Colloids and Surfaces A: Physicochemical and Engineering Aspects 686 (2024) 133431

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Preparation of PVDF mixed matrix membrane based on hydrophilic imine

type covalent organic framework(COF) for dye and salt separation
Yiwei Pan b, Zixun Li b, Shusu Shen a, b, *, Dapeng Liu a, b, Ganwei Zhang a, b
a
Jiangsu Engineering Research Center for Separation and Purification Materials and Technology, 1 Kerui Road, Suzhou 215009, China
b
School of Environmental Science and Engineering, Suzhou University of Science and Technology, 1 Kerui Road, Suzhou 215009, China

G R A P H I C A L A B S T R A C T

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

Keywords: Due to its high porosity, excellent chemical stability, and low density, covalent organic frameworks have been
Covalent organic frameworks widely researched in membrane separation technology. This study prepared COF-LZU1 PVP/PVDF membranes
Blend membrane with different loadings of covalent organic framework (0–0.8 wt% COF-LZU1) synthesized by the room tem­
Dye/salt separation
perature method incorporated into a polyvinylpyrrolidone (PVP) /polyvinylidene fluoride (PVDF) matrix. The
Membrane modification
addition of hydrophilic COFs improved the hydrophilicity of the membrane, reducing the water contact angle on
the membrane surface from 79◦ (PVDF membrane) to 58◦ (optimized membrane, M0.4). The water permeance of
membranes was improved by 2.3 times by incorporating 0.4 wt% COF-LZU1 nanoparticles. Moreover, the
rejection ratio for eriochrome black T (CBT), acid red (AR), congo red (CR), and methylene blue (MB) are all
higher than 94.5%. Furthermore, it exhibits excellent permeance of 19.37 L⋅m− 2⋅h− 1⋅bar− 1 in the mixed solution
of CR and NaCl, with respective rejection of 96.3% and 1.6%. The BSA filtration test demonstrated that after
three cycles, the FRR of COF-LZU1 PVP/PVDF membrane reached 91.52%. Generally speaking, incorporating
COF-LZU1 into PVDF polymer matrix can lead to the preparation of membranes with excellent anti-fouling
properties for dye separation and dye/salt separation purposes.

* Corresponding author at: Jiangsu Engineering Research Center for Separation and Purification Materials and Technology, 1 Kerui Road, Suzhou 215009, China.
E-mail address: shusushen@mail.usts.edu.cn (S. Shen).

