Journal of Colloid and Interface Science 484 (2016) 107–115

Contents lists available at ScienceDirect

Journal of Colloid and Interface Science

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

Regular Article

Anti-bacterial properties of ultrafiltration membrane modified by

graphene oxide with nano-silver particles
Jingchun Li, Xuyang Liu, Jiaqi Lu, Yudan Wang, Guanglu Li, Fangbo Zhao ⇑
College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China

g r a p h i c a l a b s t r a c t

AgNO3

GO Ag/GO

membrane
casng soluon

phase inversion

a r t i c l e i n f o a b s t r a c t

Article history: To improve the anti-biofouling properties of PVDF membranes, GO-Ag composites were synthesized and
Received 12 July 2016 used as membrane antibacterial agent by a simple and environmentally friendly method. As identified by
Revised 23 August 2016 XRD, TEM and FTIR analysis, AgNPs were uniformly assembled on the synthesized GO-Ag sheets. The
Accepted 24 August 2016
membranes were prepared by phase inversion method with different additional amounts (0.00–
Available online 30 August 2016
0.15 wt%) of GO-Ag composites. The GO-Ag composites modified membranes show improved
hydrophilicity, mechanical property and permeability than unmodified PVDF membrane. Specially, the
Keywords:
antibacterial properties and inhibition of biofilm formation were greatly enhanced based on conventional
GO-Ag composites
Polyvinylidene fluoride (PVDF)
inhibition zone test and anti-adhesion of bacterial experiment. The modified membranes also reveal a
Antibacterial remarkable long-term continuous antimicrobial activity with slower release rate of Ag+ compared to
Anti-biofouling AgNPs/PVDF membrane.
Ó 2016 Elsevier Inc. All rights reserved.

1. Introduction problems always exist in an emerging separation/desalination

Ultrafiltration (UF) has a wide application in drinking water
production and wastewater treatment due to its low cost and high
liquid separation efficiency [1,2]. However, membrane fouling
⇑ Corresponding author.
E-mail address: zfbhit@163.com (F. Zhao).
membrane process, which limits the practical applications. For all
types of fouling, biofouling is the most complicated and inevitable
in membrane separation process, since the biofilm is not easily
removed and results in a decrease in water flux and selectivity
[3,4]. In addition, higher operating and maintenance cost is
required for cleaning of biofouling on membrane by mechanical
or chemical approaches [5]. Hence, to overcome such disadvan-

http://dx.doi.org/10.1016/j.jcis.2016.08.063
0021-9797/Ó 2016 Elsevier Inc. All rights reserved.
108 J. Li et al. / Journal of Colloid and Interface Science 484 (2016) 107–115

tages, various strategies have been proposed to suppress the bio-
fouling of membrane process in recent years [6,7]. A common
strategy employed to prevent biofilm growth and membrane foul-
ing is the addition of antibacterial nanoparticles, such as titanium
dioxide (TiO2), silicon dioxide, and zinc oxide (ZnO), to the mem-
brane backbone materials during membrane preparation [8–10].
Another effective way to mitigate the membrane fouling was to
increase the membrane layer hydrophilicity [11]. A more hydro-
philic membrane surface was usually less susceptible to be fouled
under the same separation conditions [12].
Polyvinylidene fluoride (PVDF) is a common material for ultra-
filtration membrane preparation for its excellent chemical stability
and thermal performance [13]. However, the inherent hydropho-
bicity of the PVDF membrane is easy to be contaminated by bacte-
ria and causes biofouling on the surface or in the pores of
membranes during wastewater treatment process [14]. Based on
this mechanism, a number of works have been reported to increase
the hydrophilic properties of PVDF membranes by blending metal-
lic and non-metallic nanoparticles into PVDF matrix [1,15,16].
In recent years, graphene oxide (GO) has been used as modifier
in polymer membranes to enhance the mechanical strength and
hydrophilic properties of membranes due to its large specific sur-
face area and abundant oxygen-containing surface groups [17–
19]. Due to its strong inhibitory and biocidal effects [20,21] silver
nanoparticles (AgNPs) and silver composite have been used to
decrease membrane biofouling [22–24]. In our previous study,
the hydrophilicity, permeability and in situ antibacterial properties
were improved for the Ag-embedded nano-sized titanium dioxide
(Ag-n-TiO2) modified polyvinyl chloride (PVC) membranes [25].
However, the nanoscale AgNPs are hard to be fixed in the
membrane firmly by physical blending and thus Ag+ is easily
isolated from chemical groups in the complex and actual water
condition [26].
Silver nanoparticles assembled on graphene oxide sheets (GO–
Ag) have been exploited as a novel antibacterial agent [27]. GO’s
functional groups provide ideal nucleation sites for AgNPs. There-
fore, AgNPs can strongly attach to the GO surface [27]. In addition,
GO can be easily dispersed into polymer matrix, and increases the
compatibility of membrane casting solution. Therefore, in this
paper we report the fabrication of a novel type of PVDF mixed
membrane by embedding GO-Ag composites. Since few of litera-
tures have reported the application of GO-Ag composites as

AgNO3

Fig. 1. Principles of the reactions of modified GO.

