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Nanocomposite Membranes via the Co-deposition of Polydopamine/

Polyethyleneimine with Silica Nanoparticles for Enhanced Mechanical
Strength and High Water Permeability

Article  in  ACS Applied Materials & Interfaces · December 2016

DOI: 10.1021/acsami.6b13761

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Nanocomposite Membranes via the Codeposition of Polydopamine/

Polyethylenimine with Silica Nanoparticles for Enhanced Mechanical
Strength and High Water Permeability
Yan Lv,†,‡ Yong Du,†,‡ Wen-Ze Qiu,†,‡ and Zhi-Kang Xu*,†,‡
†
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering,
Zhejiang University, Hangzhou 310027, China
‡
Key Laboratory of Adsorption and Separation Materials & Technologies of Zhejiang Province, Hangzhou 310027, China
*
S Supporting Information

ABSTRACT: A defect-free and stable selective layer is of critical significance

for thin film composite membrane with excellent separation performance and
service durability. We report a facial strategy for fabricating thin film
nanocomposite (TFN) nanofltration membranes (NFMs) based on the
codeposition of polydopamine, polyetheylenimine, and silica nanoparticles.
Tripled water flux can be obtained from the TFN NFMs as compared with
those NFMs without silica nanoparticles. This is ascribed to the improved
wettability of the membrane surfaces and the enlarged pore sizes of the
selective layer. The interfacial compatibility of the inorganic fillers and the
polymer matrices can be enhanced by the electrostatic interactions of silica
nanoparticles with polyethylenimine and the adhesive characteristics of polydopamine, resulting in a defect-free selective layer
and then good rejection for both bivalent cations and neutral solutes. The rigid silica nanoparticles also improve the surface
mechanical strength of the TFN NFMs effectively and lead to structural stability and compaction resistance during the long-term
filtration process.
KEYWORDS: nanofiltration membrane, nanocomposite, silica nanoparticles, polydopamine, mussel-inspired chemistry

1. INTRODUCTION used to enhance water permeation flux, thermal stability, and

It is well accepted that the water crisis caused by population
growth and industry is threatening the survival and develop-
ment of human society all over the world.1,2 How to get clean
water with high quality has become a world matter of concern.
Various membrane technologies have been developed to
produce clean water since the 1960s. Among them, nano-
filtration is drawing much attention in the fields of drinkable
water production, seawater desalination and wastewater
treatment due to its superiorities of high water permeability,
suitable retention to multivalent ions or organic molecules
(200−1000 Da), and low operation pressure.3−5 In general,
most nanofiltration membranes (NFMs) have been prepared
from polymer.6,7 They have a thin film composite substructure,
typically consisting of, for example, a polysulfone sublayer on a
nonwoven support, and a selective layer that is made of
polyamide.8 In recent years, nanocomposite membranes have
become a focused research area,9−19 which consist of a
polymeric bulk matrix with various inorganic fillers and then
provide a promising access to combine the merits of inorganic
fillers with polymers and to take in the synergistic effect
between the two materials. Thin film nanocomposite (TFN)
membranes have been prepared by mixing inorganic nanoma-
terials into the selective layer to improve water permeation flux,
solute rejection, and mechanical durability as well as antifouling
property.10 For examples, silica nanoparticles (SiO2 NPs) were
service durability;11−14 TiO2 NPs or nanotubes were found to
promote water permeation flux and antifouling property;15,16
silver NPs could enhance antibacteria performance;17 and
carbon-based nanomaterials were applied to raise mechanical
strength and ion selectivity of TFN NFMs.18,19 In these cases,
the interfacial compatibility must be improved between the
polyamide matrices and the inorganic fillers to achieve ideal
structures and high performance for these TFN NFMs.20
Plenty of efforts have been devoted to this problem by
modifying the inorganic fillers, developing organic nano-
particles and synthesizing molecule of frameworks containing
organic ligands, which can be used to avoid defective voids and
structural instability to some extent.21−24 However, there still
remains a major challenge to develop facile and environmental
friendly methods to enhance the interfacial stability and
consequently achieve TFN NFMs with high performances.
Dopamine, known as a mussel-inspired “bio-glue”, has been
widely evaluated for the surface modification of various
materials because it can be oxidized and self-polymerizes
under alkaline condition to form polydopamine (PDA)
coatings with great adhesive strength.25−27 Most recently,
Received: October 27, 2016
Accepted: December 21, 2016
Published: December 21, 2016

