Showcasing a study on the graphene oxide quantum As featured in:

dot incorporated reverse osmosis membrane by

Zhining Wang et al. from Ocean University of China.

Pressure-assisted preparation of graphene oxide quantum

dot-incorporated reverse osmosis membranes: antifouling
and chlorine resistance potentials

A graphene oxide quantum dot incorporated thin film

nanocomposite reverse osmosis membrane was developed
by filtration-assisted interfacial polymerization. The prepared
membrane exhibited excellent performance, high antifouling
capacity and improved chlorine resistance.

See Zhining Wang et al.,

J. Mater. Chem. A, 2016, 4, 16896.

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Pressure-assisted preparation of graphene oxide

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16896
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quantum dot-incorporated reverse osmosis
membranes: antifouling and chlorine resistance
potentials†

Xiangju Song,a Quanzhu Zhou,b Tian Zhang,a Haibo Xub and Zhining Wang*a

Received 3rd August 2016
Accepted 12th September 2016
DOI: 10.1039/c6ta06636d
www.rsc.org/MaterialsA
Graphene-based nanomaterials have opened a new era in the fabrication of novel membranes with
outstanding performance. In this study, we propose a new method of fabricating a graphene oxide
quantum dot (GOQD)-incorporated thin-film nanocomposite (TFN) membrane for reverse osmosis (RO)
applications. Inspired by free-standing graphene membranes prepared by vacuum filtration, an aqueous
suspension of GOQD/m-phenylenediamine (MPD) was first filtered onto a polysulfone (PSf) substrate to
obtain a cushion layer. A GOQD-incorporated polyamide (PA) selective layer was then constructed by
interfacial polymerization between MPD and trimesoyl chloride (TMC). This method can easily be scaled
up owing to its simple preparation procedures. The newly developed TFN membrane exhibited stable
high performance with a flux of 37.5 L m
2 h
1 and a NaCl rejection of 98.8% at 16 bar. Remarkably, this
represents a 51.8% increase in permeate flux relative to a GOQD-free TFC membrane without
compromising the solute rejection. In addition, the GOQD-incorporated TFN membrane displayed
long-term durability over 120 h of RO testing. More importantly, the introduction of GOQD into the TFN
membrane resulted in improved antifouling and chlorine resistance properties, which are greatly desired
in the membrane desalination and water reclamation processes.

characteristics in comparison with conventional thin-lm

1 Introduction
Water crises represented the top global risk of 2015 and it is
believed that these will be a continuing environmental and social
problem in the coming decade.1 Membrane separation technology,
in particular reverse osmosis (RO), has become the most effective
means of producing large quantities of freshwater from abun-
dantly available brackish water or seawater owing to the advan-
tages of a high permeate ux, ease of operation, and low process
costs.2,3 Among novel RO membranes, thin-lm nanocomposite
(TFN) membranes fabricated by incorporating nanomaterials into
a dense polyamide (PA) layer have emerged as a promising solu-
tion to the bottlenecks of current membrane desalination tech-
nologies.4–9 TFN membranes can provide enhanced separation
a
Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education,
Ocean University of China, Qingdao 266100, PR China. E-mail: wangzhn@ouc.edu.cn
b
College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao
266100, PR China
† Electronic supplementary information (ESI) available: Characterization of GO;
characterization of GO-incorporated membranes; photographs of the prepared
membranes; SEM and AFM images of GO-incorporated membranes; RO
performance of GO-incorporated membranes; photographs of the
GO-incorporated membranes before and aer RO testing; SEM images of the
polyamide layers of TFC and TFN-GOQD5.0 membranes; comparison of the RO
performance of membranes prepared with and without the assistance of
pressure. See DOI: 10.1039/c6ta06636d
composite (TFC) membranes. The structure and physical and
chemical properties of the membranes can be tuned by the
introduction of selected nanomaterials to meet the needs of
specic water treatment applications. Certain TFN membranes
have helped to overcome the trade-off between water permeability
and solute selectivity and have also demonstrated excellent anti-
fouling capacity and improved bactericidal effects.10,11
Recently, the advent of graphene oxide (GO) has opened a new
era in the fabrication of TFN membranes with high separation
performance owing to its distinctive two-dimensional structure
and single-atom layer motif, high mechanical strength, good
exibility, cost-effectiveness and scalable production.4,12–18 GO-
containing membranes promise to improve water permeability
by permitting the rapid diffusion of water through the nanopores
in GO,19–21 the two-dimensional nanochannels between GO
akes,22,23 and the nanocorridors between GO and the polymer
matrix.24 The unique structure and surface properties of GO also
impede the adsorption of hydrophobic foulants and provide
strong antimicrobial characteristics to prevent colonization of
the membrane by a wide variety of microorganisms.25–28 In
addition, GO akes incorporated into the membranes hinder
dissolved active chlorine ions from contacting the PA selective
layer, which results in efficient chlorine resistance without the
loss of intrinsic water permeability and solute selectivity.26,29,30