Fig. 2. Schematic diagram of the fabricated processes of GO-Ag/PVDF membrane.

 J. Li et al. / Journal of Colloid and Interface Science 484 (2016) 107–115
Table 1
Compositions of membrane casting solutions with different GO-Ag composites loading.
Membrane GO-Ag (wt%)
M-0 0 17%
M-0.05 0.05
M-0.10 0.10
M-0.15 0.15
antibacterial agent to modified PVDF-based membranes, this study
focuses on the novel modifier to enhance the antibacterial proper-
ties and mechanical properties of the modified PVDF membranes.
2. Experimental section
2.1. Materials
PVDF (Shenyang Chemical Industry Co., Ltd., China) was
employed as the base polymer. N,N-dimethyl acetamide (DMAC,
>99.5%, AR, Bodi Co., Ltd., China), polyvinyl pyrrolidone (PVP, AR,
Lanji Co., Ltd, China), and flake natural graphite powder were
obtained from Qingdao Tianhe Co., Ltd. (China). H2SO4 (purity,
98%), sodium nitrate (NaNO3), hydrogen peroxide solution (5%),
KMnO4 and ethanol applied in GO preparation were purchased
from Fuyu Co., Ltd. (China). Silver nitrate (AgNO3, >99.8%, AR, Tian-
jin Kemiou Chemical Agent Co., Ltd., China) and isonicotinic acid
(>99.5%, AR, Tianjin Guangfu Fine Chemical Research Institute)
were used to synthesize GO-Ag composites. The distilled water
was used as the non-solvent for the polymer precipitation.
2.2. Synthesis and characterization of GO-Ag composites
The precursor of GO was produced by the Hummers method
[28]. GO-Ag composites were prepared via a two-step solution
intercalation method. Firstly, 0.1 g isonicotinic acid was added into
150 mL toluene under room temperature and vibration (125 r/
min). Subsequently, 0.05 g GO nanosheets were added into the
mixture. The resulting mixture was stirring during reflux for two
hours at 60 °C to synthesize the modified GO. Next, the obtained
were vacuum drying at 60 °C. Then, 0.04 g GO, 1 mL of 0.1 mol/L
AgNO3 solution, and 100 mL methanol were mixed in 250 mL
erlenmeyer flask under the condition of 30 min magnetic stirring.
After that, the mixture was shaken at the rate of 125 r/min
(25 °C), subsequently, the mixture was centrifuged with washing
by methanol for several times, and finally, the sample was
obtained by drying at 60 °C. Fig. 1 shows the basic principles of
the reactions. The presence of Ag nanoparticles was characterized
by Transmission electron microscopy transmission electron micro-
scopy (TEM, JEM-2000EX, Japan). Before the measurement, GO-Ag
composites were suspended in 200 mL ethanol followed by ultra-
sonic treatment for 5 min and then the 0.2 mL of dispersion solu-
tions were transferred to a copper grid (400 meshes) coated with
a carbon film. The chemical structures of the GO-Ag composites
were characterized using a NEXUS 670 Fourier transform infrared
spectrometer (FT-IR, PE-100, USA). Prior to testing, the particles
were dried at 60 °C in a vacuum oven for 24 h to remove the
absorbed water. The structure of GO was analyzed by powder
XRD (Rigaku, Japan) using a TTR-III diffract meter under Cu Ka
radiation (k = 0.15406 nm).
2.3. Membrane preparation
The schematic diagram of the fabricated processes of mem-
brane is presented in Fig. 2. Both pure PVDF membranes and GO-
Ag/PVDF flat sheet membranes were prepared via the immersion
109
PVDF (wt%) PVP (wt%) DMAC (wt%)
3% 80%
17% 3% 79.95%
17% 3% 79.90%
17% 3% 79.85%
phase inversion method [29]. PVDF 17 wt% and polyvinyl pyrroli-
done (PVP) 3 wt% were applied as the polymer matrix. Four differ-
ent concentrations of GO-Ag composites (i.e., 0.0, 0.05, 0.10,
0.15 wt%) were added and dispersed in DMAC in a 25 °C ultrasonic
bath at 40 kHz for 60 min. Subsequently, the PVDF resin powder
and PVP were added to the solution at 60 °C and stirred for 24 h
to obtain homogenous solutions for casting. The solution was kept
in a drying oven overnight to remove air bubble. The solutions
were casted on a glass plate using a membrane casting machine
with the thickness of 400 lm and immediately dipped into a dis-
tilled water coagulating bath (25 °C). After complete coagulation,
the wet membranes were stored in distilled water at least 48 h
before the following investigation. Table 1 shows the compositions
of the casting solutions.
2.4. Membrane characterization
2.4.1. Viscosities of the casting solutions
The viscosity of the casting solutions was measured by a rota-
tional viscometer (NDJ-5S, Shanghai Changji instrument Co., Ltd.,
China) at 25 °C.
2.4.2. Scanning electron microscopy (SEM) and Energy dispersive
spectrometer (EDS)
The surface and cross-section of the prepared membranes were
characterized by a scanning electron microscope (JSM-6480A, JEOL,
Japan) at 10 kV in a high vacuum mode after being coated with
approximately 10 nm of gold. Samples of the membranes were fro-
zen in liquid nitrogen and then fractured. At the same time, Energy
Dispersive Spectrometer (EDS) was used to examine the GO-Ag
composites loaded on the surface of membranes.
2.4.3. Contact angle
Contact angle measurements of the membranes were per-
