Advanced Membranes 3 (2023) 100059

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Advanced Membranes
journal homepage: www.keaipublishing.com/en/journals/advanced-membranes

Bio-inspired polydopamine nanofiltration membranes modulated by

spiro-piperazine
Xufei Liu a, Huawen Peng a, Jing Lu b, Yanli Ji c, *, Shaoping Li d, Jiayin Yuan e, Qiang Zhao a, **,
Congjie Gao c
a
Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of
Science and Technology, Wuhan, 430074, China
b
Key Laboratory of Textile Fiber and Products, Ministry of Education, Wuhan Textile University, Wuhan, 430200, China
c
Center for Membrane and Water Science & Technology, Zhejiang University of Technology, Hangzhou, 310014, China
d
Hubei Three Gorges Laboratory, Yichang, 443000, China
e
Department of Materials and Environmental Chemistry, Stockholm University, Stockholm, 10691, Sweden

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

Keywords: Polydopamine (PDA) depositions, inspired by mussel foot adhesive proteins, represent a versatile method for
Dopamine preparing separation membranes. However, PDA-based nanofiltration membranes are limited by the long prep-
Co-deposition aration time and moderate flux. This work modulated PDA deposition processes with a spiro-piperazine (SPIP)
Nanofiltration
molecule containing two secondary amine groups and a quaternary ammonium salt. The SPIP could be covalently
Spiro-piperazine
inserted into PDA coating structures via Michael addition reaction to accelerate the deposition process of PDA and
reduce its aggregation. In addition, the rigid and spiro configuration of SPIP molecules provides higher fractional
free volume and leads to looser and more uniform structures in the PDA coating. As such, water permeance of
PDA/SPIP membranes is 73 L m
2 h
1 bar
1, 4.6 times improved compared with PDA control membranes, while
the dye rejection (>99% for Congo red) is maintained high. These results demonstrate that SPIP is an effective
molecule for the structure and performance engineering of mussel-inspired PDA nanofiltration membranes.

1. Introduction nanofiltration [15–19], and reverse osmosis [20]. In particular,

Mussels are known for intriguing ability of hanging themselves to wet
surfaces through adhesive plaques consisting of a family of mussel foot
proteins (mfps). Waite et al. studied the chemical compositions of mfps
[1], and found that they are rich in 3,4-dihydroxy-L-phenylalanine
(DOPA) and lysine mfps amino acids. Inspired by this, Messersmith
et al. reported that dopamine, which contains DOPA and amine groups, is
an alternative small molecule with functions analogous to it. That is,
dopamine molecules undergo spontaneous polymerization to form pol-
ydopamine (PDA) coatings and films on a broad range of substrates [2].
Since then, PDA coating technologies have been widely exploited to
prepare functional membranes [3–6], through the in-situ polymerization
of dopamine on various supporting membranes [7–9]. Moreover, PDA
coatings contain abundant functional groups (e.g., catechols, quinones,
and amines) for post-functionalization [10,11]. As a result, PDA coatings
play active roles in microfiltration [12], ultrafiltration [13,14],
PDA-based nanofiltration membranes exhibit good potential in ion sep-
aration [21,22], antibiotics removals [15,23], dye desalination [24], etc.
Nevertheless, the formation of PDA nanofiltration membranes by
dopamine polymerization usually takes several tens of hours or even days
to obtain defect-free membranes with desired thickness and structures [2,
25]. Moreover, the PDA formation is complicated, normally accompanied
by uncontrolled aggregation and inhomogeneous deposition of PDA
particles. Various approaches have been proposed to modulate the PDA
formation process. Xu et al. reported that a uniform and stable PDA
coating was obtained by CuSO4/H2O2 catalysts, allowing for ten times
quicker PDA deposition compared to conventional methods [25]. Other
oxidants, such as ammonium persulfate, were applied as a trigger to
accelerate the PDA deposition [14]. In addition, co-deposition strategies
have also been developed to tune the deposition and structures of PDA
coatings [26–28]. The incorporation of amine-rich molecules during PDA
deposition has shown great potential to produce uniform and stable