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The size of GO has been found to have an important inuence
on the performance of various GO-based membranes. Chen et al.
reported that a free-standing GO membrane composed of small
GO akes provided additional shorter paths for water molecules
to penetrate the membrane in comparison with large GO akes.31
The inuence of the size of GO on the permeation properties of
solutes in water through free-standing GO membranes has been
investigated by Sun et al.32 As the size of GO akes decreased
from several micrometers to several hundred nanometers, the
ion permeability increased signicantly, which can be attributed
to an increase in nanocapillaries formed between neighboring
GO akes. Lee et al. prepared membranes with a GO-embedded
polysulfone (PSf) substrate and found that small GO akes were
more effective in improving the membrane's mechanical prop-
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erties.33 On the one hand, small GO akes possess a large surface
area, which induces strong interfacial interactions between the
nanollers and the PSf matrix. On the other hand, the excellent
dispersion of the small GO akes contributes to an improvement
in mechanical strength. In addition, the large surface area in the
nanochannels also ensures that a more porous nanocomposite
substrate can be obtained. Perreault et al. reported another
important nding, namely, that a GO-modied membrane surface
exhibited prominent size-dependent antimicrobial activity based
on GO akes.28 A membrane surface coated with small GO akes
exhibited higher antimicrobial activity than that of membranes
coated with large GO akes, which can be explained by an increase
in oxidative behavior that resulted from the higher defect density
as the size of GO akes decreased.
Given this, we proposed to utilize graphene oxide quantum
dot (GOQD) as nanollers to fabricate novel TFN membranes.
GOQD adopt the same one-atom-thick structure as GO but have
lateral dimensions of less than 100 nm.34,35 GOQD possess
hydrophilic groups that are similar to those of GO, including
epoxy, hydroxyl and carboxyl groups. These groups help to
produce excellent dispersity of GOQD. Furthermore, GOQD
have a greater edge-to-volume ratio than micron-sized GO.36
Therefore, GOQD have great potential for use as nanollers for
fabricating high-performance membranes.37 In this study, extra
pressure was applied to lter an aqueous suspension of GOQD/
m-phenylenediamine (MPD) to accumulate and deposit a GOQD
cushion layer on a PSf substrate (Fig. 1). Subsequently, tri-
mesoyl chloride (TMC) was reacted with MPD to form a GOQD-
incorporated PA layer by interfacial polymerization. In compar-
ison with a reference TFC membrane, the TFN membrane
exhibited enhanced water permeability with retention of solute
Fig. 1 Schematic of the fabrication procedure of GOQD-incorporated
RO membranes with the assistance of pressure.
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Journal of Materials Chemistry A
selectivity, excellent stability, and improved antifouling capacity
and chlorine tolerance. These ndings have important impli-
cations for the design of high-performance TFN membranes.
2 Experimental
2.1 Materials
GOQD was kindly provided by Qingdao Haida Haixi New
Materials Co., Ltd (China). GO was obtained from Shanxi Fen-
ghuiyuan Science and Technology Co., Ltd (China). The poly-
sulfone membrane was purchased from Hangzhou Water
Treatment Center (China). m-Phenylenediamine (MPD, >99%)
and bovine serum albumin (BSA, $98%, MW ¼ 67 000 g mol
1)
were purchased from Sigma-Aldrich Chemical Co., Ltd (China).
Trimesoyl chloride (TMC, 98%) was obtained from Aladdin Co.,
Ltd (China). Other chemicals were obtained from Sinopharm
Chemical Reagent Co., Ltd (China) and were used without
further purication.
2.2 Membrane preparation
A 0.1 mg mL
1 suspension of GOQD was prepared by ultra-
sonication for 1 h. Then, 2 wt% MPD was added to obtain
a GOQD/MPD suspension. A GOQD/PSf membrane with certain
amounts of GOQD (1.0, 2.0, 5.0, and 10.0 mg) was fabricated
using various volumes of the GOQD/MPD suspension with the
assistance of N2 pressure. As shown in Fig. 1, a certain volume
of the GOQD/MPD suspension was subjected to pressure-
assisted ltration with N2 at a pressure of 2 bar using a dead-
end ltration device to deposit a cushion of GOQD/MPD onto
a PSf substrate. The composite membrane was dried in air.
A 0.1 w/v% solution of TMC/n-hexane was poured onto this
membrane for 1 min to form a GOQD-incorporated polyamide
layer via interfacial polymerization. The resulting TFN membrane
was dried in an oven at 80  C for 5 min and was then washed
and stored in DI water for at least 24 h before testing. According
to the GOQD loading (1.0, 2.0, 5.0, and 10.0 mg), the membranes
were denoted as TFN-GOQD1.0, TFN-GOQD2.0, TFN-GOQD5.0,