formed using a JYSP-360 contact angle goniometer (Jin Shengxin
Co., Ltd., China). The membranes were dried in the air for about
48 h before the measurements. The dynamic water contact angle
was measured by placing 2 lL of deionized water on the
membrane surface for multiple (P10) measurements to obtain
an average value.
2.4.4. Mechanical characterization
The mechanical properties of the membranes were measured
using an electric elastic yarn strength analyzer (YG020B, Nantong
Sansi Co., Ltd., China) at a pull rate of 2 mm/min. Every sample
was tested for 5 times to obtain an average value.
2.5. Study of antibacterial properties and anti-adhesion effect of
bacteria
Antibacterial performance was investigated by inhibition
method using E. coli bacteria [30]. One mL of E. coli bacteria sus-
pension was incubated at 37 °C and shaken at 130 rpm for 12 h.
Luria-Bertani (LB) agar solid medium was seeded with the bacteria
suspension. In order to evaluate antibacterial performance, all the
membrane samples (about 10 mm diameter) and worktable were
disinfected by autoclaving for 1 h. Membranes were then placed
110 J. Li et al. / Journal of Colloid and Interface Science 484 (2016) 107–115
14000
12000
10000
Intensity (a.u)
8000
6000
4000
2000
0 0
0 10 20 30 40
2θ (°)
Fig. 3. XRD images of (a) GO and (b) GO-Ag composites.
Fig. 4. TEM images of (a) GO and (b) GO-Ag composites.
on Luria–Bertani (LB) agar plates of E. coli incubated at 310 K for
24 h, which ensure the concentration of E. coli within 107–
109 CFU/mL.
Anti-bacteria adhesion effect was evaluated by the colony-
counting method [31]. Micro-polluted water was used as feed solu-
tion through the dead-end filtration cell (Millipore) at a pressure of
0.1 MPa. All the filtration fluid was collected and then 1 mL of solu-
tion for further expanded culture was used for solid plate culture
medium.
2.6. Membrane performance testing
The filtration experiment was conducted using an Amicon 8200
stirred dead-end filtration cell (Millipore) at a pressure of 0.1 MPa.
And the membranes had an effective area of 32.15 cm2. Prior to the
permeation testing, each membrane was first compacted at
0.20 MPa with distilled water for 20 min to obtain a steady flux.
The pure water flux was obtained by Eq. (1) [32]:
m functional groups when silver decorated on the GO. Fig. 5 shows
J¼
q:s:t
where m, t and S are mass of the permeated water (kg), the perme-
ation time (h), and membrane area (m2), respectively.
2.7. Study of silver ions release
To study the kinetics of silver ions released from the prepared
GO-Ag/PVDF membranes, 5% nitric acid was used as a simulated
fluid. The dried membranes were cut into disks in diameter of
10 mm with the same mass. The pieces of membranes were
immersed in 50 mL of the simulated fluid under ultrasonic condi-
tion for 10 h. Finally, ICP-MS was used to determine the silver con-
centration of the suspending fluid.
1200
(a) (b)
1000
Intensity (a.u)
800
600
400
200
50 60 70 80 0 10 20 30 40 50 60 70 80
2θ (°)
3. Results and discussion
3.1. Characterization of GO-Ag composites
For the characterizations of GO and GO-Ag composites, XRD,
TEM and FTIR experiments were conducted. XRD spectrum (Fig. 3
(a)) showed the typical diffraction peak of GO at 2h = 10.03° within
the structure of GO-Ag composites. The XRD test result confirmed
that GO was successfully produced by oxidation of graphite, and
some function groups were introduced to the surface and the edges
of GO sheets. As shown in Fig. 3(b), the diffraction peaks at
2h = 33°, 44° and 77° were attributed to the diffraction plane of sil-
ver crystal on GO surface. TEM image showed the typical lamellar
morphology and layer structure of GO with wrinkles and curves
(Fig. 4(a)). Fig. 4(b) showed that silver nanoparticles with a spher-
ical shape were uniformly deposited on the GO surface and no par-
ticles were observed outside the GO sheets. It was also observed
that there were no changes on the lamellar of GO with hydrophilic
ð1Þ the FTIR of GO and GO-Ag composites. GO had a strong band at
3412 cm1 majorly associated with OH stretching vibration, the
band at 1735 cm1 indicated the C@O stretching of carboxyl group
(COOH), the band at 1225 cm1 associated with CAOAC stretching
and the band at 1055 cm1 associated with CAO stretching. Com-
pared with the FTIR of GO, after the deposition of the AgNPs on the
GO sheets, some peaks in the absorption features shifted largely. A
prominent peak of 1390 cm1 was appeared. The reason was
ascribed to strong interactions between positive Ag+ and function
groups of GO sheets. Hence, the FTIR spectrum indicated the excel-
lent hydrophilic property of GO and GO-Ag composites [33]. XRD,
TEM and FTIR results showed the evenly and uniformly deposited
silver nanoparticles on the GO sheets. These results were also sim-
ilar to other reports [34].
 J. Li et al. / Journal of Colloid and Interface Science 484 (2016) 107–115 111