https://doi.org/10.1016/j.colsurfa.2024.133431
Received 18 December 2023; Received in revised form 31 January 2024; Accepted 5 February 2024
Available online 7 February 2024
0927-7757/© 2024 Elsevier B.V. All rights reserved.
Y. Pan et al.
1. Introduction
Today, with the severe destruction of the ecological environment,
the protection of water resources and the control of water pollution have
become one of the most concerning issues in modern society. Harmful
dyes with aromatic ring structures are a special type of pollutant which
possess complex structures, low biodegradability, and potential toxicity
[12]. Several methods have been investigated to remove dyes from dye
wastewater, including adsorption [43], coagulation/flocculation [37],
and biological or chemical degradation [2]. In addition, membrane
separation technology is another widely used technique [36]. Compared
to other methods, membrane separation technology is widely recog­
nized for its advantages in good selectivity, ease of operation, and high
efficiency [38]. However, dye molecules are very small in size, often at
the nanometer level. Membranes with ordinary large pore sizes are
difficult to efficiently reject dye molecules through size sieving. In order
to prepare membrane materials with small pore sizes, researchers have
modified membrane materials in various ways to optimize the filtration
performance of the membrane.
In recent years, graphene oxide [33], metal-organic frameworks
(MOFs) [28], and zeolites [23]have been widely applied in the prepa­
ration of membrane materials. Covalent organic frameworks (COFs) are
a class of crystalline materials with ordered, porous structures formed
through the reversible aggregation of light elements such as C, H, O, N,
and B under thermodynamic control [4]. They possess low density, good
chemical stability, high surface area, and simple functional design as
characteristic features [35,40]. COF-modified membranes have wide
applications in various fields, such as gas separation [7], fuel cells [19],
pervaporation [42], organic solvent nanofiltration [13], due to their
stable structure and chemical properties, which make them strong
candidates for membrane separation.
Until now, there have only been a few reports on using COFs as
additives to prepare mixed matrix membranes(MMMs) for water reme­
diation. Most studies have focused on the preparation of composite
membranes for gas and liquid separation through methods such as
interfacial polymerization or in-situ generation [14]. In 2022, Zhang
and co-workers [45] prepared imine-linked COF-modified membranes
on the surface of polyethersulfone (PES) ultrafiltration membranes using
terephthalaldehyde (PDA) and 1,3,5-tris(4-aminophenyl)benzene
(TAPB) as monomers. The hydrophilic COFs improved the
Scheme 1. Preparation process of COF-LZU1/PVP PVDF membrane.
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Colloids and Surfaces A: Physicochemical and Engineering Aspects 686 (2024) 133431
hydrophilicity of the membrane surface, facilitating the rapid passage of
water molecules through the membrane, and also significantly enhanced
its fouling resistance. Fang et al. [8] prepared a novel clover-like
structured nylon membrane between meta-position monomer m-phe­
nylenediamine (MPD) and Benzene-1,3,5-tricarbaldehyde (TFB) via
interfacial polymerization. Compared to the previous hexagonal struc­
ture COFs membranes, the modified membrane has smaller channel size
and can improve the transport pathway of water molecules. In addition,
the membrane materials prepared by the blending method are difficult
to reach very small pore sizes, and it is often difficult to trap smaller salt
ions. Therefore, they have great application prospects in the field of
dye/salt separation. In 2022, Zhou et al. [46] successfully prepared a
novel polysulfate (PSE)-based tight ultrafiltration (TUF) membrane for
dye/salt separation using a nonsolvent-induced phase separations
(NIPS) method. Experiments have shown that the optimal composition
membrane exhibits a high rejection radius of 98.1% for congo red, while
the rejection radius for NaCl is merely 0.2%. Furthermore, filtration
experiments were conducted using varying salt concentrations, and the
membrane exhibited a rejection radius for NaCl that was consistently
lower than 4.2%, demonstrating excellent performance in separating
dyes from salts.
The objective of this study is to incorporate COF into a poly­
vinylidene fluoride (PVDF) matrix in order to obtain a hydrophilic PVDF
membrane with superior dye/salt separation properties. Firstly, the se­
lection of the imine-based COF-LZU1 [5] as the building block for the
membrane is proposed. The nanoparticles of such material are synthe­
sized via the Schiff base reaction between Benzene-1,3,
5-tricarbaldehyde (TFB) and 1,4-diaminobenzene (PDA) as monomers.
Then, COF-LZU1/PVP PVDF membrane with added COFs nanoparticles
of varying content were prepared using the nonsolvent-induced phase
separations (NIPS) method. Furthermore, the anti-protein fouling
capability, as well as the separation performance for organic dyes and
salts, were investigated for these membranes, which provided a useful