and TFN-GOQD10.0. As controls, a TFC membrane and a GO-
incorporated TFN (TFN-GO) membrane were also prepared via
the same procedure, employing MPD and GO/MPD solution as
the ltrate.
2.3 Characterization
Atomic force microscopy (AFM) images of GOQD were obtained
using a Digital Instrument Nanoscope V (Veeco MultiMode)
atomic force microscope. A sample dispersion was drop-cast
onto a clean mica wafer and dried at room temperature. A FEI
TECNAI G2 F20 transmission electron microscope (TEM) oper-
ating at 200 kV was used to investigate the morphology of
GOQD. Before measurement, GOQD was sonically dispersed in
water and then dropped onto a carbon lm-coated copper grid
and dried in air for 2 h. The particle size and zeta potential of
GOQD were determined by dynamic light scattering (DLS,
Malvern Zetasizer Nano series, UK). The pH value of the GOQD
suspension was tuned by adding 0.1 M HCl or 0.1 M NaOH
solution. The chemical properties of GOQD and the membranes
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Journal of Materials Chemistry A
were investigated using a Fourier transform infrared (FTIR)
spectrometer (Tensor 27, Bruker, Germany) and micro-Raman
spectroscopy (Renishaw, UK). Raman spectra were acquired at
l ¼ 532 nm and 10 mW. For the TFN-GOQD membranes,
a micro-Raman laser probe was focused on the island-shaped
domains on the membrane surface. All the samples were
vacuum-dried at 40  C overnight before FTIR and Raman
measurements. The thermal stability of the selective layers of
the TFC and TFN membranes was investigated by thermogra-
vimetric analysis (TGA) in N2. Prior to measurement, the thin
polyamide layer on the PSf substrate was separated from the PSf
support by dissolving PSf using dichloromethane. In each run,
samples of about 5 mg were loaded into a crucible and heated
to 800  C at a rate of 10  C min
1. The gas ow rate was
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maintained at 10 mL min
1.
The surface charge of the membrane was measured by an
electrokinetic analyzer (Anton Paar SurPASS, Austria) based on
the measurement of streaming potential with 1 mM KCl as the
electrolyte solution at a pH of 7.5. Contact angle measurements
were obtained using a drop shape analysis system (DSA 100,
Kruss, Germany) to measure the hydrophilicity of the membrane.
A 5.0 mL droplet of DI water was placed on the membrane surface
using a microsyringe with a stainless-steel needle. To reduce
error, average values of the surface charge and contact angle were
obtained by measuring six different spots on at least two different
membranes. To determine the surface and cross-sectional
morphologies of the membranes, an S-4800 (Hitachi, Japan)
scanning electron microscope (SEM) was employed. AFM was
also used to analyze the surface morphology and roughness. The
root-mean-square (RMS) roughness was obtained from three
different areas of each membrane.
2.4 RO performance
The RO performance was measured using a lab-scale cross-ow
RO unit, which consisted of three parallel ltration cells with an
effective membrane area of 19.6 cm2. The average cross-ow
velocity was 17 cm s
1. A 2 g L
1 solution of NaCl was used as
a feed solution. The membrane was compacted at 18 bar for
0.5 h and then measured at 16 bar. The concentrations of NaCl
solutions were measured using a conductivity meter. During the
RO measurements, the water ux (J) and salt rejection (R) were
calculated by the following equations:38
J ¼ DVfeed/(AmDt) (1)
R ¼ (Cf
Cp)/Cf  100% (2)
where DVfeed is the change in the volume of the feed solution,
Am is the effective area of the membrane and Dt is the perme-
ation time. The parameters Cf and Cp are the salt concentrations
in the feed and permeate.
The water permeability (A) and solute permeability (B) were
calculated as follows:39
A ¼ J/DP (3)
B ¼ A(1
R)(DP
Dp)/R (4)
16898 | J. Mater. Chem. A, 2016, 4, 16896–16905
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Paper
where DP is the transmembrane pressure difference and Dp is
the difference in osmotic pressure across the membrane.
The stability and durability of the TFC and TFN-GOQD5.0
membranes were measured via continuous long-term ltration
tests with 2 g L
1 NaCl solution as the feed solution at 16 bar
and 25  C for 120 h. In the beginning, the water ux and salt
rejection were recorded every 1 h and then the intervals were
extended to 3 h and 5 h and eventually to 10 h.
A fouling test was performed using bovine serum albumin
(BSA) and humic acid (HA) as model foulants. Prior to the
fouling experiment, a RO experiment with a 2 g L
1 NaCl feed
solution was rst conducted for 3 h to determine the initial
value of the permeate ux. Then, BSA or HA was added to the
2 g L
1 NaCl solution to obtain a concentration of 0.5 g L
1. The
fouling test was continued for 21 h. Subsequently, the fouled
