGO/ the CTC degradation process. The mass spectrometry of the possible
CNTs membrane performance with other materials, bisphenol A (BPA) intermediate products is depicted in Fig. S20. Intermediate products
was selected as the target pollutant. As depicted in Fig. S19, the Co3O4/ with m/z values of 116, 150, 216, 226, 274, 318, 372, and 479 were
R-rGO/CNTs membrane shows 99.9% degradation efficiency for BPA detected by positive ionization mode of the MS spectra. Based on pre­
pollution under a water flux of 636.9 L m− 2 h− 1. We chose to compare vious reports, the possible degradation pathways of CTC are depicted in
the water treatment efficiency and the water flux of the Co3O4/R-rGO/ Fig. S21. The toxicity of CTC pollutants and possible degradation in­
CNTs membrane with those of other materials (Fig. 4h and Table S4). termediates was assessed by a toxicity estimation software tool (TEST).
The results indicate that the Co3O4/R-rGO/CNTs membrane realized an The daphnia magna LC50-48 h, fathead minnow LC50-96 h, and

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Y. Ju et al. Chemical Engineering Journal 453 (2023) 139969

mutagenicity were investigated by the quantitative structure–activity decreased, indicating that the possible existence of •SO−4 and •OH.
relationship method. As shown in Fig. S22 CTC with a daphnia magna Compared with addition of EtOH, the degradation efficiency of addition
LC50-48 h value of 3.55 mg L− 1 was considered “toxic”, while the of TBA has no obviously change, which proves that •OH plays a key role
toxicity of intermediates produced after CTC degradation gradually in the degradation process of pollutants. The existence of FFA markedly
decreased. Similarly, the CTC of the fathead minnow had an LC50-96 h inhibited the removal efficiency of CTC pollutants, demonstrating that
value of 0.32 mg L− 1, which was the “very toxic” level (Fig. S23). After 1
O2 played a dominant role during the CTC pollutant degradation pro­
degradation, the LC50-96 h values of almost all intermediates were cess. ESR measurements were used to further verify the presence of ROS.
higher, and the toxicity was obviously weakened. For mutagenicity We chose DMPO as a spin trapping agent to detect •OH and •SO−4 , and
toxicity (Fig. S24), CTC pollutants are considered mutagenic chemicals. TEMP was used to detect 1O2. The intensity ratio with 1:2:1: 2:1:2:1 of
After CTC degradation, the mutagenicity of most of the degraded in­ the characteristic peak of DMPOX can be cleanly observed, which was
termediates decreased to “mutagenicity negative”. Therefore, the design generated by the over oxidation of •SO−4 and •OH (Fig. 5b) [47,48]. In
of Co3O4/R-rGO/CNTs/PMS is an environmentally friendly water TEMP-1O2 spectra, the standard 1:1:1 triplet signal ascribed to 1O2 can
treatment system. It is important to note that toxic intermediates are be easily recognized, demonstrating the existence of 1O2 in the Co3O4/R-
produced during the degradation process, so a high degree of oxidation rGO/CNTs/PMS system. According to the above results, the main ROS in
or mineralization is required to ensure the safety of the treated water. the activation process of PMS by Co3O4/R-rGO/CNTs was 1O2.

3.4.2. Investigation of the electron transfers in the Co3O4/R-rGO/CNTs/

3.4. Mechanism analysis of PMS activation by Co3O4/R-rGO/CNTs
PMS system
The electron transfers between Co3O4/R-rGO/CNTs and PMS were
3.4.1. Identification of reactive oxygen species
investigated by electrochemical impedance spectroscopy (EIS) and
Quenching experiments and electron spin resonance (ESR) tests were
linear sweep voltammetry (LSV). The EIS curve is shown in Fig. 5c.
carried out to explore the contribution of different ROS to the degra­
Co3O4/R-rGO/CNTs has a smaller semicircle diameter than R-rGO/CNTs
dation of CTC pollutants during the activation of PMS by the Co3O4/R-
and Co3O4, proving that Co3O4/R-rGO/CNTs exhibited lower resistance
rGO/CNTs membrane. We chose benzoquinone (BQ), tert-butyl alcohol
and easier electron transfer. Therefore, Co3O4/R-rGO/CNTs is a good
(TBA), and furfuryl alcohol (FFA) as scavengers for •O−2 , •OH, and 1O2,
candidate to act as an electron transfer mediator during the PMS acti­
respectively. Ethanol (EtOH) is generally considered an effective scav­
vation process. The LSV curve was depicted in Fig. 5d, when only
enger for both •SO−4 and •OH. As depicted in Fig. 5a, it is apparent that
Co3O4/R-rGO/CNTs was present, there was no apparent current
the CTC removal efficiency slightly declines after the addition of BQ,
response. With the addition of PMS, the current density markedly
suggesting that •O−2 play a minor role in the Co3O4/R-rGO/CNTs/PMS
increased, suggesting that PMS interacted with Co3O4/R-rGO/CNTs to
system. After the addition of EtOH, the degradation efficiency partially