attempt for the preparation of COF membranes with dye/salt separation
performance and anti-protein fouling membranes.
Y. Pan et al.
2. Experimental
2.1. Materials
Polyvinylidene fluoride (PVDF, FR904, 99.99%) was purchased from
Inner Mongolia San Aifu Wan Hao Fluorine Chemical Co., Ltd. 1,4-dia­
minobenzene (PDA, 99%), benzene-1,3,5-tricarbaldehyde (TFB,
97.0%), 1,4-dioxane (99.7%), polyvinyl pyrrolidone (PVP, K30), acetic
acid (99.5%), 2-propanol(99.5%),acetone (99.9%), congo red (CR), acid
red 66 (AR 66), eriochrome black T (CBT), methyl blue (MB), NaCl
(99.0%), Na2SO4 (99.0%), MgSO4 (99.0%), MgCl2 (99.0%) were ob­
tained from Adamas. N,N-dimethyl acetamide (DMAc, 99.8%) and
tetrahydrofuran (THF, 99.0%) were accessed from Macklin. Bovine
serum albumin (BSA) and methanol (99.5%) were supplied by Aladdin.
Sodium dihydrogen phosphate and disodium hydrogen phosphate were
provided by Greagent. Ethanol (95%) was purchased from Sigma-
Aldrich. Deionized (DI) water was purified using the Milli-Q system
from Millipore.
2.2. Synthesis of COF-LZU1 nanoparticles
COF-LZU1 nanoparticles is synthesized using a room temperature
method [22]. TFB (32 mg) was dissolved in 1,4-dioxane (20 mL), fol­
lowed by the addition of PDA (32 mg). The mixture was stirred
magnetically for 30 min and sonicated for 10 min to ensure a uniform
dispersion of the mixture in the solution. Then slowly add acetic acid (3
M, 0.4 mL), seal the bottle and allow it to sit undisturbed at room
temperature for three days. The obtained yellow precipitate was washed
three times with tetrahydrofuran, acetone, and methanol, respectively.
After drying in a vacuum oven at 120 ℃ for 24 h, the COF-LZU1
nanoparticles were obtained.
2.3. Preparation of membranes
As shown in Scheme 1, the COF-LZU1/PVP PVDF membrane was
prepared using the nonsolvent-induced phase separation (NIPS) method.
Dissolve COF-LZU1 nanoparticles with different contents (0, 0.2, 0.4,
0.8 wt%, labeled as M0, M0.2, M0.4, M0.8) in DMAc solution, and then
disperse them evenly in the solution by ultrasonication for 15 min. Next,
add 16 wt% PVDF and 0.5 wt% PVP to the final mixture, and stir at 60 ◦ C
for 24 h. Afterwards, the polymer solution was left to stand at 60 ◦ C for
15 h in order to remove any excess air bubbles in the solution. Subse­
quently, a 300 µm casting Gardner knife was used to cast the polymer
solution onto a glass plate, and then the cast solution was immersed in a
30 ± 2 ℃ water bath to complete the solvent exchange process. Finally,
immerse the obtained membrane in DI water for 24 h.
2.4. Characterization of COF-LZU1 nanoparticles and membranes
Qualitative analysis of the chemical groups present in the COF-LZU1
nanoparticles and the prepared membranes was carried out using an
FTIR spectrometer (Thermo Fisher) with a scanning range of 400 cm− 1
to 4000 cm− 1. The morphology of the membrane, as well as the surface
and cross-section of COF-LZU1 nanoparticles, were observed using a
scanning electron microscope (SEM, Phenom Pro). The atomic force
microscope (AFM, Bruker) was used to investigate the roughness and
topological structure of the membrane surface. The chemical composi­
tion of the membrane surface was examined using X-ray photoelectron
spectroscopy (XPS). The crystallinity of the prepared COF was recorded
using an X-ray diffractometer (XRD, Bruker AXS) with a 2 Theta range of
2–40 and a scanning step of 0.02. The surface wettability of the mem­
brane was evaluated by measuring the water contact angle (WCA) at
different locations on the membrane using a contact angle meter (Ramé-
Hart 500-F4).
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Colloids and Surfaces A: Physicochemical and Engineering Aspects 686 (2024) 133431
2.5. Determination of membrane porosity and mean pore radius
By using the weight analysis method, the porosity (ε, %) of the
membrane can be estimated. Firstly, accurately measure the weight of a
1 × 1 cm2 dry membrane. Then, immerse the membrane in 2-propanol
for 24 h and weigh it again after wiping off any liquid on the surface
with a tissue. The average weight of wet and dry films with at least 6
replicas.And the Eq. (1) for porosity is as follows:
W2 − W1
ε= × 100% (1)
ρAd
Where ε represents the porosity of the membrane (%); W2 represents the
weight of the membrane in a wet state (g); W1 represents the weight of
the membrane in a dry state (g); ρ represents the density of 2-propanol
(g⋅cm− 3); d represents the cross-sectional thickness of the membrane
(cm); A represents the area of the membrane (cm2).
Calculating the mean pore radius (rm, μm) of a membrane using
Guerout Elford Ferry Eq. (2) [26]:
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
(2.9 − 1.75ε) × 8ηdQ
rm = (2)
εAΔP
Where rm represents the mean pore radius of the membrane (μm); ε
represents the porosity of the membrane (%); η represents the viscosity
of 2-propanol (Pa⋅s); d represents the cross-sectional thickness of the
membrane (cm); Q represents the volume of pure water passing through
the membrane per unit time (m3⋅s− 1); A represents the area of the
membrane (cm2); Δp represents the operating pressure (Pa).
2.6. The separation performance of membrane