15000 700
650
14000
600

13000 550
500

Viscosity/ (Pa·s)
GO
12000 450
Transmitance/%

Thickness/mm
1225
1055 400
11000
GO-Ag 350
10000 300
1389 250
9000
1725 200

8000 150
100
3412 -0.05 0.00 0.05 0.10 0.15 0.20
GO-Ag content/%

Fig. 6. Viscosity of casting solutions and thickness of memranes.

4500 4000 3500 3000 2500 2000 1500 1000 500
Wavenumber/cm-1

Fig. 5. FTIR images of (a) GO and (b) GO-Ag composites.
3.2. Characterization of modified PVDF membranes
3.2.1. Viscosity of casting solutions and thickness of membranes
Fig. 6 reveals the viscosities of PVDF casting solution and thick-
ness of membranes with different GO-Ag composites loading. An
increase in casting solution viscosity and thickness was observed
with the addition of GO-Ag composites. With the increase of
viscosity, the motion of polymer solution molecules was inhibited
by the flow resistance, resulting in decreased fluidity and worse
film-forming. In addition, the high viscosity also decelerates the
diffusions of nonsolvent into the polymer during phase separation
process. Hence, a thicker and dense membrane was produced [35].
3.2.2. Membrane microstructure and EDS analysis
Fig. 7 shows images of surface and cross-section of membranes
with different GO-Ag composites contents. All the modified PVDF
membranes have typical asymmetric structures. From these SEM
images, finger-like voids could be observed as GO-Ag composites
concentration increased from 0.05 to 0.15 wt%. GO-Ag composites
loading at 0.1 and 0.15 wt% resulted in membranes with larger
finger-like pore structure. Haider et al. also reported similar
phenomena in the literature [36]. The changes in substrate mor-
phology could be attributed to the higher exchange rate between
solvent and non-solvent due to the addition of small amount of
hydrophilic GO-Ag composites.
Energy dispersive spectrometer (EDS) was used to examine
whether the GO-Ag composites have been assembled on the
modified membranes. Fig. 8 depicts the EDS elemental analysis of

Fig. 7. SEM images of (a) 0.05 wt% GO-Ag modified membrane, (b) 0.10 wt% GO-Ag modified membrane and (c) 0.15 wt% GO-Ag modified membrane.
112 J. Li et al. / Journal of Colloid and Interface Science 484 (2016) 107–115

pure PVDF membrane and modified membranes. Compared with
the unmodified membrane, it was found that the EDS analyses of
the modified membranes contained significant characteristic peaks
of silver. These characteristic peaks verified the successful incorpo-
ration of GO-Ag structure. In addition, the intensity of silver peaks
in EDS spectrum increased with the GO-Ag composite
concentrations.
3.2.3. Contact angle and water flux of membrane
The contact angle was almost in accord with membrane perme-
ability. For instance, the pure PVDF membrane showed the largest
water contact angle of 82.06° due to the intrinsic hydrophobic
characteristic of PVDF. Addition of 0.05, 0.1 and 0.15 wt% GO-Ag
composites decreased the water contact angle to 70.6°, 64.6° and
63.4°, which could be attributed to the hydrophilic functional

(a) Element Wt% At%

CK 50.62 61.85
FK 49.38 38.15
AgL 00.00 00.00
Matrix Correction ZAF

(b) Element
CK
Wt%
55.62
At%
69.40
FK 33.14 26.15
ClK 10.21 04.32
AgL 01.03 00.14
Matrix Correction ZAF

(c)

Fig. 8. EDS images of (a) PVDF membrane, (b) 0.10 wt% GO-Ag modified membrane and (c) 0.15 wt% GO-Ag modified membrane.
 J. Li et al. / Journal of Colloid and Interface Science 484 (2016) 107–115 113

90 mainly determined by hydrophilicity of membrane [37]. Loading

200 Water flux Contant angle GO-Ag composites into the membrane casting solution resulted
85 in an increased pure water flux from 110.5 L/m2 h to 177.5 L/
m2 h. GO-Ag composites with hydrophilic functional groups
80
Water flux / (L/m 2 .h)

150
(Fig. 5) could attract water molecules inside the membrane and

Contant angle (°)

75 promoted them to pass through membranes [38].