* Corresponding author.
** Corresponding author.
E-mail addresses: yanliji@zju.edu.cn (Y. Ji), zhaoq@hust.edu.cn (Q. Zhao).

https://doi.org/10.1016/j.advmem.2022.100059
Received 1 October 2022; Received in revised form 2 December 2022; Accepted 4 December 2022
Available online xxxx
2772-8234/© 2022 The Authors. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
X. Liu et al.
Fig. 1. Schematic preparation of (a) SPIP-PDA, (b) PDA/PIP, and (c) PDA membranes.
structures in PDA membranes in shortened time [18,19,21,29]. These
molecules (such as polyethyleneimine and piperazine) provide an alka-
line environment for dopamine polymerization. Meanwhile, the Michael
addition and Schiff-base reaction between the added molecules and
dopamine could accelerate the deposition process and reduce the PDA
aggregation [30]. However, it is not clear what the effects of these
molecules are in the aggregation structures of PDA coatings and to what
extent we could modulate their separation performance. In this regard,
multifunctional regulators with rigid structures are expected to provide
additional interspaces between PDA aggregates, which could increase
water permeance while maintaining the solute rejection capability [19].
Herein, a spiro piperazine (SPIP) molecule containing two secondary
amine groups and a quaternary ammonium salt was designed and syn-
thesized to modulate mussel-inspired PDA coatings. Due to the twisted
conformation of the spiro structure and the high rigidity, SPIP molecule
is expected to increase the free volume of as-prepared PDA/SPIP mem-
branes. Meanwhile, SPIP could be covalently inserted into PDA coating
via Michael addition, resulting in loose structures. The resultant mem-
brane displayed high permeance (~73 L m
2 h
1 bar
1) and efficient dye
desalination performance (>99% for Congo red, <5% for NaCl). These
results indicate the great potential of molecular design in improving
mussel-inspired membranes in nanofiltration.
2. Experimental
2.1. Materials and chemicals
Polysulfone (PSF) supporting membranes with molecular weight cut-
off (MWCO) ca. 20 kDa were supplied by the Development Centre of
Water Treatment Technology, Hangzhou, China. Dopamine hydrochlo-
ride (DA), Congo red (CR), and piperazine (PIP) were acquired from
Aladdin Industrial Corporation (Shanghai, China). Methyl blue (MB),
Evans blue (EB), Rose bengal (RB), and Alcian blue 8GX (AB) were
purchased from Beijing InnoChem Science & Technology Co., Ltd.
Anhydrous ethanol and inorganic salts were provided by Sinopharm
Chemical Reagent Limited Corporation (Beijing, China). All reagents
were used without further purification, and all water used was deionized.
2.2. Synthesis of SPIP molecule
An aqueous solution of Bis(2-chloroethyl)amine hydrochloride (13.7
2
Advanced Membranes 3 (2023) 100059
g/80 mL) was added into an aqueous solution of piperazine (6 g/30 mL)
dropwise. After that, 7.4 g CaCO3 was added to the mixture and reacted
at 50  C for 10 h. After the removal of the solid by filtration, excessive
water in the reaction mixture was removed by rotation evaporation, and
the residue mixture was added dropwise to ethanol. After adjusting the
pH value of the mixture to 6, a large amount of white precipitation was
generated. Then, the precipitation was collected and washed with
ethanol for 3 times. After being dried by vacuum, the product was ob-
tained as white powder. The chemical structure of the SPIP was further
determined by 1H NMR and organic element analysis (Fig. S1), and the
purity (96%) was calculated.
2.3. Preparation of PDA, PDA/PIP, and PDA/SPIP membranes
Preparation of PDA/SPIP membranes. SPIP (43 mg) was dissolved in