The separation performance of the composite membrane was eval­
uated on a cross-flow filtration device with an effective membrane area
of 8.55 cm2. The experimental pressure is 1 bar. Prior to data collection,
each membrane was pre-pressed with pure water at a pressure of 2 bar
for 30 min to maintain a stable state.
According to Eq. (3), the water permeance of the membrane is
calculated as:
V
J= (3)
A × Δt × P
Where J represents the membrane water permeance (L⋅m2⋅h− 1⋅bar− 1), V
represents the volume of feed solution (L), A represents the effective
area of the membrane (m2), Δt is the filtration time (h), and P represents
the operating pressure (bar).
The separation performance of dye (30 mg⋅L− 1), BSA (1000 mg⋅L− 1)
and dye/salt (dye 30 mg⋅L− 1, salt 1000 mg⋅L− 1) was measured by
filtering different mixed solutions. After pressurization of pure water for
0.5 h, the mixed solution was filtered for 90 min.The calculation of
rejection ratio can reference Eq. (4):
( )
R = 1−
C0
× 100% (4)
C
Where R represents the rejection ratio (%); C represents the dye con­
centration in the feed solution (mg⋅L− 1); and C0 represents the dye
concentration in the filtrate (mg⋅L− 1). The concentration of the dye and
BSA were measured using an ultraviolet spectrophotometer (UV3600,
Japan). The concentration of the salt was measured using an atomic
absorption spectrophotometre(AA-7000 F/G, Japan).
2.7. Anti-protein fouling performance of membrane
Evaluate the anti-protein fouling performance of separation mem­
branes through the cyclic experiment of mixing pure water and BSA
solution. Firstly, under a pressure of 1 bar, the pure water was used for
Y. Pan et al.
Fig. 1. (a) FT-IR spectra, (b) XRD patterns and (c) SEM image of the COF-LZU1 nanoparticles.
Fig. 2. (a)FTIR spectra of membranes. XPS spectra (b) of M0 and M0.4; Convoluted high-resolution N1s of (c) M0 and (d) M0.4.
pressurization for 30 min. The pure water permeance (J0) was recorded.
Then, the BSA mixed solution was filtered for 30 min and its permeance
(J1) was recorded. After washing with ethanol, the pure water per­
meance of the membrane (J2) was measured again. The two testing
processes, involving the mixed solution and pure water, were conducted
as a cyclic procedure with three repetitions in the experiment. In the
above experiment, water permeance was recorded every 6 min. The
equation（5）for calculating the flux recovery rate (FRR) of composite
membranes is as follows:
J2
FRR = × 100%
J0
Where FRR represents flux recovery rate (%), J0 represents pure water
flux of the membrane at the start of the cycle experiment
(L⋅m2⋅h− 1⋅bar− 1), and J2 represents pure water flux of the membrane
Colloids and Surfaces A: Physicochemical and Engineering Aspects 686 (2024) 133431
after each subsequent cleaning cycle (L⋅m2⋅h− 1⋅bar− 1).
3. Results and discussion
3.1. Characterization of COF-LZU1 nanoparticles
Fig. 1(a) shows the FTIR spectrum of COF-LZU1 nanoparticles. The
peak at 1697 cm− 1 represents the stretching vibration of C–
–O in TFB.
The band at 3375 cm− 1 corresponds to the stretching vibration of N-H
bonds in PDA (the spectral bands at 3375 cm− 1 and 3300 cm− 1 are
(5) attributed to the asymmetric and symmetric stretching vibrations of N-H
bonds in PDA respectively. For COF-LZU1, the above peak disappeared,
and the appearance of the C––N bond (1618 cm− 1) was confirmed [6],
indicating successful synthesis of COF-LZU1 nanoparticles. Fig. 1(b)
displays the XRD pattern of the COF-LZU1 nanoparticles. In the strong
4
Y. Pan et al.
Table 1
Semi-quantitative element contents (atomic) of membranes.
Membrane C（%） N（%） O（%） F（%）
M0 59.3 2.1 7.1 31.5
M0.4 59.7 2.4 8.2 29.5
peak at 2θ = 4.8◦ , it can be attributed to the (100) reflection. This
represents that the prepared COF-LZU1 nanoparticles have good crys­
tallinity [21]. As shown in Fig. S3, the BET surface area of the COF-LZU1
nanoparticles is approximately 273.7 m2⋅g− 1. Fig. 1(c) shows the size
and microstructure of COF-LZU1 observed through SEM imaging. It can
be observed that the synthesized COF-LZU1 nanoparticles are spherical,
which is consistent with the common forms of COFs, mainly being
sheet-shaped or spherical [47].
3.2. Characterization of membrane
3.2.1. Surface chemistry analysis of membrane
The FTIR spectra of membranes with different contents of COF-LZU1
were shown in Fig. 2(a). The FTIR spectrum of COF-LZU1/PVP PVDF
membrane did not show any diffraction peak of C– –N, which could be
attributed to the low content of COFs, thus making it difficult to observe
significant changes in the ATR-FTIR spectrum [1]. The peaks at
1236 cm− 1 and 1170 cm− 1 are attributed to the stretching vibrations of
C-F, while the peak at 1400 cm− 1 corresponds to the bending vibration
of C-H. These vibrations can be observed in the PVDF membrane. The
characteristic peak at 1670 cm− 1 represents the C–
–O bond in PVP.
As shown in Fig. 2(b), the chemical bonding composition and surface
elemental content of M0 and M0.4 were analyzed by XPS. At 285 eV (C
1 s), 531 eV (O 1 s), 399 eV (N 1 s) and 687 eV (F 1 s), there are four
peaks in the M0 and M0.4. Table 1 presents the contents of carbon (C),