70
100 3.2.4. Mechanical characterizations
65 The mechanical strength of ultrafiltration membranes is a key
factor to evaluate their practical applicability [39]. Fig. 10 shows
50 60 the mechanical property of pure and modified membranes in terms
of tensile strength and elongation at break. As shown in Fig. 10, the
55 modified membranes have a pronounced improvement in elonga-
tion at break, compared with the pure PVDF membrane. Further-
0 50
0.00 0.05 0.10 0.15 more, the tensile strength of the modified membranes increased
GO-Ag content (wt %) with the additional concentration of GO-Ag composites of
P0.10 wt%. This test result implies that GO-Ag composites have
Fig. 9. Contact angle and pure water permeation flux of membranes.
an excellent interface compatibility with PVDF polymer matrix,
and can enhance the mechanical stability of modified hybrid mem-
600
branes. However, when the modified hybrid membranes were
14 blended with a higher concentration of GO-Ag composites (i.e.,
550
0.15 wt%), tensile strength decreased probably due to the aggrega-
500 tion of GO-Ag composites. Hence, the optimal concentration is
12
450 determined to be 0.10 wt% of GO-Ag composites in PVDF polymer
Elogation at break /%
Tensile strength /cN

400 10 matrix.
350
8 3.3. Antimicrobial properties of membranes
300
250 6
3.3.1. Inhibition ring test
200
The inhibition ring test was used to evaluate the antibiotic
150 4
effect against Escherichia Coli (E. coli). The GO/PVDF membranes
100 (P0.1, P0.15), GO-Ag/PVDF membranes (M0.1, M0.1) and pure PVDF
2
50 (M0) membrane samples were tested. GO/PVDF membranes were
0 0 employed to serve as a control test, which helps to clarify the
-0.05 0.00 0.05 0.10 0.15 0.20 antibacterial property caused by GO itself or GO-Ag composites.
GO-Ag contnet/wt% As shown in Fig. 11, no antibacterial effect was detected in the pure
PVDF membrane. Only a small and faint inhibition ring was
Fig. 10. Mechanical property of GO-Ag/PVDF membranes.
observed around the outer edge of the GO/PVDF membrane. There-
fore, GO/PVDF membrane has very limited bacterial toxicity
against E. coli. In contrast, the GO-Ag/PVDF membrane presents a
groups of silver decorated GO on the surface of the membranes clear inhibition ring, which indicated the inhibition of the E. coli
(Fig. 9). These functional groups would make the membrane more growth of the GO-Ag composites. In addition, the test result high-
hydrophilic. In generally, the water flux through membranes is lighted the significant effect of the incorporated amount of Ag

Fig. 11. Inhibition ring of membranes (M0 pure PVDF membrane. P0.1, P0.15 GO/PVDF membrane. M0.1, M0.15 GO-Ag/PVDF membrane).
114 J. Li et al. / Journal of Colloid and Interface Science 484 (2016) 107–115

Fig. 12. Colonies formed on the unmodified (a) and modified membrane surface with 0.10 wt% (b), and 0.15 wt% (c) of GO-Ag composites.

nanoparticle on the antibacterial property of the membranes. The
antibacterial effect can be explained by the release of Ag+ from
the GO–Ag composites to the surface of agar media, which pre-
vented the bacteria growth in the area close to the nanocomposite
modified membrane.
3.3.2. Anti-adhesion effect of bacteria
Fig. 12 shows much lower concentrations of bacteria attached
to modified membranes of 0.10 wt% and 0.15 wt% of GO-Ag com-
posites (Fig. 12(b) and (c)) in contrast with the pure sample
(Fig. 12(a)). Only 13 CFU/mL of bacterial communities and 3 CFU/
mL were found in the filtration fluid collected through the 0.1
and 0.15 wt% GO-Ag modified membranes. In contrast,
6.7  103 CFU/mL of bacterial communities appeared in the filtra-
tion fluid of the unmodified membrane (See Table 2). Hence, the
GO-Ag/PVDF membrane has exhibited significant improvement in
the property of anti-bacteria adhesion and prohibited biofilm for-
mation in the short term.
These two experiments inferred that GO-Ag/PVDF membranes
exhibited novel antibacterial properties and resistance to biofoul-
ing. It also demonstrated that GO–Ag nanosystems can be used
Table 2
The bacterial communities of outflow.
in a variety of industrial applications that require materials with
antibacterial and anti-adhesion properties.
3.3.3. Release of silver ions from membranes
The antimicrobial activity of silver nanoparticles largely
depends on the release of silver ions [36,40]. The silver released
from the silver modified membrane is beneficial for the antimicro-
bial performance. However, the rapid depletion of silver has
limited its application on long-term continuous membrane opera-
tion. In this work, we investigated the release of silver ions from
GO-Ag/PVDF (0.1 and 0.15 wt%) blending membranes and silver
nanoparticle/PVDF (0.1 and 0.15 wt%) membranes. Fig. 13 shows
that AgNPs/PVDF membranes have exhibited a much higher con-
centration of Ag+ than that of GO-Ag/PVDF membrane. The reason
is that physically blended AgNPs could be easily separated out
from the membrane. Such fast release of silver ions prevents Ag/
PVDF membrane from long-term continuous application and may
also cause secondary pollution of water, or even serious safety
problems due to possible high concentrations of silver ions. In con-
trast, the continuous release of Ag+ concentration of GO-Ag/PVDF
membranes has been within the scope of safety [41]. The results
found that GO could efficiently control the releasing of Ag+, proba-
bly due to the anchoring sites provided by the function groups of
GO for the growth of the AgNPs.