membrane was cleaned using DI water for 2 h at 6 bar with
a cross-ow velocity of 72 cm s
1 and then the ux recovery was
measured using a 2 g L
1 NaCl feed solution for 3 h. The
recovery rate (FRR) and total fouling rate (Rt) were calculated as
follows:40
FRR ¼ JR/J0  100% (5)
Rt ¼ (J0
JS)/J0  100% (6)
where J0 is the initial ux, JR is the recovered ux aer washing
and JS is the steady ux for BSA or HA solution.
The chlorine resistance of the membrane was investigated by
immersing the membrane in NaClO solutions of different
concentrations. Firstly, the membrane was tested using a 2 g L
1
NaCl feed solution to measure the initial water ux and salt
rejection. Next, the membrane was exposed to a NaClO solution
(100, 500, 1000, 1500, 2000, 3000 and 5000 ppm) at a pH of 4 for
1 h. Aer chlorination, the membrane was rinsed thoroughly
with DI water and stored in DI water for 24 h before further
testing. Finally, the water ux and salt rejection of each chlorine-
treated membrane were measured.
3 Results and discussion
3.1 GOQD characterization
The chemical and physical properties of GOQD are shown in
Fig. 2. Fig. 2A and B show an AFM image of GOQD and its height
distribution. The height of GOQD varied from 0.4 nm to 1.8 nm,
whereas 83% of the materials were less than 1 nm in height,
which meant that a majority of GOQD comprised 1–3 graphene
layers.41,42 Dynamic light scattering (DLS) measurements were
conducted and it was found that GOQD had an approximate
diameter distribution of 7.5–21 nm (average diameter of 11 nm),
as shown in Fig. 2C. These results correlated well with previ-
ously reported ndings.35,43
A TEM image of GOQD (Fig. 2D) revealed a dot-like
morphology. The crystal structure of GOQD was investigated
using HR-TEM, as shown in Fig. 2E, which reveals a group of
parallel crystal planes with lattice spacings of 0.203 nm and
0.339 nm, respectively, which match the (100) and (002) crystal
planes of graphite.44 In addition, the corresponding fast Fourier
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Fig. 2 Characterization of GOQD. (A) AFM image of GOQD, (B) height distribution of GOQD from (A), (C) size distribution of GOQD obtained
from dynamic light scattering (DLS) measurements, (D) TEM image of GOQD, (E) high-resolution transmission electron microscopy (HR-TEM)
image of GOQD; the insets show fast Fourier transform (FFT) patterns, (F) size distribution of GOQD from (D), (G) zeta potential of GOQD at
different pH values, (H) FTIR spectrum, and (I) Raman spectrum of GOQD.
transform (FFT) patterns (inset in Fig. 2E) display these repre-
sentative characteristics. By determining the size of well-dispersed
GOQD from the TEM image (Fig. 2F), a narrow distribution of
5–12 nm was observed. As shown in Fig. 2G, GOQD were negatively
charged over a wide pH range and the zeta potential attained
a minimum value of
36.5 mV at a pH of 7, owing to the ionization
of COOH groups to COO
groups.45
FTIR analysis was employed to reveal the chemical nature of
the functional groups on the surface of GOQD. Fig. 2H shows
peaks at 3436 cm
1, 1720 cm
1, 1635 cm
1, and 1072 cm
1,
which were attributed to the stretching vibrations of hydroxyl
moieties, the stretching vibrations of the carbonyl unit in
carboxyl groups, the asymmetrical stretching vibrations of
carboxylate groups and the stretching vibrations of epoxy
groups, respectively.46 To further reveal the structural properties
of GOQD, Raman spectroscopic analysis was employed. The two
characteristic peaks of the D band at 1347 cm
1 and the G band
at 1590 cm
1 can be observed in Fig. 2I. In general, the D band
provides evidence of the presence of structural defects and
disorders in the graphite lattice generated by vacancies, edges,
and epoxide and hydroxyl groups47,48 and the G band is associ-
ated with the sp2 hybridization of graphitic carbon.49 Therefore,
the ratio of the peak intensity of the D band to that of the G band
(ID/IG) demonstrates the extent of surface defects. GOQD exhibi-
ted a higher value of ID/IG (1.12) than that of GO (0.94, as shown
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Journal of Materials Chemistry A
in Fig. S1 in the ESI†), which indicated that there were more
structural defects or disorders on GOQD nanosheets as a result of
the higher edge-to-volume ratio of GOQD than that of GO.50
3.2 Membrane characterization
Fig. 3 illustrates the chemical and physical properties of the TFC
and GOQD-incorporated TFN membranes. To conrm the
successful interfacial polymerization of polyamide and the
incorporation of GOQD in the PA layer, ATR-FTIR and micro-
Raman analysis were performed. Fig. 3A shows the FTIR spectra
of the TFC and TFN-GOQD5.0 membranes. The TFC membrane
exhibited characteristic peaks at 1660 cm
1, 1610 cm
1 and
1542 cm
1, which corresponded to amide I C]O stretching
vibrations, hydrogen-bonded C]O stretching vibrations, and