nitrogen (N), oxygen (O), and fluorine (F) on the surface of the mem­
brane. PVDF substrate contains a certain amount of F and C elements,
while O and N elements primarily come from PVP. Compared to PVP/
PVDF membranes, the M0.4 has a decreased fluorine (F) content from
31.5% to 29.5% and an increased oxygen (O) content from 7.1% to
8.2%. Due to the addition of COF-LZU1, the content of C and N elements
increased from 59.3% and 2.1% to 59.7% and 2.4%, respectively. From
Fig. 3. AFM images of modified PVDF membranes with different amounts of COF-LZU1.
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Colloids and Surfaces A: Physicochemical and Engineering Aspects 686 (2024) 133431
Fig. 2(c) and Fig. 2(d), it can be observed that for M0 membranes, there
is only one peak present at 399.08 eV in the N1s spectrum, which is
mainly attributed to the N atom in N-(C)3 of PVP. In comparison, the N1s
spectrum from the M0.4 exhibits two peaks: one at 399.28 eV and the
other at 398.78 eV, which can be attributed to the N atom in the N-(C)3
group of PVP and the C-N = C group of COF-LZU1 respectively [30].
This also confirms the successful fabrication of COF-LZU1/PVP PVDF
membrane.
3.2.2. Surface membrane morphologies
The impact of COF-LZU1 nanoparticles content on the surface
topography, morphology, and internal structure of the prepared mem­
branes were observed through AFM (Fig. 3) and SEM (Fig. 4 and Fig. 5).
As shown in Fig. 3(a)-(d), the calculation of surface roughness param­
eters of membranes with different amounts of COF-LZU1 using scanning
sizes of 5 µm was performed with the gwyddion software (64Bit). As
shown in Table 2, the parameters for calculating membrane roughness
mainly include the average roughness (Sa) and the root mean square
(Sq) of the Z data. The Sa of the M0 membrane is approximately
19.5 nm, slightly larger than other membranes. By adding COF-LZU1
nanoparticles into the PVDF membrane, the roughness parameters of
MMM were slightly reduced, with the M0.4 membrane having the
lowest roughness parameter. This may be due to the addition of small
amounts of COFs nanoparticles causing slight electrostatic interactions,
resulting in membranes having a smoother surface [31]. In addition,
studies have shown that the use of NIPs method to prepare membrane
materials with added COFs nanoparticles results in their migration to­
wards the surface of the membrane, leading to a decrease in the
roughness parameter [27]. However, as the amount of nanoparticles
added increases, it is observed that the roughness parameter of M0.8
slightly increases. This is mainly due to the excessive addition of
COF-LZU1, which causes the viscosity of the casting solution to increase,
thereby reducing molecular displacement and phase transformation rate
[41,49]. Generally, membranes with rough surfaces are more suscepti­
ble to contamination during use and are more difficult to clean [25,34].
Therefore, modified membranes with a smoother surface have better
anti-fouling ability [3].
Fig. 4 exhibit SEM images of the varying COF concentrations
observed on the surface of the membranes at different magnifications. It
Y. Pan et al.
Fig. 4. SEM images of membrane surface at different magnifications: M0 (a,b), M0.2 (c,d), M0.4 (e,f) and M0.8 (g,h).
can be observed that COF membranes with different contents all have a
surface with small pores. As the content of COF-LZU1 increases, the
membrane surface shows a trend of decreasing roughness followed by
increasing roughness, which is consistent with the previous character­
ization results obtained from AFM analysis (Fig. 3). Furthermore, there
are no evident cracks on the surface of the membrane. Fig. 5 displays the
SEM images of cross-sections of membranes with varying COF contents
at different magnifications. The image illustrates that COF-LZU1 is
evenly dispersed within the membrane and appears in a spherical shape,
indicating good compatibility between COF-LZU1 and PVDF polymer.
With the increase in COF content, the number of observable nano­
particles in the image also increases.
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Colloids and Surfaces A: Physicochemical and Engineering Aspects 686 (2024) 133431
3.2.3. Membrane porosity, mean pore radius and water contact angle
As shown in Table 3, the porosity of the membrane increased from
49.9% to 59.2% as the COF content increased from 0% to 0.4 wt%, and
the pore size decreased from 4.7 nm to 3.6 nm. The porosity and pore
size variation of the membrane may be attributed to the improvement of
thermodynamic stability by COF-LZU1 in the casting solution during the
phase transformation, which could lead to an increased rate of phase
transformation [20]. Additionally, it is possible that during the mem­
brane preparation process, the porous material COF-LZU1 migrated to
the surface of the membrane, resulting in the formation of additional
micro-porous structures on the membrane surface. However, when the
quantity of COF exceeds 0.4 wt%, there is a slight decrease in the
porosity of the membrane. This is related to the fact that the addition of
Y. Pan et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 686 (2024) 133431