an ethanol-H2O (v/v ¼ 2/5, 14 mL) mixed solvent, in which 18.6 mg DA
was added and dissolved (pH ¼ 10.8). Subsequently, PSFsupporting
membranes were pasted onto the glass plate and fully immersed in the
SPIP-DA mixture solution for 0.5 h. After that, the as-prepared mem-
branes were washed with H2O for 3 times, dried at 60  C for 15 min, and
soaked in deionized water before use. The resulting membrane was
denoted as PDA/SPIP. In addition, the membranes fabricated via
different deposition time and SPIP content were named PDA/SPIP(x) or
PDA/SPIPy%, respectively. Herein, x represents the deposition time, i.e,
15, 30, and 45 min, and y ranges from 0 to 0.8.
PDA/PIP membranes were prepared in the same method, except that
PIP (43 mg) was used in the first step instead of SPIP. PDA control
membranes were prepared in the same method, without adding SPIP or
PIP molecules.
2.4. Characterizations
The Nuclear Magnetic Resonance spectroscopy (1H NMR) was con-
ducted using Bruker AV400 (Switzerland). Organic element analysis was
performed on a Vario EL cube (Germany). Chemical structures of mem-
branes were characterized by X-ray photoelectron spectroscopy (XPS,
Thermo ESCALAB 250Xi, USA). Dynamic light scattering (DLS) was
conducted on a Malvern Zetasizer Nano S90. The surface hydrophilicity
of membranes was evaluated by contact angle on an OCA20 data physics.
Microstructures of membranes were observed via field-emission scanning
electron microscopy (SEM, SU 8010, Hitachi Japan), transmission
X. Liu et al.
Fig. 2. Optical photographs of (a) PDA/SPIP and (b) PDA solution; (c) The UV–Vis curves of PDA/SPIP and PDA solution (30 min reaction time); (d) Effect of reaction
time in the absorbance of PDA/SPIP (at 375 nm) and PDA solution (at 450 nm).
electron microscopy (TEM, Tecnai G2 20, FEI Netherlands), and atomic
force microscope (AFM, 9700-SPM, Shimadzu Japan), respectively. The
zeta potential of membranes was tested using SurPASS Anton Paar
electrokinetic analyzer (GmbH, Austria) in the pH range of 3.0–10.0
(0.001 M KCl) at 25  C, and each point was tested 3 times for the average
value.
2.5. Simulation methods
Initially, we loaded periodic cubic cells with dimensions of 10 nm.
The restrained electrostatic potential (RESP) charge generation topology
was used to describe the partial atomic charge required [31]. The inte-
gration time step was 1 fs, and the electrostatic interaction and van der
Waals interaction were calculated using the cut-off radius of 1.2 nm. The
steep algorithm was used to minimize energy via a general Amber force
field (GAFF) [32]. V-rescale thermostat and Berendsen barostat were
used to monitor and control temperature and pressure changes. Appellate
methods use our code to drive the Gromacs-2019.6 program [33]. After
21-step equilibration [34], the simulation boxes sizes for model PDA,
3
Advanced Membranes 3 (2023) 100059
PDA/PIP, and PDA/SPIP are about 4.5 nm  4.5 nm  4.5 nm, 4.8 nm 
4.8 nm  4.8 nm, and 5.2 nm  5.2 nm  5.2 nm, respectively.
2.6. Nanofiltration performance
The nanofiltration performance (i.e. water flux and dye/salt rejection)
was estimated using cross-flow membrane filtration equipment at 25  C
under 1.0 bar operating pressure. Specifically, it is necessary to pre-
compacted (pressure: 4 bar) for at least 0.5 h for each membrane
before data collection. The flux (J, L m
2 h
1) of membranes was
calculated by the following equations:
V
J¼
At
where V, A, and t are the permeate volume (L), effective membrane area
(22.06 m2), and operation time (h), respectively.
The dye rejection was evaluated with 1 g L
1 dye solution (CR, MB,
EB, RB, and AB), and the CR rejection was further tested with 0.1–1 g L
1
X. Liu et al. Advanced Membranes 3 (2023) 100059