amide II N–H stretching vibrations, respectively.30 In the case of
the TFN-GOQD5.0 membrane, the broad band at approximately
3440 cm
1 was intensied, which conrmed the incorporation
of GOQD nanosheets with abundant carboxylic acid and
hydroxyl groups.51 In the Raman results (Fig. 3B), the TFC
membrane exhibited three characteristic peaks at 1457 cm
1,
1525 cm
1, and 1635 cm
1, which were produced by aromatic
rings in the PSf substrate and C]O groups in the PA layer.52,53
The TFN-GOQD5.0 membrane exhibited a typical D band at
1346 cm
1 and a G band at 1584 cm
1, which demonstrated the
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Fig. 3 Characterization of the prepared membranes. (A) ATR-FTIR
spectra, (B) micro-Raman spectra, (C) zeta potential and (D) contact
angle of the TFC and GOQD-incorporated membranes. The micro-
Raman spectrum of TFN-GOQD5.0 was obtained by focusing the laser
spot on the island-shaped domains on the membrane surface.
incorporation of GOQD into the membrane. It is supposed that
carboxyl groups on GOQD reacted with the amine groups of
MPD in the mixed solution. During the interfacial polymeriza-
tion process, carboxyl groups on GOQD formed covalent bonds
via condensation reactions with terminal carboxyl groups of
TMC in the linear portion of polyamide. Both factors made the
selective layer more compact, which improved the stability of
the membrane.
The surface charge and contact angle of the prepared
membranes are shown in Fig. 3C and D. Both parameters
decreased with an increase in the GOQD content. The presence
of numerous negatively charged oxygen-containing groups on
GOQD was believed to increase the surface charge density. These
oxygen-containing groups also provided excellent hydrophilicity
to GOQD. Accordingly, larger amounts of GOQD in the PA layer
endowed the TFN membrane with higher hydrophilicity.26 A
similar phenomenon was also observed for the GO-incorporated
TFN membranes (Fig. S2 in the ESI†).
Fig. 4 shows the morphologies and structures of the prepared
membranes as characterized by SEM and AFM. The TFC
membrane exhibited a rough ridge-and-valley structure (Fig. 4A),
which indicated the successful formation of a PA active layer.54 As
shown in Fig. 4B and C, the GOQD-incorporated TFN membranes
exhibited a different surface morphology. As the GOQD content
increased in the TFN membrane, the upper surface appeared to
have more protruding domains with a blocky shape, which were
composed of grainy structures. As shown in the cross-sectional
SEM images (Fig. 4D–F), GOQD impeded the diffusion of MPD
molecules, which resulted in a lower thickness of the polyamide
layer.
The surface morphology and RMS roughness of the prepared
RO membranes were also investigated using AFM. Evidently, both
TFC and TFN membranes possessed rough upper surfaces.
16900 | J. Mater. Chem. A, 2016, 4, 16896–16905
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Fig. 4 SEM images of surface morphology and cross-sectional
morphology and AFM images of the prepared membranes. SEM and
AFM (scan size 1 mm  1 mm, z-scale 1 mm) images of (A, D and G) TFC,
(B, E and H) TFN-GOQD5.0, and (C, F and I) TFN-GOQD10.0
membranes.
However, based on the RMS roughness values calculated from the
AFM images, it was concluded that the TFN membrane was
rougher than the TFC membrane, which was attributed to the
appearance of island-shaped protrusions. A mixture of GOQD and
MPD was pressed and ltered onto a PSf substrate to form
a cushion before adding TMC. Fig. S3† shows homogeneous
GOQD/MPD cushion lms when the GOQD content was less than
5 mg. The color of the membrane became darker with an increase
in the GOQD content (Fig. S3 in the ESI†). During the interfacial
polymerization process, MPD needed to penetrate the GOQD layer
to react with TMC. The steric hindrance of the GOQD layer
decreased the diffusion of MPD and thereby retarded the forma-
tion of the PA layer. Moreover, GOQD were squeezed out from the
layer to form agglomerates, which resulted in a signicant
increase in RMS roughness. The introduction of GOQD led to
additional nanocorridors, reduced the thickness of polyamide
and increased its roughness, which promoted the permeation of
water through the membrane.
When GO was used in place of GOQD, at surface
morphologies were observed in SEM and AFM images (Fig. S4 in
the ESI†). GO was of a larger size than GOQD and therefore
deposition of a GO layer on the PSf substrate resulted in more
severe steric hindrance. The GO layer blocked the diffusion of
MPD such that a poor-quality PA layer was formed and
a resulting at surface morphology was found.26
3.3 Membrane performance
To determine the effects of GOQD on RO performance, a series
of prepared TFN membranes were tested using 2 g L
1 NaCl as
This journal is © The Royal Society of Chemistry 2016