© 2016 American Chemical Society 2966 DOI: 10.1021/acsami.6b13761

ACS Appl. Mater. Interfaces 2017, 9, 2966−2972
ACS Applied Materials & Interfaces
Figure 1. Schematic diagram of the preparation process and the suggested structures of TFN NFMs.
PDA-based coatings have been suggested as the selective or
intermediate layer for thin film composite NFMs.28−32 It has
been demonstrated in our previous work that incorporating
low-molecular-weight polyethylenimine (PEI) in the dopamine
solution can promote the homogeneous polymerization of
dopamine and the uniform codeposition of PDA−PEI to result
in smooth and electropositive coatings.33 Dopamine can also
help to improve the dispersion of inorganic fillers in aqueous
solution and enhance the surface interactions in an interfacial
polymerization process.22 Therefore, the codeposition of PDA
with PEI and nanomaterials provides a promising solution to
construct defect-free and stable selective layer for TFN NFMs.
In this work, novel TFN NFMs have been fabricated via the
codeposition of PDA/PEI/SiO2 NPs followed by cross-linking
and PEI grafting. SiO2 NPs are introduced into the selective
layer of TFN NFMs to improve the nanofiltration performance,
mechanical strength and structural stability due to their
inherent hydrophilicity, rigidity and electronegativity. The
interfacial compatibility can be facilitated between the positively
charged PDA/PEI matrices and the negative charged SiO2
NPs.13,22 The embedded SiO2 NPs endows these TFN NFMs
with high water permeation flux while maintaining high
rejection performance for multivalent cations. Furthermore,
the as-prepared TFN NFMs exhibit relatively high surface
strength and excellent structural stability during a long-term
separation process.
2. EXPERIMENTAL SECTION
Materials. Polyacrylonitrile ultrafiltration membranes (PAN,
MWCO ranging from 10 to 30 kDa) were purchased from Shanghai
MegaVision Membrane Engineering & Technology Co. Ltd. (China).
Dopamine hydrochloride and PEI (Mw = 600 Da) were procured
from Sigma-Aldrich (USA) and Aladdin (China), respectively. L-
Lysine, tetraethyl orthosilicate, tris(hydroxymethyl) aminomethane,
ethanol, sodium hydroxide (NaOH), hydrochloric acid (HCl) solution
(12 mol/L), glutaraldehyde (GA) solution (50 wt %), and inorganic
salts were all obtained from Sinopharm Chemical Reagent Co., Ltd.
and used without further treatment. Ultrapure water (18.2 MΩ) was
produced from an ELGA Lab Water system (France).
Synthesis of SiO2 NPs. SiO2 NPs with the diameter of about 10
nm were prepared according to an amino-acid-catalyzed method
reported by Yokoi et al. (Figure S1 in Supporting Information, SI).34,35
Briefly, 0.2 g L-lysine was dissolved in 50 mL of ultrapure water first,
and then 3.815 mL of tetraethyl orthosilicate was added to the solution
and the mixture was vigorously stirred at 60 °C for 24 h. Finally, the
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mixture was dialyzed for 3 days to remove residual lysine and the
obtained silica nanoparticle solution is colorless and transparent.