Fig. 3. (a) XPS survey spectra and high-resolution N 1s spectra of (b) PDA and (c) PDA/PIP, and (d) PDA/SPIP membranes.

Fig. 4. SEM surface (a–c), and cross-section (d–f) images, and (g–i) TEM cross-section images of (a, d, g) PDA, (b, e, h) PDA/PIP, and (c, f, i) PDA/SPIP membranes.

CR aqueous feed solution. And the dye/salt separation performance was 0.1 g L
1 CR molecules. The solute rejection (R, %) can be calculated
evaluated with a mixture feed solution containing various concentrations using the following equation:
(10, 20, 30, and 50 g L
1) salts (Na2SO4, NaCl, MgSO4, and MgCl2) and

4
X. Liu et al. Advanced Membranes 3 (2023) 100059

Fig. 5. AFM images of (a) PDA, (b) PDA/PIP, and (c) PDA/SPIP membranes.

Fig. 6. (a) Water contact angle, (b) zeta potential and (c) permeance and rejection of PDA, PDA/PIP, and PDA/SPIP membranes (feed: 0.1 g L
1 CR solution), (d) effect
of CR concentration on nanofiltration performance of the PDA/SPIP membrane.

 
Cp spectrophotometer (METASH UV-6100), respectively.
R¼ 1
 100% (2)
Cf
3. Results and discussion
where Cp and Cf represent the permeate concentration and feed con-
centration. The concentrations of salt and dye solutions were determined As shown in Fig. 1, the mussel-inspired dopamine deposition yields
by electrical conductivity meter (DDS-357A) and UV–Vis