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the feed solution at 16 bar. As shown in Fig. 5A, the TFC
membrane exhibited a permeate ux of 24.7 L m
2 h
1 (LMH)
with a NaCl rejection of 98.5%. The permeate ux of the TFN
membrane increased with an increase in GOQD content and
the NaCl rejection was maintained at a high level (>98.5%).
TFN-GOQD5.0 achieved a ux of 37.5 LMH, which represented
a 51.8% increase in comparison with that of the TFC membrane
without GOQD. The NaCl rejection of TFN-GOQD5.0 was 98.8%.
This increase in permeate ux was attributed to the addition of
GOQD, which affected the water permeability of the membrane
in the following ways. Firstly, the incorporation of GOQD
improved the hydrophilicity of the membrane.55 Secondly,
nanochannels between GOQD nanosheets served as a perme-
ation route, which shortened the paths of water through the
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membrane.56 Moreover, some voids were unavoidably intro-
duced into the thin lm layer at the surface of GOQD. These
nanocorridors also facilitated the permeation of water through
the membrane.57 In addition, the greater roughness also played
an important role in increasing water ux as a result of the
larger effective contact area between water molecules and the
membrane. However, the incorporation of GOQD did not
provide high selectivity and the dense PA layer was the only
determining factor of the membrane's salt permeability.30,58 In
other words, the incorporation of a selected amount of GOQD
(less than 5.0 mg) maintained an integrated PA layer on top of
the TFN membrane.
A further increase in GOQD in the membrane (TFN-
GOQD10.0) resulted in a decline in the NaCl rejection to 81.0%.
This phenomenon agreed well with the solute permeability (B)
shown in Fig. 5B, where TFN-GOQD10.0 exhibited an extremely
high solute permeability. At higher GOQD contents, it was
found that GOQD aggregated and prevented the diffusion of
MPD, which resulted in the formation of defects in the PA layer.
Both water and the solute could penetrate the membrane
through these defects.
As a control, the RO performance of GO-incorporated TFN
membranes is shown in Fig. S5 (ESI†). As can be seen, the
permeate ux increased with an increase in GO content, but the
salt rejection dramatically decreased. This is consistent with the
SEM images of this membrane shown in Fig. S4 (ESI†), where
only a low-quality PA layer was formed on the GO/MPD cushion.
Membrane stability is of great importance in RO applica-
tions. The long-term stability of membranes that contain
carbon materials (such as CNT, GO, GOQD, and so forth) for use
Fig. 5 Performance of the prepared membranes with different GOQD
contents. (A) RO flux (J) and salt rejection (R), and (B) water perme-
ability (A) and solute permeability (B).
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Journal of Materials Chemistry A
in water treatment and desalination applications remains
a challenge. Fig. 6A illustrates the water ux and salt rejection of
the TFC and TFN-GOQD5.0 membranes during a 120 h
continuous RO test. Both TFC and TFN-GOQD5.0 membranes
exhibited very stable uxes and rejections. Fig. 6B shows
photographs of the TFC and TFN-GOQD5.0 membranes before
and aer RO operation. As shown, there was hardly any differ-
ence in the morphologies of these membranes aer the RO test.
This demonstrated that a robust PA layer was formed on the
TFN-GOQD5.0 membrane. However, the active layer of the
GO-incorporated membranes peeled away from the top of the
membranes aer the RO test (Fig. S6 in the ESI†). The poor
stability of the TFN-GO membranes further demonstrated that
an unintegrated PA layer had been formed as a result of the
severe steric hindrance of GO, which strongly hindered the
diffusion of MPD.
3.4 Antifouling capacity
Membrane fouling is one of the main issues that affect the
efficiency of membranes during their use in RO. The onset of
fouling causes a sharp decline in ux and increases the main-
tenance costs. To investigate the antifouling capacity of the
prepared membranes, the TFC and TFN-GOQD5.0 membranes
were assessed for RO fouling and cleaning employing bovine
serum albumin (BSA) as a model protein foulant and humic
acid (HA) as a natural organic foulant.59 To ensure that the
transverse hydrodynamic force was identical for the membrane
fouling, the fouling tests were conducted using the same initial
permeate ux of 24.7 LMH. As shown in Fig. 7A and C, the uxes
dramatically decreased when BSA or HA was added to the feed
solutions and reached a steady value aer a 21 h fouling test.
Subsequently, the recovered uxes were measured aer the
fouled membranes were rinsed. The results of the fouling tests
indicated that the incorporation of GOQD signicantly
improved the antifouling capacity of the RO membranes. As
shown in Fig. 7B, the TFC membrane exhibited a total fouling
rate (Rt) for BSA of 41.7% and a recovery rate (FRR) of 83.8%.
The TFN-GOQD5.0 membrane exhibited higher BSA resistance
with an Rt of 29.2% and an FRR of 93.5%. A similar trend was
observed in the fouling test that used HA (Fig. 7D). The TFC
Fig. 6 Long-term separation performance of the TFC and TFN-
GOQD5.0 membranes as a function of time using 2 g L
1 NaCl solution
at 16 bar and 25  C. (A) Water flux and salt rejection, (B) photographs of
TFC (B1 and B3) and TFN-GOQD5.0 (B2 and B4) membranes before
and after the RO test.
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Fig. 7 Antifouling behavior of the TFC and TFN-GOQD5.0
membranes in RO processes. (A) Time-dependent flux for BSA, (B)
fouling resistance for BSA, (C) time-dependent flux for HA, and (D)
fouling resistance for HA.
membrane exhibited an Rt of 48.7% and an FRR of 69.2% and
the TFN-GOQD5.0 membrane exhibited an Rt of 32.5% and an
FRR of 90.0%.
The improved antifouling properties of the experimental
membranes resulted from the increase in surface hydrophilicity
on incorporating GOQD.60 Higher surface hydrophilicity can
reduce the adsorption of foulants on the membrane surface,
thus mitigating surface fouling. In addition, the higher surface
hydrophilicity also promoted the desorption of hydrophobic
Fig. 8 (A) Separation performance of the TFC and TFN-GOQD5.0 membranes, (B) ATR-FTIR spectra of the TFC membrane, (C) ATR-FTIR spectra
of the TFN-GOQD5.0 membrane, and (D) SEM images of the TFC and TFN-GOQD5.0 membranes before and after chlorination.
16902 | J. Mater. Chem. A, 2016, 4, 16896–16905
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Paper
foulants from the surface during the rinsing process and led to
better ux recovery.61 Furthermore, both BSA and HA contain
negative charges at a pH of 7.62 This increased the amount of
negative surface charge in the TFN-GOQD5.0 membrane and
produced stronger electrostatic repulsion between the foulants
and the TFN membrane.63
3.5 Chlorine resistance
In a practical RO process, a chlorine detergent is commonly
used as a disinfectant to control biofouling and/or as
a membrane-cleaning agent for chemical washing. However,
the PA matrix is vulnerable to active chlorine, which will reduce
the salt rejection of the membrane and degrade the selective
layer.64 To investigate the chlorine resistance of the prepared
membranes, the TFC and TFN-GOQD5.0 membranes were
tested by comparing the changes in salt rejection aer exposing
the membranes to 100–5000 ppm h chlorine (Fig. 8A). The salt
rejection of the TFC membrane signicantly decreased from
98.5% to 59.4% aer exposure to 5000 ppm h active chlorine.
Chlorination destroyed the hydrogen bonds in the polyamide
chains, which caused severe conformational deformation of the
polyamide chains. This resulted in partial destruction of the
polyamide layer and an increase in salt passage.65,66 The
TFN-GOQD5.0 membrane exhibited a lesser decline in salt
rejection from 98.8% to 83.6% aer chlorination at 5000 ppm h.
The salt rejection remained higher than 90% aer chlorination at
3000 ppm h. These results indicated that the chlorine tolerance of
the TFN-GOQD5.0 membrane was improved in comparison with
that of the TFC membrane.
To further investigate the chemical changes in the TFC and
TFN-GOQD5.0 membranes before and aer chlorination,
ATR-FTIR was employed to analyze the characteristic peaks of
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Paper Journal of Materials Chemistry A