Membrane Bacteria on membrane (CFU/L) 4. Conclusions

3
Pure membrane 6.7  10
0.10% GO-Ag/PVDF membrane 1.3  10 Herein, we report the successful synthesis of GO-Ag nanocom-
0.15% GO-Ag/PVDF membrane 3 posites and the application as a novel antibacterial agent to modify
PVDF membrane. The GO-Ag composites modified PVDF
membranes efficiently inhibited the bacterial growth, exhibited
9.5 improved anti-bacteria adhesion properties, and prevented the
9.0 formation of biofilms on the membrane surface. In addition, the
8.5 GO-Ag/PVDF membranes presented enhanced hydrophilic proper-
8.0
ties with improved permeability and strengthened mechanical
7.5
Concentration of silver/ppm

7.0 properties. The investigation on silver release kinetics showed

6.5 much slower rate of Ag+ from the GO-Ag/PVDF membrane than
6.0 AgNPs/PVDF membrane, which indicated its longer period of con-
GO-Ag/PVDFmembrane
5.5
Silver/PVDFmembrane tinuous operation in the wastewater treatment. The novel proper-
5.0
4.5 ties of GO-Ag PVDF membrane can be attributed to GO’s function
4.0 groups that served as the chemi-sorption sites for Ag+ and AgNPs.
3.5
3.0
2.5 Acknowledgement
2.0
1.5
1.0 This work was supported by the National Natural Science
0.5 Foundation of China (21574033), the Natural Science Foundation
0.0 of Heilongjiang Province (E201252, LC201404), Project of Applica-
0.00 0.05 0.10 0.15 0.20
GO-Ag content/wt% ble Technology Research and Development of Harbin City
(2013DB4BG010), and the Fundamental Research Funds for the
Fig. 13. Concentration of Ag+ released from the tested samples. Central Universities (HEUCF20161014).
 J. Li et al. / Journal of Colloid and Interface Science 484 (2016) 107–115 115