Fig. 5. a) Quenching experiments in the Co3O4/R-rGO/CNTs/PMS system. b) Spin-trapping EPR spectra. c) EIS analysis of different samples. d) LSV analysis of the
different reaction systems. e) In-situ Raman spectra of different reaction systems. f) ATR-IR spectra of different reaction systems. Adsorption model of g) C–C–PMS,
h) O–H–PMS, i) C– – O-PMS, and j) Co3O4-PMS.

8
Y. Ju et al. Chemical Engineering Journal 453 (2023) 139969

form the metastable reactive complex [49]. In regard to the coexistence calculations [55]. The possible active sites of PMS activation include
of PMS and CTC pollutants, the current density is further enhanced, Co3O4, O–H, C–C and C– – O. The optimized structures of the four
implying electron transfer from CTC pollution (electron donors) to the models are presented in Fig. 5g-j. To explore the activation effect of
Co3O4/R-rGO/CNTs-PMS complex (electron acceptor) [50]. Co3O4/R-rGO/CNTs on PMS, the adsorption energy of Co3O4-PMS,
Additionally, in-situ Raman and in-situ attenuated total reflection O–H–PMS, C–C–PMS, and C– – O-PMS models were investigated. As
infrared (ATR-IR) were used to explore the surface chemistry evolution shown in Table S5, the adsorption energies of O–H, C–C, and C– –O
of Co3O4/R-rGO/CNTs during the PMS activation process. The in-situ were 4.543 eV, − 4.427 eV and − 5.428 eV, respectively. The adsorption
Raman spectra of PMS and Co3O4/R-rGO/CNTs/PMS are illustrated in energy of active site O–H was 4.543 eV, which is ascribed to the gen­
Fig. 5e. The peaks at 1061 and 982 cm− 1 in PMS solution correspond to eration of H2O during the adsorption process. Compared with the
the stretching vibration of the O–O bond in HSO−5 , the symmetrical adsorption energies of C–C, C– – O exhibited higher adsorption energies.
stretching vibration of SO2−
4 , respectively. In the Co3O4/R-rGO/CNTs/ Furthermore, the O–O bond length of PMS (lO-O 1.350 Å) was signifi­
PMS system, we observed a new peak at 918 cm− 1, which could be the cantly prolonged from 1.478 Å (O–H–PMS) to 1.466 Å (C–C–PMS)
complex formed by Co3O4/R-rGO/CNTs and PMS. After the addition of and 1.489 Å (C– – O-PMS), which was beneficial for the cleavage of the
Co3O4/R-rGO/CNTs, the peaks of PMS disappeared at 1061 cm− 1, which O–O bond. The above results demonstrated the strongest charge
proved that the addition of Co3O4/R-rGO/CNTs caused the rupture of transfer between C– – O and PMS. The C– – O might be the major active
the peroxide bond of PMS and produced ROS. ATR-IR spectra are site for PMS activation through non-radical pathways. In addition, the
depicted in Fig. 5f, and the sharp peaks at 713 cm− 1, 1101 cm− 1, and fracture energy of the active site of Co2+ is − 6.807 eV, which proves that
1242 cm− 1 were assigned to the symmetric or asymmetric stretching Co2+ causes the rupture of the peroxide bond in PMS to produce •OH
vibrations of the O–O bonds of PMS. With the addition of Co3O4/R- [56]. Based on the above discussion, the possible active sites of PMS
rGO/CNTs, the characteristic peak of PMS red shifts, which indicates the – O and Co2+ in Co3O4/R-rGO/CNTs.
activation are C–
existence of electron-donating/withdrawing reactions between Co3O4/
R-rGO/CNTs surface active sites and PMS [51,52]. The ATR-IR results 3.5. The possible mechanism of PMS activation by Co3O4/R-rGO/CNTs
demonstrate that there exists a strong interaction between the Co3O4/R-
rGO/CNTs surface and PMS [53]. Therefore, from the above experi­ Based on these results, we propose a possible mechanism of PMS
mental results, we can demonstrate that the non-radical electron activation. Co3O4/R-rGO/CNTs activated PMS with both radical and
transfer process occurs in the activation process of PMS by Co3O4/R- non-radical pathways, while the latter played a dominant role in the
rGO/CNTs [54]. First, PMS and CTC pollution adsorbed on the surface of degradation of CTC. As shown in Fig. 6, according to theoretical calcu­
Co3O4/R-rGO/CNTs surface. Meanwhile, the adsorbed PMS is activated lations results, cobalt divalent and C–
– O in Co3O4/R-rGO/CNTs as the
to form complexes. Finally, the complexes will obtain electrons from the main active site activation of PMS generates reactive species that
CTC pollution to decompose pollutants. degrade antibiotic contaminants. In the radical pathway, the divalent
cobalt of Co3O4/R-rGO/CNTs as an electron donor provides an electron
3.4.3. Exploration of the possible catalytic active sites to activate PMS to generate •SO−4 and •OH, while the •SO−4 reacts with
The possible active site of the activation of PMS by Co3O4/R-rGO/ OH− to generate •OH (equation: 5–7). The non-radical route, carbonyl
CNTs was further explored by density functional theory (DFT) (C–– O) functional groups of Co3O4/R-rGO/CNTs as the main active sites