Preparation of the TFN NFMs. A typical process is schematically
presented in Figure 1 for the preparation of TFN NFMs. First, PAN
ultrafiltration membranes were hydrolyzed in NaOH solution (1.5
mol/L) for 1 h at 50 °C, and immersed into HCl solution (1 mol/L)
for protonization overnight at 25 °C. Then, they were washed by
ultrapure water for several times and stored in ultrapure water.
Dopamine hydrochloride (2 mg/mL) was dissolved in Tris−HCl
buffer solution (pH = 8.5, 50 mmol/L) with a certain content of SiO2
NPs for 15 min followed by the addition of PEI (1 mg/mL). PAN
membranes were prewetted by ethanol and then immersed into the
freshly prepared deposition solution to deposit for certain time at 25
°C. The as-prepared membranes (PDA/PEI/SiO2-modified mem-
branes) were washed by ultrapure water overnight and cross-linked
with a GA solution as described in our previous work.30 Additionally,
surface grafting by PEI solution (2 mg/mL) was adopted in order to
maintain the electro-positive characteristic of the membrane surfaces
with different contents of SiO2 NPs. Finally, these TFN NFMs were
rinsed several times and stored in ultrapure water for further
characterization and evaluation.
Membrane Characterization. Chemical structures of the
membrane surfaces were characterized by attenuated total reflectance
Fourier transform infrared spectrometry (FT-IR/ATR, Nicolet 6700,
USA) with spectra collected from 400 to 4000 cm−1 by cumulating 32
scans at a resolution of 4 cm−1. Element components were further
analyzed by X-ray photoelectron spectrometry (XPS, ThermoScien-
tific, USA) using Al Kα excitation radiation (1486.6 eV) with a survey
depth of 5−10 nm. Field emission scanning electron microscopy
(FESEM, Hitachi, S4800, Japan) and transmission electron micros-
copy (TEM, Hitachi 7700, Japan) were used to characterize the
morphologies of the membrane and the distribution of SiO2 NPs in
the selective layer, respectively. The membranes were dehydrated
using graded ethanol solutions and fractured in liquid nitrogen to
prepare sectional samples for FESEM detection. For TEM, the dried
membranes were frozen and cut by cryoultramicrotome (Leica UC7/
FC7, Germany) to obtain the cross-sectional samples. The dynamic
water contact angles (WCAs) were measured by a DropMeter A-200
contact angle system (MAIST VisionInspection & Measurement Co.
Ltd., China) in ambient environment to evaluate the wettability of the
membrane surfaces. The membrane surface potentials were detected
using a streaming potential method by an electrokinetic analyzer
(SurPASS Anton Paar, GmbH, Austria) with KCl (1 mmol/L)
solution as electrolyte solution. pH values were adjusted by NaOH
(0.1 mol/L) and HCl (0.1 mol/L) solutions during the measurement.
Surface strength of the membranes was expressed by Young’s
modulus measured by atomic force microscopy (AFM, MultiMode 8,
USA). Deflection-displacement loading curves of different membranes
DOI: 10.1021/acsami.6b13761
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ACS Applied Materials & Interfaces Research Article