5
X. Liu et al.
Fig. 7. Simulated free volume of (a) PDA, (b) PDA/PIP, and (c) PDA/SPIP membranes. (d) Fractional free volume and (e) pore size distribution for PDA, PDA/PIP, and
PDA/SPIP membranes.
PDA coatings on PSFsupporting membranes through the oxidative
polymerization of dopamine. When SPIP (Fig. 1a) or PIP (Fig. 1b) mol-
ecules were added to the dopamine reaction system, they would mainly
react with dopamine molecules by Michael addition, i.e., the reaction
between amino groups and unsaturated alkenes. Parallel to the SPIP-DA
Michael addition reaction, dopamine molecules will undergo oxidative
polymerization as well. As such, SPIP (or PIP) molecules were incorpo-
rated into the SPIP-PDA (or PIP-PDA) membranes, leading to micro-
structure changes in corresponding membranes.
Fig. 2a shows the optical photographs of PDA/SPIP solution with
increasing reaction time. The color of PDA-SPIP solution turned from
colorless to brownish yellow in the first 3 minand gradually deepened
with increasing time. According to previous reports [30,35,36], changes
in the color of PDA-SPIP solution are attributed to the oxidative copo-
lymerization of dopamine and SPIP. By contrast, the PDA solution
(without SPIP) showed a very weak brownish color in the first 3 min, and
only a faint change in color was observed in 10 min (Fig. 2b). Fig. 2c
shows the UV–Vis absorption spectra of PDA/SPIP and PDA solution at
30 min reaction time. An adsorption peak at 450 nm appeared in the PDA
solution, which shifted to 375 nm in the PDA/SPIP solution. The 450 nm
peak is attributed to the C– – C–C–
– O structure of quinone [30], and the
blue shift is caused by the reduced conjugation degree of PDA, as a result
of the Michael addition between SPIP and DA. In addition, the absor-
bance of PDA solution in the visible region is higher than that of
PDA/SPIP solution, corresponding to the turbidity decline in the photo-
graphs (Fig. 2a and b) [30,36]. Overall, the UV–Vis absorbance of the
PDA/SPIP (at 375 nm) and PDA (at 450 nm) solution increase with
6
Advanced Membranes 3 (2023) 100059
increasing reaction time (Fig. 2d). The same rule also applies to the
change in the number of particles captured by DLS (Fig. S2). The addition
of SPIP molecules promoted the nucleation of dopamine, thereby accel-
erating the polymerization to form PDA and generating more aggregates.
Fig. 3 shows the XPS spectra and high-resolution N 1s spectra of PDA,
PDA/PIP, and PDA/SPIP membranes. There are two peaks in the spec-
trum of the PDA membrane (Fig. 3b), which are ascribed to the C– – N–C
at 401.5 eV and N–H at 400.2 eV [37,38], respectively. The new peak at
400.1 eV appears in the spectrum of the PDA/PIP (Fig. 3c) and PDA/SPIP
membrane (Fig. 3d), representing the tertiary amine (N-(C)3) due to the
Michael addition for SPIP or PIP to PDA [22]. Meanwhile, the charac-
teristic peak of quaternary ammonium group (-Nþ, 403 eV) in SPIP
molecular also appears in Fig. 3d. These results confirm the incorporation
of SPIP in PIP/SPIP membranes.
Both the PDA (Fig. 4a) and PDA/SPIP (Fig. 4c) membranes exhibit
relatively smooth surfaces, with only sporadic visible particles scattered
locally. The comparison shows that the incorporation of SPIP molecules
has a negligible effect on the surface morphology of the PDA membrane,
indicating that similar aggregated structures were formed during PDA
deposition and PDA/SPIP co-deposition. In contrast, a large number of
50 nm-sized particles were formed on the surface of PDA/PIP membrane
(Fig. 4b). From the cross-sectional morphologies, a thin top-layer on the
PSFsupporting membrane can be observed in Fig. 4d–i. According to the
result measured by SEM images (Fig. 4d–f), the average thickness of PDA,
PDA/PIP and PDA/SPIP membranes are ca. 92, 112, and 107 nm,
respectively. The thickness measurements in TEM images (Fig. 4g–i) are
consistent with that in SEM images.
X. Liu et al.
Fig. 8. Effect of SPIP content on (a) permeance and (b) CR rejection of PDA/SPIP membrane. (c) The permeance and CR rejection of PDA/SPIP membranes obtained
by different deposition times. (d) The separation performance of PDA/SPIP membranes was tested with 0.1 g L
1 CR, MB, EB, RB, and AB, respectively.
AFM images were scanned in the area of 2 μm  2 μm and the average
surface roughness (Rq) was marked (Fig. 5). The Rq values of PDA, PDA/
PIP, and PDA/SPIP membranes are 3.5 nm, 9.4 nm, and 4.3 nm,
respectively, indicating that PDA and PDA/SPIP membranes feature
relatively smooth surfaces. From 3D images of these membranes (Fig. 5,
bottom panel), smaller protuberances can be found in the 3D image of the