band and amide II band for the TFC membrane signicantly

Fig. 9 TGA curves of the selective layers separated from the TFC and
TFN-GOQD5.0 membranes.
the membranes at different active chlorine capacities. As shown
in Fig. 8B and C, the peaks at 1660 cm
1 and 1545 cm
1 cor-
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declined as the chlorination became more intensive. Aer chlo-
rination at 5000 ppm h, both peaks were very weak, which
demonstrated the degradation of the PA selective layer.66 For the
TFN-GOQD5.0 membrane, the decrease in the peak intensities of
the amide I band and amide II band was relatively smaller than
that for the virgin TFC membrane, which indicated that the
incorporated GOQD appeared to protect the PA matrix from
chlorine.
Fig. 8D shows surface SEM images of the TFC and TFN-
GOQD5.0 membranes before and aer chlorination. For the
TFC membrane, some of the ridge and valley structures dis-
appeared aer chlorination. When the TFC membrane was
treated with active chlorine at 5000 ppm h, some defects were

responded to amide I band C]O stretching vibrations and
amide II band N–H in-plane bending vibrations, respectively.
These two peaks were sensitive to chlorine and changed
remarkably aer chlorination. The intermolecular hydrogen
bonds between polyamide chains became weaker and were
broken on exposure to chlorine. Therefore, the peak at 1660 cm
1
shied to a higher frequency with an increase in active chlorine
capacity.65,66 It is worth noting that the intensity of the amide I
observed. These were attributed to the collapse of polyamide
chains or the separation of the polyamide layer from the PSf
substrate. For the TFN-GOQD5.0 membrane, less damage can
be observed in the SEM images.
As shown in Fig. 9, the TGA curves of the selective layers of
the TFC and TFN-GOQD5.0 membranes provided some
evidence of the increase in thermal stability on loading with
GOQD. A major weight loss at approximately 500  C was

Table 1 Comparison of performance of GO- and GOQD-containing RO membranes

Flow Feed
Pressure rate (NaCl, J R Chlorine resistance
Approach (bar) (cm s
1) ppm) (LMH) (%) Durability Antifouling (NaClO, ppm h)