References [22] S.-H. Park, S.H. Kim, S.-J. Park, S. Ryoo, K. Woo, J.S. Lee, T.-S. Kim, H.-D. Park, H.
Park, Y.-I. Park, J. Cho, J.-H. Lee, Direct incorporation of silver nanoparticles
onto thin-film composite membranes via arc plasma deposition for enhanced
[1] Z. Wang, H. Yu, J. Xia, F. Zhang, F. Li, Y. Xia, Y. Li, Novel GO-blended PVDF
antibacterial and permeation performance, J. Membr. Sci. 513 (2016) 226–235.
ultrafiltration membranes, Desalination 299 (2012) 50–54.
[23] A. Ananth, G. Arthanareeswaran, A.F. Ismail, Y.S. Mok, T. Matsuura, Effect of
[2] W. Gao, H. Liang, J. Ma, M. Han, Z.-L. Chen, Z.-S. Han, G.-B. Li, Membrane fouling
bio-mediated route synthesized silver nanoparticles for modification of
control in ultrafiltration technology for drinking water production: a review,
polyethersulfone membranes, Colloids Surf., A 451 (2014) 151–160.
Desalination 272 (2011) 1–8.
[24] J.-H. Li, X.-S. Shao, Q. Zhou, M.-Z. Li, Q.-Q. Zhang, The double effects of silver
[3] X. Zhu, R. Bai, K.-H. Wee, C. Liu, S.-L. Tang, Membrane surfaces immobilized
nanoparticles on the PVDF membrane: surface hydrophilicity and antifouling
with ionic or reduced silver and their anti-biofouling performances, J. Membr.
performance, Appl. Surf. Sci. 265 (2013) 663–670.
Sci. 363 (2010) 278–286.
[25] Z. Yu, Y. Zhao, B. Gao, X. Liu, L. Jia, F. Zhao, J. Ma, Performance of novel a Ag-n-
[4] S. Ciston, R.M. Lueptow, K.A. Gray, Bacterial attachment on reactive ceramic
TiO2/PVC reinforced hollow fiber membrane applied in water purification:
ultrafiltration membranes, J. Membr. Sci. 320 (2008) 101–107.
in situ antibacterial properties and resistance to biofouling, RSC Adv. 5 (2015)
[5] A. Razmjou, A. Resosudarmo, R.L. Holmes, H. Li, J. Mansouri, V. Chen, The effect
97320–97329.
of modified TiO2 nanoparticles on the polyethersulfone ultrafiltration hollow
[26] A. Pugliara, K. Makasheva, B. Despax, M. Bayle, R. Carles, P. Benzo, G.
fiber membranes, Desalination 287 (2012) 271–280.
BenAssayag, B. Pécassou, M.C. Sancho, E. Navarro, Y. Echegoyen, C. Bonafos,
[6] C.S. Ong, P.S. Goh, W.J. Lau, N. Misdan, A.F. Ismail, Nanomaterials for biofouling
Assessing bio-available silver released from silver nanoparticles embedded in
and scaling mitigation of thin film composite membrane: a review,
silica layers using the green algae Chlamydomonas reinhardtii as bio-sensors,
Desalination 393 (2016) 2–15.
Sci. Total Environ. 565 (2016) 863–871.
[7] E. Filloux, J. Wang, M. Pidou, W. Gernjak, Z. Yuan, Biofouling and scaling control
[27] A.F. de Faria, D.S. Martinez, S.M. Meira, A.C. de Moraes, A. Brandelli, A.G. Filho,
of reverse osmosis membrane using one-step cleaning-potential of acidified
O.L. Alves, Anti-adhesion and antibacterial activity of silver nanoparticles
nitrite solution as an agent, J. Membr. Sci. 495 (2015) 276–283.
supported on graphene oxide sheets, Colloids Surf., B, Biointer. 113 (2014)
[8] V. Svetlichnyi, A. Shabalina, I. Lapin, D. Goncharova, A. Nemoykina, ZnO
115–124.
nanoparticles obtained by pulsed laser ablation and their composite with
[28] X. Wang, W. Dou, Preparation of graphite oxide (GO) and the thermal stability
cotton fabric: preparation and study of antibacterial activity, Appl. Surf. Sci.
of silicone rubber/GO nanocomposites, Thermochim. Acta 529 (2012) 25–28.
372 (2016) 20–29.
[29] X. Hu, Y. Yu, Y. Wang, J. Zhou, L. Song, Separating nano graphene oxide from
[9] S.V. Otari, H.M. Yadav, N.D. Thorat, R.M. Patil, J.K. Lee, S.H. Pawar, Facile one pot
the residual strong-acid filtrate of the modified Hummers method with
synthesis of core shell Ag@SiO2 nanoparticles for catalytic and antimicrobial
alkaline solution, Appl. Surf. Sci. 329 (2015) 83–86.
activity, Mater. Lett. 167 (2016) 179–182.
[30] S.J. Kazmi, M.A. Shehzad, S. Mehmood, M. Yasar, A. Naeem, A.S. Bhatti, Effect of
[10] S. Selvam, R. Rajiv Gandhi, J. Suresh, S. Gowri, S. Ravikumar, M. Sundrarajan,
varied Ag nanoparticles functionalized CNTs on its anti-bacterial activity
Antibacterial effect of novel synthesized sulfated b-cyclodextrin crosslinked
against E. coli, Sens. Actuat., A 216 (2014) 287–294.
cotton fabric and its improved antibacterial activities with ZnO, TiO2 and Ag
[31] M.S. Jang, S. Sahastrabuddhe, C.-H. Yun, S.H. Han, J.S. Yang, Serum bactericidal
nanoparticles coating, Int. J. Pharm. 434 (2012) 366–374.
assay for the evaluation of typhoid vaccine using a semi-automated colony-
[11] J.-L. Han, X. Xia, Y. Tao, H. Yun, Y.-N. Hou, C.-W. Zhao, Q. Luo, H.-Y. Cheng, A.-J.
counting method, Microb. Pathog. 97 (2016) 19–26.
Wang, Shielding membrane surface carboxyl groups by covalent-binding