PDA/SPIP membrane (Fig. 5c), most likely because the Michael addition
reaction between SPIP and DA molecules could accelerate the nucleation
of PDA to generate more nanoaggregates during the co-deposition pro-
cess. The increased number of nanoaggregates can also be verified by the
DLS result (Fig. S2). These microstructures are consistent with the surface
morphologies observed by SEM images (Fig. 4a–c).
In addition, PDA, PDA/PIP, and PDA/SPIP membranes show similar
water contact angle (Fig. 6a), i.e., 64.8 , 63.8 , and 63.7 , indicating
similar hydrophilicity. Fig. 6b shows that the zeta potentials of PDA,
PDA/PIP, and PDA/SPIP membranes decrease with increasing pH values
of aqueous solution. The iso-electric point of PDA, PDA/PIP, and PDA/
SPIP membranes are 4.4, 4.6, and 5.2, respectively. Thus, all three
membranes are negatively charged at pH 7.0, which is reasonably due to
the abundance of hydroxyl groups in the PDA segments. The PDA/SPIP
membrane shows the highest iso-electric point (5.2), reasonably because
more amine groups and quaternary ammonium were introduced, both of
which would somehow offset the negatively charged density of the
membrane surface.
Subsequently, the separation performance of PDA, PDA/PIP, and
PDA/SPIP membranes was tested with 0.1 g L
1 CR dye aqueous solution
(Fig. 6c). All of the PDA, PDA/PIP, and PDA/SPIP membranes exhibit
high CR rejection (>97%), indicating the defect-free layer of PDA, PDA/
PIP, and PDA/SPIP membranes. The water permeance of PDA/SPIP
membrane is ~73 L m
2 h
1 bar
1, which is ca. 4.6 times that of the PDA
membrane (~16 L m
2 h
1 bar
1), while the CR rejection (>99%) is
maintained high. Fig. 6d displays the effect of CR concentration on the
7
Advanced Membranes 3 (2023) 100059
separation performance of PDA/SPIP membrane. It is seen that both the
CR rejection and water permeance decreases with increasing the CR
concentration, which is a common phenomenon for nanofiltration
membranes [39]. Noteworthy, the water permeance of PDA/SPIP
membrane remains at ~62 L m
2 h
1 bar
1 with CR rejection of ~87%,
even with a tenfold increase in CR concentration in the feed.
Subsequently, free volumes of PDP (Fig. 7a), PDP/PIP (Fig. 7b), and
PDP/SPIP (Fig. 7c) membranes were simulate to interpret the high per-
meance of the PDP/SPIP membrane, in which the blue area in the boxes
represents the free volume. Fig. 7d shows that the fractional free volume
for PDA, PDA/PIP, and PDA/SPIP are 15.72%, 18.73%, and 22.32%,
respectively. Thus, the sequence of membrane fractional free volume
(PDA/SPIP > PDA/PIP > PDA) is consistent with the sequence of water
permeance (Fig. 6c). The biggest fractional free volume for PDA/SPIP
could stem from the spiro-structure and larger sizes of SPIP molecules
compared to PIP molecules. When it comes to pore size distribution
(Fig. 7d), the peak value of pore size distribution for these membranes
are actually close, i.e., centering at 4.3  0.2 Å. In addition, larger pores
(7.5–10 Å) appear in the PDP/SPIP membrane. It is speculated that the
addition of rigid, spiro-structure and larger SPIP molecules could enlarge
the pore size of the PDA coating, generating more free volume for
accelerating the water molecules transport through the membrane.
The effect of SPIP content on permeance and CR rejection of PDA/
SPIP membranes was shown in Fig. 8a and b. With increasing the SPIP
content from 0 to 0.8%, the permeance increases from 16 to 174 L m
2
h
1 bar
1, while only a slight decrease in CR rejection was observed.
During the pressure-driven process, structure of PDA/SPIP0.8% mem-
brane is too loose to withstand compaction, resulting in a sharp drop in
permeance, which stabilized at around 114 L m
2 h
1 bar
1 after 30 h.
Considering permeance, rejection and stability, the SPIP content of 0.4%
was the optimal content to study the effect of deposition time. With the
extension of deposition time, a thicker and more compact PDA layer
X. Liu et al.
Fig. 9. Effect of different salt concentrations on permeance and salt rejection of PDA/SPIP membrane: (a) Na2SO4, (b) NaCl. (c) The CR/salt selectivity of PDA/SPIP
membrane. (d) Operation stability of PDA/SPIP membrane for CR/NaCl. (feed: 0.1 g L
1 CR solution mixed various concentrations salt, a: 10–50 g L
1 Na2SO4; b:
10–50 g L
1 NaCl; c: 10 g L
1 Na2SO4, NaCl, MgCl2, or MgSO4; d: 50 g L
1 NaCl.)
Fig. 10. Comparison of the recently reported bio-inspired membranes for dye
desalination.
would be obtained by the continuous accumulation of nanoaggregates.
According to the performance shown in Fig. 8c, the PDA/SPIP membrane
obtained by deposition time of 30 min exhibited the optimized separa-