Fig. 5. SEM cross sections morphology images of membrane surface at different magnifications: M0 (a,b), M0.2 (c,d), M0.4 (e,f) and M0.8 (g,h).

Table 2 Table 3
Roughness parameters of modified PVDF membranes. Membrane porosity, mean pore radius and water contact angle.
Membrane Sa（nm） Sq（nm） Membrane Porosity（%） Mean pore radius (nm) water contact angle (◦ )

M0 19.5 ± 1.7 22.4 ± 2.5 M0 49.9 ± 2.5 4.7 ± 0.3 79.0 ± 1.3
M0.2 14.8 ± 1.6 17.5 ± 1.9 M0.2 54.8 ± 3.6 4.3 ± 0.3 68.6 ± 3.1
M0.4 12.3 ± 1.0 14.7 ± 1.3 M0.4 59.2 ± 2.5 3.6 ± 0.3 58.3 ± 3.8
M0.8 13.7 ± 1.1 17.2 ± 1.6 M0.8 57.2 ± 3.2 4.0 ± 0.4 63.5 ± 2.7

nanoparticles increases the viscosity of the casting solution, which is Hydrophilicity is a crucial parameter affecting the performance of
unfavorable for the formation of membrane pores [9]. It can be deter­ membranes. We measured the static water contact angle of the mem­
mined that introducing 0.4 wt% of COF into PVDF substrate would in­ brane to evaluate its hydrophilic properties. The water contact angle of
crease the porosity and reduce the pore size of the membrane. membrane is shown in Table 3. The water contact angle of M0 is

7
Y. Pan et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 686 (2024) 133431

Fig. 6. Dye separation performance of membrane (a) the impact of COF-LZU1 content on permeance and CR rejection, (b) the rejection and permeance of M0.4 for
different dyes.

approximately 79.0◦ . As the hydrophilic COF-LZU1 is added to 0.4 wt%,

the water contact angle of M0.4 decreases to approximately 58.3◦ . This
could be due to the increase in membrane surface porosity, which allows
water droplets to spread more effectively on the membrane surface upon
contact [17]. However, with the increase in COF content, the water
contact angle of the modified membrane increased to approximately
63.5◦ . The cause of this phenomenon may be due to an excessive addi­
tion of particles, leading to a roughening of the membrane surface which
hinders the diffusion of water molecules on the membrane surface [18].
Therefore, compared to M0, the COF-LZU1/PVP PVDF membrane is
more hydrophilic.