[32] Z. Xu, J. Zhang, M. Shan, Y. Li, B. Li, J. Niu, B. Zhou, X. Qian, Organosilane-
graphene oxide to improve anti-fouling property and the simultaneous
functionalized graphene oxide for enhanced antifouling and mechanical
promotion of flux, Water Res. 102 (2016) 619–628.
properties of polyvinylidene fluoride ultrafiltration membranes, J. Membr.
[12] L.-L. Hwang, M.-Y. Wey, J.-C. Chen, Effects of membrane compositions and
Sci. 458 (2014) 1–13.
operating conditions on the filtration and backwashing performance of the
[33] J.J. Song, Y. Huang, S.-W. Nam, M. Yu, J. Heo, N. Her, J.R.V. Flora, Y. Yoon,
activated carbon polymer composite membranes, Desalination 352 (2014)
Ultrathin graphene oxide membranes for the removal of humic acid, Sep. Purif.
181–189.
Technol. 144 (2015) 162–167.
[13] S. Rajabzadeh, T. Maruyama, Y. Ohmukai, T. Sotani, H. Matsuyama, Preparation
[34] X.-F. Sun, J. Qin, P.-F. Xia, B.-B. Guo, C.-M. Yang, C. Song, S.-G. Wang, Graphene
of PVDF/PMMA blend hollow fiber membrane via thermally induced phase
oxide–silver nanoparticle membrane for biofouling control and water
separation (TIPS) method, Sep. Purif. Technol. 66 (2009) 76–83.
purification, Chem. Eng. J. 281 (2015) 53–59.
[14] G. Zeng, Y. He, Z. Yu, Y. Zhan, L. Ma, L. Zhang, Preparation and characterization
[35] Z.J. Yu, X.Y. Liu, F.B. Zhao, X.Y. Liang, Y. Tian, Fabrication of a low-cost nano-
of a novel PVDF ultrafiltration membrane by blending with TiO2-HNTs
SiO2/PVC composite ultra-filtration membrane and its antifouling
nanocomposites, Appl. Surf. Sci. 371 (2016) 624–632.
performance, J. Appl. Polym. Sci. 132 (2) (2015).
[15] L.-C. Wang, K. Cui, L.-B. Wang, H.-X. Li, S.-F. Li, Q.-L. Zhang, H.-B. Liu, The effect
[36] M.S. Haider, G.N. Shao, S.M. Imran, S.S. Park, N. Abbas, M.S. Tahir, M. Hussain, W.
of ethylene oxide groups in alkyl ethoxy carboxylates on its scale inhibition
Bae, H.T. Kim, Aminated polyethersulfone-silver nanoparticles (AgNPs-APES)
performance, Desalination 379 (2016) 75–84.
composite membranes with controlled silver ion release for antibacterial and
[16] H. Shi, Y. He, Y. Pan, H. Di, G. Zeng, L. Zhang, C. Zhang, A modified mussel-
water treatment applications, Mater. Sci. Eng., C 62 (2016) 732–745.
inspired method to fabricate TiO2 decorated superhydrophilic PVDF
[37] Y. Zhao, Z. Xu, M. Shan, C. Min, B. Zhou, Y. Li, B. Li, L. Liu, X. Qian, Effect of
membrane for oil/water separation, J. Membr. Sci. 506 (2016) 60–70.
graphite oxide and multi-walled carbon nanotubes on the microstructure and
[17] H.-R. Chae, J. Lee, C.-H. Lee, I.-C. Kim, P.-K. Park, Graphene oxide-embedded
performance of PVDF membranes, Sep. Purif. Technol. 103 (2013) 78–83.
thin-film composite reverse osmosis membrane with high flux, anti-
[38] G. Zhang, S. Lu, L. Zhang, Q. Meng, C. Shen, J. Zhang, Novel polysulfone hybrid
biofouling, and chlorine resistance, J. Membr. Sci. 483 (2015) 128–135.
ultrafiltration membrane prepared with TiO2-g-HEMA and its antifouling
[18] N.F.D. Aba, J.Y. Chong, B. Wang, C. Mattevi, K. Li, Graphene oxide membranes
characteristics, J. Membr. Sci. 436 (2013) 163–173.
on ceramic hollow fibers – microstructural stability and nanofiltration
[39] S. Lee, B.G. Choi, D. Choi, H.S. Park, Nanoindentation of annealed
performance, J. Membr. Sci. 484 (2015) 87–94.
Nafion/sulfonated graphene oxide nanocomposite membranes for the
[19] S. Zinadini, A.A. Zinatizadeh, M. Rahimi, V. Vatanpour, H. Zangeneh,
measurement of mechanical properties, J. Membr. Sci. 451 (2014) 40–45.
Preparation of a novel antifouling mixed matrix PES membrane by
[40] A. Martínez-Abad, J.M. Lagarón, M.J. Ocio, Characterization of transparent
embedding graphene oxide nanoplates, J. Membr. Sci. 453 (2014) 292–301.
silver loaded poly(l-lactide) films produced by melt-compounding for the
[20] Z. Zhang, P. Gao, M. Li, J. Cheng, W. Liu, Y. Feng, Influence of Silver
sustained release of antimicrobial silver ions in food applications, Food Control
nanoparticles on nutrient removal and microbial communities in SBR
43 (2014) 238–244.
process after long-term exposure, Sci. Total Environ. 569–570 (2016) 234–243.
[41] X. Song, P. Gunawan, R. Jiang, S. Su, J. Leong, K. Wang, R. Xu, Surface activated
[21] D.T. Thuc, T.Q. Huy, L.H. Hoang, B.C. Tien, P. Van Chung, N.T. Thuy, A.-T. Le,
carbon nanospheres for fast adsorption of silver ions from aqueous solutions, J.
Green synthesis of colloidal silver nanoparticles through electrochemical
Hazard. Mater. 194 (2011) 162–168.
method and their antibacterial activity, Mater. Lett. 181 (2016) 173–177.