tion performance of both high permeance (~73 L m
2 h
1 bar
1) and CR
rejection (>99%). In addition, the separation performance of PDA/SPIP
membranes was also tested with different dyes (Table S1). For negatively
charged dyes (CR, MB, EB, and RB), the pH values of feed are 6.45, 7.21,
8.13, and 7.29, respectively, at which the membrane is negatively
8
Advanced Membranes 3 (2023) 100059
charged since the feed pH is higher than the isoelectric point of the
membrane (5.2). For positively charged dye (AB), the pH value of feed is
4.86 (<5.2), at which the membrane shows a positive surface charge.
Collectively, the PDA/SPIP membrane exhibited high permeance (>70 L
m
2 h
1 bar
1) and appreciable dye rejection (>97%). Thus the mem-
brane shows good potential in dye desalination.
The dye/salt separation performance of PDA/SPIP membrane was
tested with the CR solution (0.1 g L
1) mixed with various concentrations
(from 10 to 50 g L
1) of Na2SO4 (Fig. 9a) or NaCl (Fig. 9b). The addition
of salts could reduce the dye aggregation and improve the dispersibility
of dye in the feed solution [40,41]. The PDA/SPIP membrane shows
stable CR rejection (>95%) at all salt concentrations (10–50 g L
1),
though with slightly reduced water permeance. Meanwhile, the Na2SO4
rejection of the PDP/SPIP membrane is <11%, and the NaCl rejection is
<5%. The salt rejection of PDA/PIP decreases with the increase of salt
concentration, which is due to the concentration polarization of high salt
concentration that impairs charge repulsion to ions [42]. Fig. 9c shows
the CR/NaCl selectivity (~23) of the PDA/SPIP membrane, which is
caused by the negative charge of the membrane surface [43,44].
Furthermore, the dye/salt separation stability of the PDA/SPIP mem-
brane was examined with a mixture feed solution containing 0.1 g L
1 CR
and 50 g L
1 NaCl. After filtrating for 30 h, the CR rejection of PDA/SPIP
membrane keeps stable at above 98%, and the water permeance was
stable at around 70 L m
2 h
1 bar
1.
The dye desalination performance of the mussel-inspired PDA/SPIP
membrane was compared with other bio-inspired nanofiltration mem-
branes reported previously (Fig. 10). The CR rejections of these mem-
branes are higher than 98%, while the water permeance varies widely.
Therefore, it is crucial to improve the permeance nanofiltration mem-
branes while maintaining the rejection recently. For example, g-C3N4 was
introduced to the co-deposition of PDA/polyethylenimine (PEI)
X. Liu et al.
membranes to loosen its structures, resulting in a permeance of 28.4 L
m
2 h
1 bar
1 and the CR rejection of 99.3% [45]. The permeance of
graphene oxide (GO) composite loose nanofiltration membrane obtained
by bio-inspired co-deposition can reach 48.4 L m
2 h
1 bar
1, while the
CR rejection is 98.8% [46]. Moreover, Xu et al. used a bio-inspired
coating, catechol, to prepare loose nanofiltration membranes by modi-
fying MIL-101(Fe) [47], with permeance and CR rejection been 43.2 L
m
2 h
1 bar
1 and 99.7%, respectively. It is seen that the permeance of
PDA/SPIP membrane prepared in this work outperformed most of the
state-of-the-art bio-inspired nanofiltration membranes reported in the
literature [48–51].
4. Conclusions
This work aims to modulate mussel-inspired PDA coatings for high
permeance nanofiltration membranes. We successfully synthesized a
SPIP molecule to co-deposit with PDA. The SPIP molecule accelerates the
deposition process of PDA coating and reduces the aggregation of PDA,
allowing for the building up of a loose and uniform nanostructure in the
PDA coating by covalent insertion into the PDA layer. As a result, the
resultant PDA-based nanofiltration membrane exhibited significantly
improved water permeance while maintaining the solute rejection
capability. These results indicate the great potential of SPIP co-deposited
PDA membranes in nanofiltration applications.
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 (22178139), Key R&D Program of Hubei Province
(2022BCA079) and Hubei Three Gorges Laboratory (No. SC212001).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https
://doi.org/10.1016/j.advmem.2022.100059.
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High-flux nanofiltration membranes tailored by bio-inspired co-deposition of Technology (HUST). He earned PhD degree at Zhejiang Uni-
hydrophilic g-C3N4 nanosheets for enhanced selectivity towards organics and salts, versity, and started independent research since 2017 at HUST,
Environ. Sci.: Nano 6 (2019) 2958–2967, https://doi.org/10.1039/c9en00692c. after post-doc research at Zhejiang University, the Max Planck
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