were obtained, and the Young’s modulus of the membrane surface was
calculated by the following eq 1:36,37

k
z=d+ d
(π /2)[E /(1 − v 2)]tan α (1)
where E is the Young’s modulus, d and z are the cantilever deflection
and piezo displacement, respectively. k is the spring constant of the
cantilever (k = 39 N/m, provided by the supplier, Nanosensors,
Switzerland), ν is Poisson’s ratio (ν = 0.5), and α is the opening angle
of the cone (α = 35°).
Membrane Performance Evaluation. The filtration performance
of the as-prepared TFC NFMs was tested using a laboratory scale
cross-flow flat membrane module with an effective membrane area of
7.07 cm2. A series of polyethylene glycol (PEG) with different
molecular weights (200, 400, 600, 1000, 1500, and 2000 Da) were
used as electroneutral solutes to detect the molecular weight cutoff
(MWCO) of the membranes.31 Various salts, including MgCl2, CaCl2,
MgSO4, Na2SO4, and NaCl were used as solutes in feed solutions at a
concentration of 1000 mg/L to test the separation performance of the
TFN NFMs. All of the filtration experiments were operated under 0.6
MPa at 30 °C with a fixed cross-flow rate of 30 L/h. The water flux
(Fw, L/m2 h) was calculated by the following eq 2:
Q
Fw =
A·t (2)
2
where Q (L), A (m ), and t (h) represent the volume of permeated
water, the effective membrane area, and the permeation time,
respectively.
And the rejection (R, %) was calculated by the following eq 3:
⎛ Cp ⎞
R = ⎜1 − ⎟ × 100%
⎝ Cf ⎠ (3)
where Cp (mg/L) and Cf (mg/L) are the solute concentrations in
permeate and feed, respectively. The concentration of salt solution was
detected by an electrical conductivity meter (Mettler Toledo, FE30,
China). Moreover, the structural stability was evaluated according to
the variation of the nanofiltration performance during a long-term
operation process. In detail, the NFMs were continuously tested on
the apparatus for 120 h with the water flux and salt rejection measured
every 6 h. All of the experimental results presented were repeated at
least three times.
Figure 2. (A) XPS spectra of the composite NFMs with (a) and
3. RESULTS AND DISCUSSION without (b) SiO2 NPs, and (B) FT-IR/ATR spectra of the prepared
membranes containing SiO2 NPs at different fabrication steps. (C)
Surface Structures of the Prepared TFN NFMs. Typical TEM image from the cross section of the TFN NFMs with
Chemical structures of the membrane surfaces were charac- SiO2 NPs in the selective layer.
terized by XPS and FT-IR/ATR. Our previous work indicates
that composite NFMs can be facilely fabricated by the NPs. After cross-linking with GA, the peak of CN enhances
codeposition of PDA/PEI followed by cross-linking with slightly ascribed to the reaction between aldehyde groups and
GA.30 XPS spectra (Figure 2A) show that, compared with amine groups whereas other peaks change little. The peaks of
composite NFMs without SiO2 NPs, new peaks of Si 2s and Si CN, NH, and CN increase obviously due to the PEI
2p arise in the spectrum of TFN NFMs. The deconvoluted grafting on to the membrane surface through Michel addition
spectra of C 1s, O 1s, and N 1s further exhibit the binding between PEI and PDA and Shiff base reaction between PEI and
energy of CC (CC), CN (CO), CN, CO, and GA. Besides, the intensity of SiO peak decreases because of
SiO in detail (Figure S2 in SI). The atomic percentage is the coverage by PEI chains. Chemical composition on the
calculated as 2.92% for Si element in the membrane surface, membrane surfaces varies consistently with above results at
indicating SiO2 NPs are successfully embedded into the different fabrication steps (Table S1 in SI).
selective layer (Table S1 in SI). Additionally, TEM was used to observe the distribution of
In accordance with these results, FT-IR/ATR spectra of the SiO2 NPs in the selective layer of TFN NFMs. It depicts that
TFN NFMs with SiO2 NPs shows a new peak at 1107 cm−1 the SiO2 NPs are embedded in the selective layer with slight
ascribed to SiOSi stretching vibration, and the intensity of aggregation, which can act as rigid cross-linking sites to improve
OH vibration peak at 3400 cm−1 is enhanced due to the the mechanical strength of the membrane surface and the
abundant hydroxyl groups on the surfaces of SiO2 NPs (Figure stability of the selective layer (Figure 2B, Figure S4a in SI).
S3 in SI). In detail, it can be seen that peaks arise at 1107, 1398, Surface Morphology and Property of the TFN NFMs.
1566, and 1663 cm−1 due to the SiO, CN, NH, and Figure 3 shows the surface morphology of the composite
CN vibrations after the codeposition of PDA−PEI/SiO2 NFMs with and without SiO2 NPs embedded, which are of
2968 DOI: 10.1021/acsami.6b13761
ACS Appl. Mater. Interfaces 2017, 9, 2966−2972
ACS Applied Materials & Interfaces Research Article

Figure 3. Surface morphologies of the composite NFMs without (a) and with (b) SiO2 NPs. (c) Dynamic water contact angles and (d) surface ζ-
potentials at various pH values of the composite NFMs with (tilted ◪) and without (◑) SiO2 NPs. (The deposition time is 4 h, and the
concentration of SiO2 NPs is 0.5 mg/mL.)

Figure 4. (a) Deflection−displacement loading curves of composite NFMs with and without SiO2 NPs (the deposition time is 4 h, the concentration
of SiO2 NPs is 0.5 mg/mL), and (b) effect of the concentration of SiO2 NPs on the Young’s modulus of the membrane surfaces of the TFN NFMs.