3.3. Dye rejection property of membrane

The filtration experiment was conducted with pure water pre-

pressurization at 2 bars, and the dye solution with a concentration of
30 mg⋅L− 1 was filtered under cross-flow filtration at a pressure of 1 bar
for 90 min. Different membranes with varying COF content show the
results for Congo red rejection and water permeance as depicted in Fig. 6
(a). The rejection ratio of M0 membrane is 86.6%. As the COF content
increases, the rejection of M0.2, M0.4, and M0.8 membranes increase to
89.7%, 98.4%, and 95.9% respectively. Size sieving and Donnan effect
are the main separation mechanisms in the process of separating dyes.
The increase in dye rejection may be due to the decrease in membrane
pore size (Table 3) and the reduction of negative charges on the mem­
brane surface. Compared with M0, due to COF-LZU1 carrying positive
charges [10], the charge of the membranes will be slightly transferred to
the positive charges, resulting in a decrease in the negative charge on the
membrane surface. Furthermore, the water permeance of the M0
membrane was 6.9 L⋅m− 2⋅h− 1⋅bar− 1, while for the M0.2 and M0.4
membranes, the water permeance increased to 11.7 and
18.0 L⋅m− 2⋅h− 1⋅bar− 1 respectively. Afterwards, the water permeance of
the M0.8 membrane decreased to 13.9 L⋅m− 2⋅h− 1⋅bar− 1, possibly due to
changes in porosity and hydrophilicity. Therefore, M0.4 was chosen as
the optimal modified membrane.
As shown in Fig. 6(b), it can be observed that the rejection of CBT
(461 Da), AR (556 Da), CR (697 Da), and MB (799 Da) by M0.4 mem­
brane are all above 94.5%. Among them, the molecular weight of CR is
slightly smaller than that of MB, but the rejection (98.4%) is higher than
that of MB (96.1%). This may be because CR is more prone to aggre­
gation in solution compared to MB. Therefore, due to sieving and elec­
trostatic repulsion effects, the rejection order is as follows: eriochrome
black T(CBT)<acid red(AR)<methyl blue(MB)<congo red(CR).
Fig. 7. Separation performance of dye/salt mixed solution by M0.4.
3.4. Separation performance of dye/salts
The dye/salt separation performance of M0.4 was evaluated using a
mixed solution of CR (30 mg⋅L− 1) and salt (1000 mg⋅L− 1). As shown in
Fig. 7, the rejection of CR by M0.4 in mixed solutions of Na2SO4, NaCl,
MgSO4, and MgCl2 are 97.2%, 96.3%, 95.4%, and 96.6% respectively.
At the same time, the rejection of the salts are 4.5%, 1.6%, 3.5%, and
2.8% respectively. It was found in the experiment that the water per­
meance of the mixed solution (~19.4 L⋅m− 2⋅h− 1⋅bar− 1) was slightly
higher than that of the pure CR solution (~18.0 L⋅m− 2⋅h− 1⋅bar− 1).
There are scholarly references indicating that mixed solutions with
added salt can disperse dye molecules more uniformly compared to
aqueous solutions [8,11]. Therefore, dispersing the dye uniformly can
reduce concentration polarization on the surface of the membrane,
resulting in an increase in water permeance [15]. Furthermore, due to
the respective hydrated radii of Mg2+, Na+, SO2- -
4 , and Cl being 0.43 nm,
0.36 nm, 0.38 nm, and 0.33 nm, the rejection of M0.4 for NaCl is the
lowest. the rejection of sulfate is higher than that of chloride, which may
be due to the negatively charged surface of the membrane, resulting in a
better rejection effect for bivalent ions (SO2- -
4 ) than monovalent ions (Cl ).
The results showed that M0.4 exhibited excellent performance in the
dye/salt separation experiment. Furthermore, a comparison of the
dye/salt separation performance was made between the M0.4 mem­
brane prepared in this experiment and loose nanofiltration membranes

8
Y. Pan et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 686 (2024) 133431

Table 4
Comparison of the dye/salt separation performances of M0.4 with other membranes reported in literatures.
Polymer Modifier / Modification methods Permeance (L⋅m− 2⋅h− 1⋅bar− 1) Dye rejection Molecular weight (g⋅mol− 1) Salt rejection Ref.

PES TiO2-HMDI / Surface 15.3 Congo red: 97.4% 697 NaCl: 2.7% Zhang et al.,[44]
PAN COF-TpTGCl / Surface 24.0 Methyl blue: 99.0% 799 NaCl: 2.6% Sheng et al.,[29]
PES ZHT (1 wt%) / Blending 14.1 Reactive red 49: 90.3% 577 NaCl: 0.4% Wang et al.,[39]
PAN GO (0.2 wt%) / Blending 5.5 Methyl blue：100% 799 NaCl: 10.9% Qiu et al.,[24]
PES GO-PSBMA (0.22 wt%) / Blending 12.0 Reactive red 49: 97.2% 1470 Na2SO4: 10.0% Zhu et al.,[48]
PES MoS2-PSBMA (1 wt%) / Blending 18.1 Reactive black 5: 98.2% 992 NaCl: 1.1% Liang et al.,[16]
PVDF COF-LZU1 (0.4%) / Blending 19.4 Congo red: 96.3% 697 NaCl: 1.6% This work
Na2SO4: 3.5%