Fig. 6. Possible activation mechanism of PMS by Co3O4/R-rGO/CNTs.

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Y. Ju et al. Chemical Engineering Journal 453 (2023) 139969

that activate PMS through nucleophilic addition to generate 1O2, is excellent degradation performance for antibiotics pollutants, including
depicted in equations 8–11 [57]. Then, the reactive species of •SO−4 , •OH, TC, LEV, NOR, SMX, and CTC pollutants, reaching 95.6%, 95.4%,
and 1O2 attacked the CTC pollutant to produce small molecules. In 91.9%, 97.4%, and 99.3%, respectively, at a water flow up to 636.9 L
addition, non-radical electron transfer process also exists in the catalyst m− 2 h− 1. The main reasons can be summarized as follow: (1) Rotary-
system. Electrons are transferred from the CTC contaminants (electron angle 3D printing created plentiful interlaced macropores that disrupt
donor) to the PMS (electron acceptor) via catalysts (electronic bridge), the unidirectional flow of water as well as enhance the contact time of
thereby facilitating the decomposition of the CTC. pollutants on the catalytic membrane; (2) The interconnected micro-
cellular structure provides abundant anchor site for catalysts as well
Co2+ + HSO−5 → Co3+ + ⋅SO−4 + OH − (5)
as abundant active sites for catalytic reactions. Therefore, the interlaced
macropores and interconnected micro-cellular structures are integral to
⋅SO−4 + OH − → SO2−4 + HO⋅ (6)
obtaining desirable degradation performance for pollutants. Further­
more, the catalytic mechanism was explored by quenching experiment,
Co2+ + HSO−5 → Co3+ + SO2−4 + HO⋅ (7)
ESR test, electrochemical measurements, and DFT analysis. Experi­
mental and theoretical results shown that the main active sites in the
catalytic process are the functional group C– – O and the divalent cobalt.

(8)

(9)

(10)

(11)

In the process of Co3O4/R-rGO/CNTs membrane activation of PMS,

reactive oxygen species (ROS) are generated through the synergistic
action of radical and non-radical pathways to degrade antibiotic pol­
lutants. Hence, this work provides a sustainable and promising catalytic
membrane that not only efficiently and rapidly degrades antibiotic
contaminants in water, but also has potential application prospects in
the field of environmental remediation.

CRediT authorship contribution statement

4. Conclusion
Yujun Ju: Conceptualization, Methodology, Investigation, Writing –
In summary, we designed a nano-cube Co3O4 to be decorated on a original draft, Data curation. Jianwei Zhang: Methodology, Data
rotary 3D-printed rGO/CNT (Co3O4/R-rGO/CNTs) membrane with hi­ curation, Investigation. Qinyu Cai: Formal analysis. Zhengze Zhang:
erarchical porous structures, which can be utilized to rapidly and effi­ Investigation, Formal analysis. Yan Zhao: Software. Jianguo Cui:
ciently degrade antibiotic contaminants in water by activating PMS. The Software. Ruien Hou: Methodology. Yi Wei: Formal analysis. Zhiqiang
results shown that the Co3O4/R-rGO/CNTs membrane exhibited an Liang: Supervision, Writing – review & editing. Fengjuan Chen:

10
Y. Ju et al. Chemical Engineering Journal 453 (2023) 139969

Supervision, Writing – review & editing, Funding acquisition, Resources. [13] J. Miao, Y. Zhu, J. Lang, J. Zhang, S. Cheng, B. Zhou, L. Zhang, P.J.J. Alvarez,
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