great importance for rejection and permeation performance.
The membrane surfaces are defect-free without visible pores. It
can be seen that the TFN NFMs exhibit a lot of nodules on the
membrane surfaces, while the composite NFMs without SiO2
NPs are relatively smooth. These nodules should be attributed
to the aggregation of SiO2 NPs. Moreover, the selective layer
increases from 55 to about 500 nm (Table S2 in SI) with
deposition time, which is much thicker than that of the
composite NFMs without SiO2 NPs.30
The surface wettability of the TFN NFMs is essential for
water permeation performance, which was evaluated by time-
dependent and static water contact angle (WCA) measure-
ments (Figure 3c, Figure S5 in SI). WCA is lower on the TFN
NFMs surfaces than those of the composite NFMs without
SiO2 NPs. It decreases further with increased SiO2 NPs and
2969
increases slightly with the prolonged deposition time (Figure
S5 in SI). These results should be ascribed to the inherent
hydrophilicity of the embedded SiO2 NPs and the resulted
rough surface morphology (Figure S6 in SI). The TFN NFMs
show good surface wettability and can be quickly infiltrated by
water, which is beneficial for the permeation performance.
On the other hand, the surface potential plays a very crucial
role for NFMs in the retention of charged solutes during the
nanofiltration process because of the Donnan exclusion effects
to co-ion at the interphase of the membrane and the solution.
Figure 3d reveals that the membrane surfaces are positively
charged with pH value ranging from 4 to 8 for those composite
NFMs without SiO2 NPs, which is due to the abundant amino
groups of the codeposited and the grafted PEI chains. It is
interesting that the membrane surfaces show a lower ζ-
DOI: 10.1021/acsami.6b13761
ACS Appl. Mater. Interfaces 2017, 9, 2966−2972
ACS Applied Materials & Interfaces
Figure 5. (a) MWCOs and (b) separation performances for different salts of the TFN NFMs. Compaction resistance of the composite NFMs (c)
with and (d) without SiO2 NPs with operation time (MgCl2 as solute). Test conditions: all inorganic salt concentration is 1000 mg/L, 30 °C, pH =
6, 0.6 MPa, cross-flow rate = 30 L/h.
potential for the prepared TFN NFMs than those composite
NFMs without SiO2 NPs. And the ζ-potential changes with the
SiO2 NPs and the deposition time (Figure S7 in SI). This is
because the synthesized SiO2 NPs are negatively charged (with
ζ-potential of −30.4 mV) whereas the PEI chains are positively
charged when the pH value is lower than 10.5 (isoelectric
point). Therefore, our TFN NFMs are still positively charged
when the nanofiltration process is typically conducted at pH
6.0.
Mechanical Strength of the Membrane Surfaces. SiO2
NPs are expected to act as cross-linking sites for enhancing the
mechanical strength of the membrane surface and thus
increasing the compaction resistance of the selective layer as
mentioned above. Young’s modulus (E) of the selective layer
was calculated from the indentation curves detected by AFM
(Figure 4a). E of the membrane surface is improved to 43.97
GPa for the TFN NFMs as compared with 14.29 GPa for the
composite NFM without SiO2 NPs. This value gradually
increases to 75 GPa with the concentration increases of SiO2
NPs from 0 to 2.0 mg/mL (Figure 4b). It can be attributed to
the increased amount of rigid inorganic nanoparticles in the
selective layer. It should be noticed that the error bars become
bigger as the SiO2 NPs concentration increases, indicating an
enlarged data dispersivity of Young’s modulus. This should be
ascribed to the increased nanoparticle agglomeration, which is
also consistent with the results shown in the TEM images
(Figure S4b in SI).
Nanofiltration Performance of the TFN NFMs. The
separation performance of the composite NMFs was evaluated
with a typical cross-flow nanofiltration process. We studied the
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effects of the deposition time and the concentration of SiO2
NPs on the nanofiltration performance in detail as they could
influence the surface topology and the thickness of the selective
layer (Figure S8 in SI). 4 h is adopted as an optimized
deposition time after considering both the permeation flux of
water and the rejection of MgCl2. The rejection increases
slightly with the deposition time because the compactness and
the surface potential of the selective layer reaches a steady state
when the deposition is longer than 4 h (Figure S7b, Figure S8a,
and Figure S9 in SI). On the other hand, the water flux declines
due to the increased thickness of the selective layer whereas the
surface morphology and the wettability remain changeless in
these cases (Table S2, Figure S5b, Figure S8b, Figure S9, and
Figure S10 in SI). We also determined MWCOs of the TFN
NFMs with different concentrations of SiO2 NPs by neutral
solute filtration using PEGs. It can be seen that the MWCO