Fig. 8. Anti-protein fouling performance of PVDF membrane (a) BSA permeance and rejection of membranes with different COF-LZU1 content, (b) the permeance of
membranes in fouling and washing cycles.

prepared in other studies (Table 4). The M0.4 membrane not only has a smooth surface of the M0.4 membrane makes it difficult for BSA mole­
considerable dye rejection rate, but also has a higher permeance and cules to cover the membrane pores, making them easier to wash off and
ultra-low salt rejection rate. Clearly, COF-LZU1/PVP PVDF membrane resulting in a higher FRR value.
has broad application prospects in the field of dye/salt separation.
4. Conclusions
3.5. Membrane anti-protein fouling performance
Membranes were prepared by incorporating COF-LZU1 into the
polyvinylpyrrolidone (PVP) or polyvinylidene fluoride (PVDF) matrix.
Compared to the M0 membrane, the water permeance of M0.4 is 2.3
The synthesized COF-LZU1 nanoparticles and prepared membranes
times higher than that of M0. From Fig. 8(a), it can be observed that the
were comprehensively characterized. Compared with PVP/PVDF
BSA solution permeance and rejection of M0.4 were higher than those of
membranes, the addition of COF-LZU1 can reduce the surface roughness
other membranes, which may be attributed to the improvement of hy­
of membranes, improve the hydrophilicity and porosity of the mem­
drophilicity, porosity and mean pore radius (Table 3) due to the addition
brane surface, decrease the membrane rejection, and significantly
of COF-LZU1 nanoparticles. In general, the addition of COF-LZU1 can
enhance water permeance and anti-fouling performance. The rejection
enhance the anti-fouling performance of membranes.
ratio for eriochrome black T (CBT), acid red (AR), congo red (CR), and
In the experiment, a continuous three-cycle contamination washing
methyl blue (MB) were all above 94.5%, indicating excellent separation
experiment was conducted to evaluate the fouling resistance perfor­
performance. The membrane with the optimal COF concentration had a
mance of the membrane [32]. The water permeance of the mixed so­
water permeance of 19.37 L⋅m− 2⋅h− 1⋅bar− 1 and rejection of 96.3% and
lution BSA through the PVDF membrane is shown in Fig. 8(b). After
1.6% for CR and NaCl, respectively, in a mixed solution. Therefore, the
30 min of filtration, the pure water permeance of the PVDF membrane
COF-LZU1 PVP/PVDF membrane has great potential for applications in
exhibited a slight decrease. After replacing pure water with a mixed
the dye and dye/salt separation field.
solution, the membrane’s permeability to BSA was observed to be lower
than the permeability to pure water, which was caused by BSA mole­
cules blocking the membrane pores. Then, we immersed the membrane CRediT authorship contribution statement
in ethanol under ultrasound for 8 min. Experimental findings suggest
that due to the irreversibility of membrane fouling, the water permeance Pan Yiwei: Writing – original draft, Methodology, Conceptualiza­
cannot be completely restored after cleaning. After three cycles of tion. Li Zixun: Investigation, Data curation. Shen Shusu: Writing – re­
experimentation, the FRR of M0.4 membrane can reach 91.5%, which is view & editing, Supervision, Funding acquisition. Liu Dapeng: Formal
better in terms of fouling resistance against BSA compared to M0 analysis. Zhang Ganwei: Writing – review & editing.
(76.7%), M0.2 (82.3%), and M0.8 (85.6%). This may be due to the fact
that the size of BSA molecules is about 10 nm, which is much larger than Declaration of Competing Interest
the average pore size of the membrane, making it difficult to enter the
membrane pores and causing blockage. In addition, the hydrophilic and The authors declare that they have no known competing financial

9
Y. Pan et al.
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data Availability
No data was used for the research described in the article.
Acknowledgements
Financial supports from the National Natural Science Foundation of
China (No. 51608342), Suzhou Industrial Foresight and Key Core
Technology Projects (SYC2022147) and Jiangsu Collaborative Innova­
tion Center of Technology and Material of Water Treatment
(XTCXSZ2022-9) are thanked.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.colsurfa.2024.133431.
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