GO in PSf support, 15.5 22.2 2000 84 98.2 — — —

PA as selective layer33
rGO/TiO2 in PA 15 — 2000 51.3 99.45 — 500 mg L
1 BSA, 4000 ppm h, pH ¼ 4,
selective layer 3 h, Rt: 25% R decreased 3%
(rGO/TiO2 dispersed in
aqueous solution of MPD)68
GO in PA selective layer 20.68 — 2000 59.4 93.8 J and R — —
(GO dispersed in were stable
TMC/hexane solution)51 aer 72 h
GO in PA selective layer 15.5 — 2000 16.6 99 — Diluted PAO1 in 48 000 ppm h,
(GO dispersed in 1/100 TSB, 24 h, pH ¼ 7,
aqueous solution of MPD)26 attached biovolume R decreased <1%
of cells decreased 98%
CNTa/GO in PA selective 15.5 8.4 2000 58.96 96.2 J decreased — 20 000 ppm h,
layer (CNTa/GO dispersed 15% aer R decreased 10%
in aqueous solution of MPD)29 72 h
GO/aGO LbL on PA30 15.5 — 2000 14.0 96.4 — 100 ppm BSA, 6000 ppm h,
12 h, Rt: 15% pH ¼ 10, R declined
by <4%;
60 000 ppm h,
pH ¼ 10, R decreased
>80%
aPES/aGO/GO LbL 55 — 32 000 28.4 98.4 — — 300 ppm NaClO,
assembly69 R decreased 14.4%
GO covalently 27.6 21.4 2925 41.4 97.8 — 107 units per mL E. coli —
bonded to PA27 in contact with membrane
for 1 h, number of viable
E. coli cells decreased 64.5%
GOQD in PA selective 16.0 17.0 2000 37.5 98.8 J and R were 500 ppm BSA, 21 h, Rt 29.2%, 5000 ppm h, pH ¼ 4,
layer (GOQD/MPD stable aer FRR 93.5%; 500 ppm HA, 21 h, R decreased 15%
ltered onto PSf) 120 h Rt: 32.5%, FRR 90.0%
(present work)

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Journal of Materials Chemistry A
observed for both membranes, which was consistent with the
thermochemical decomposition of polyamides.67 The mass of
the polyamide layer of the TFC membrane continued to
decrease gradually with an increase in temperature, whereas the
mass of the selective layer of TFN-GOQD5.0 was almost
unchanged. Therefore, the incorporation of GOQD increased
both the chlorine tolerance and the thermal stability of the TFN
membranes.
It was known that GOQD hindered the diffusion of organic
molecules; therefore, they could also block active chlorine.9 The
reduced diffusion rate of OCl
ions favored the increase in
chlorine resistance. In addition, hydrogen bonding between
GOQD and the polyamide layer made the polymer chains more
compact and inhibited the replacement of amidic hydrogens,
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which contributed to both chlorine tolerance and thermal
stability.26 Another possibility lay in the protection of active sites
in residual MPD by electron-rich GOQD from being attacked by
active chlorine. Charge exclusion could impede the contact of
OCl
with the membrane surface and thus prevent active
chlorine from disrupting the PA selective layer.
Table 1 summarizes the performance of GO- and GOQD-
containing RO membranes reported in the recent literature.
The TFN-GOQD5.0 membrane exhibited comparable ux and
excellent NaCl rejection. It was worth mentioning that the
TFN-GOQD5.0 membrane exhibited a very stable ux and rejec-
tion during the extended RO test, which suggested outstanding
durability during membrane processes. In addition, the TFN
membrane prepared in the present work possessed excellent
antifouling capacity and chlorine resistance, which are greatly
desired in membrane desalination and water reclamation
processes.
4 Conclusions
In summary, a novel GOQD-incorporated TFN membrane was
developed by pressure-ltering a GOQD/MPD cushion layer onto
a PSf substrate prior to interfacial polymerization. In compar-
ison with a reference TFC membrane, the TFN membrane
exhibited a higher permeate ux and maintained an excellent
NaCl rejection efficiency. Furthermore, the TFN membrane
possessed outstanding stability, excellent antifouling capacity,
and improved chlorine resistance. The GOQD-incorporated TFN
membrane has the potential for applications in membrane
ltration processes such as reverse osmosis, forward osmosis,
and nanoltration on the basis of its high water permeability
and solute selectivity, as well as its antifouling capacity and
chlorine tolerance.
Acknowledgements
The authors are grateful for the nancial support from the
National Natural Science Foundation of China (21476219) and
the Science and Technology Development Plan of Shandong
province (2014GSF116006). We would like to thank Qingdao
Haida Haixi New Materials Co., Ltd (China) for providing
GOQD. This is MCTL contribution no. 100.
16904 | J. Mater. Chem. A, 2016, 4, 16896–16905
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Paper
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