increases from 200 Da to over 2000 Da with the concentration
of SiO2 NPs from 0 to 2.0 mg/mL (Figure 5a). It means the
selective layer becomes loose when the SiO2 NPs are
incorporated into the membrane surface. This is reasonable
because the SiO2 NPs are more rigid than the deposited PDA/
PEI matrix and they will aggregate at high concentration
(Figure S6 in SI).6,7 Therefore, the rejection to MgCl2
decreases dramatically with the concentration of SiO2 NPs,
which are resulted from the loose selective layer and the
decreased surface potential (Figure S7a and Figure S8b in SI).
However, the water flux of TFN NFMs increases to 70 L/m2 h
due to the improved surface wettability and the loose structures
(Figure S5a and Figure S8b in SI). Thus, 0.5 mg/mL is chosen
DOI: 10.1021/acsami.6b13761
ACS Appl. Mater. Interfaces 2017, 9, 2966−2972
ACS Applied Materials & Interfaces
as the optimized concentration of SiO2 NPs for the preparation
of TFN NFMs.
Various salt solutions were then used to evaluate the
separation performances of the TFN NMFs prepared under the
optimized conditions (Figure 5b). The rejection ratio reaches
as high as 90% for bivalent cations whereas it is lower than 30%
for monovalent cations. The salt rejection obeys the order of
CaCl2 ≅ MgCl2 > MgSO4 > Na2SO4 > NaCl, which is
reasonable for positively charged NFMs and mainly determined
by the Donnan and dielectric effects under typical conditions. It
can be seen that the rejection for Na2SO4 is higher than that for
NaCl because the hydration ion radius of SO42− is larger than
that of Cl−. Additionally, it should be noticed that, the water
flux of TFN NFMs reaches as high as 32 L/m2 h, which is
about triple of the composite NFM without SiO2 NPs (Figure
S8b in SI). This indicates that the incorporation of SiO2 NPs
into the selective layer improves the water permeability of the
composite NFMs effectively.
Moreover, we evaluated the structural stability and
compaction resistance of the selective layer with a long-term
operation process of continuous filtration for 120 h. Both of the
water flux and the rejection maintain stable during this process,
indicating good structural stability for the TFN NFMs (Figure
5c). However, the water flux decreases by about 30% whereas
the rejection increases from 87% to 95% for the composite
NFMs without SiO2 NPs (Figure 5d). It can be deduced that
the improvement of the compaction resistance is closely related
to the addition of SiO2 NPs. The enhanced structural stability is
beneficial for the stable separation performance of the
composite NFMs, which is promising for practical nano-
filtration operation.
4. CONCLUSION
In summary, novel TFN NFMs are fabricated via the
codeposition of PDA, PEI, and SiO2 NPs followed by GA
cross-linking and PEI grafting. The dense, hydrophilic, and
positively charged selective layers endow these TFN NFMs
with high rejection for bivalent cations and neutral molecules
accompanied by tripled water flux compared with those
composite NFMs without SiO2 NPs. The structural stability
and mechanical strength of the selective layer are also enhanced
due to the rigidity of SiO2 NPs and their good compatibility
with the PDA/PEI matrices, which is beneficial for the
compaction resistance during long-term filtration process. In
brief, we propose here a promising strategy to construct TFN
NFMs with defect-free, stable, and compaction resistant
selective layers.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.6b13761.
TEM image and size distribution of the synthesized SiO2
NPs, high-resolution XPS spectra of the TFN NFM, FT-
IR/ATR spectra of the composite NFMs, TEM images of
the selective layer from the cross-section of the TFN
NFMs, SEM images from the membrane surfaces of the
TFN NFMs with different deposition times and
concentrations of SiO2 NPs, SEM images the membrane
cross sections of the TFN NFMs and thickness of the
selective layer with different codeposition times, water
contact angles and ζ-potentials of the TFN NFMs with
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Research Article
different deposition times and concentrations of SiO2
NPs, effects of deposition time and concentration of SiO2
NPs on the nanofiltration performances of the TFN
NFMs (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: xuzk@zju.edu.cn.
ORCID
Zhi-Kang Xu: 0000-0002-2261-7162
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
Financial support is acknowledged to the National Natural
Science Foundation of China (Grant no. 21534009), the Open
Research Fund Program of Zhejiang Provincial Collaborative
Innovation Center Program 2011 (Grant no. 2016ZD04), and
Zhejiang Provincial Collaborative Innovation Center Program
2011 (Grant no. G1504126001900).
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2972 DOI: 10.1021/acsami.6b13761

ACS Appl. Mater. Interfaces 2017, 9, 2966−2972

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