1437 © IWA Publishing 2019 Water Science & Technology | 79.

8 | 2019

Optimized anti-biofouling performance of bactericides/

cellulose nanocrystals composites modified PVDF
ultrafiltration membrane for micro-polluted source water
purification
Guoquan Zhang, Jinling Lv and Fenglin Yang

ABSTRACT

The covalently functionalized cellulose nanocrystal (CNC) composites were synthesized by bonding Guoquan Zhang† (corresponding author)
Jinling Lv†
common bactericides, such as dodecyl dimethyl benzyl ammonium chloride (DDBAC), ZnO and Fenglin Yang
Key Laboratory of Industrial Ecology and
graphene oxide (GO) nanosheets, onto the CNC’s surface. Then, the DDBAC/CNC, ZnO/CNC and Environmental Engineering, Ministry of
Education, School of Environmental Science and
GO/CNC nanocomposites modified polyvinylidene fluoride (PVDF) ultrafiltration membranes were
Technology,
fabricated by a simple one-step non-solvent induced phase separation (NIPS) process. The resultant Dalian University of Technology,
Dalian 116023,
hybrid membranes possessed porous and rough surfaces with more finger-like macropores that China
E-mail: guoquanz@126.com
even extended through the entire cross-section. The hydrophilicity, permeability, antibacterial and
†
The first two authors contributed equally to this
antifouling performance and mechanism of the hybrid ultrafiltration membranes were evaluated and work.
compared in detail, aiming at screening a superior hybrid membrane for practical application in
micro-polluted source water purification. Among these newly-developed hybrid membranes, GO/
CNC/PVDF exhibited an enhanced perm-selectivity with a water flux of 230 L/(m2 h bar) and humic
acid rejection of 92%, the improved antibacterial activity (bacteriostasis rate of 93%) and antifouling
performance (flux recovery rate (FRR) of >90%) being due to the optimized pore structure, higher
surface roughness, incremental hydrophilicity and electronegativity. A lower biofouling level after
three weeks’ filtration of the actual micro-polluted source water further demonstrated that
embedding the hydrophilic and antibacterial GO/CNC nanocomposite into the polymer matrix is an
effective strategy to improve membrane anti-biofouling ability.
Key words | antibacterial, antifouling, cellulose nanocrystals, graphene oxide, quaternary
ammonium, ZnO

INTRODUCTION

Membrane filtration technology has been widely used in
removing soluble/suspended particulates, microorganisms
and some organic matters from contaminated water. How-
ever, membrane fouling is the major obstacle to the
widespread application of membranes in water recycling
and wastewater treatment. Membrane fouling has been gen-
erally recognized to happen in two ways: one is the direct
accumulation/deposition and adsorption of foulants onto
the membrane surface or within membrane pores. Another
way is biofouling, derived from the irreversible bacterial
adhesion, growth, and multiplication of sessile cells to the
membrane surface. Previous reports (Meng et al. ,
) demonstrated that the enhanced hydrophilicity and
doi: 10.2166/wst.2019.137
electronegativity can efficiently improve membrane surface
water affinity and inhibit membrane pore blocking or cake
layer formation, leading to a higher permeate flux. In
addition, endowing a membrane antibacterial function can
effectively prevent biofouling (Huang et al. ). Accord-
ingly, developing a membrane with high hydrophilicity,
strong electronegativity, and effective biocidal property is
essential for membrane biofouling mitigation.
Cellulose nanocrystal (CNC), the crystalline portions of
cellulose that are typically obtained by acid hydrolysis of cel-
lulosic materials, is a promising nanofiller for improving
water filtration membrane performances in view of its
environmental friendly advantages, large aspect ratio, high

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 1438 G. Zhang et al. | Hybrid PVDF membrane for micro-polluted source water purification
chemical resistance, good mechanical strength and strong
hydrophilicity (Bai et al. ; Voisin et al. ). It was
reported (Lv et al. , a) that only a small amount
of CNC added into the poly(vinylidene fluoride) (PVDF)
membrane was enough to give the membrane high water
flux, strong mechanical strength, and thermostability.
Even so, however, the intrinsic CNC does not have any
antibacterial activity, thus the functionalized CNC should
be developed to endow the CNC composite with effective
antibacterial ability. In the past decade, graphene oxide
(GO) blended membranes have exhibited more superior
performance in improving the mechanical strength, electro-
negativity, hydrophilicity and antimicrobial activity of
membranes, due to their uniform dispersion, accelerated
charge transfer and increased cytotoxic effect of physical
piercing and oxidative stress by means of the adequate
exposure of the active edges of GO nanosheets (Liu et al.
; Feng et al. ). However, GO nanosheets will leach
from the membrane surface during the long-term filtration
process and thus cannot maintain high efficiency in inhibit-
ing bacterial colonization. In order to fully exert GO
nanosheets’ functions, it is highly desirable to immobilize
GO nanosheets into the polymer matrix membranes via a
reinforcing agent. The hydroxyl groups of CNC and the
abundant oxygen-containing groups of GO sheets allow
them to be integrated facilely in one pot via hydrogen bond-
ing interactions (Ouyang et al. ), and the presence of
CNC provides more cross-linking points between the GO
sheets and CNC, which facilitates the efficient dispersion
of GO sheets and CNC (Lv et al. b). In this context,
using GO/CNC composites as nanofillers would efficiently
improve the hydrophilicity, antibacterial and antifouling
properties of the functionalized PVDF membranes. Besides,
ZnO is also frequently used as an antibacterial agent (Zhao
et al. ), due to its outstanding optoelectronic property,
high hydrophilicity, and broad antibacterial spectrum. The
hybridization of cellulose and its derivatives with ZnO
nanoparticles not only overcomes ZnO nanoparticle aggre-
gation but also endows the ZnO/cellulose composite with
superior antibacterial activity compared to both ZnO and
cellulose (Lefatshe et al. ). On the other hand, organic
antibacterial agents such as quaternary ammonium com-
pounds (Ye et al. ; Zhang et al. a, b) are also
widely used in antibacterial and anti-biofouling membranes
in terms of their efficient bacteria killing capability and
inhibitory effect on bacterial growth. As a quaternary
ammonium type antibacterial agent, dodecyl dimethyl
benzyl ammonium chloride (DDBAC) has a broad
spectrum, highly efficient disinfection and algae killing
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Water Science & Technology | 79.8 | 2019
activity. To the best of our knowledge, there is no previous
report about direct blending of DDBAC/CNC composites
with PVDF to simultaneously improve hydrophilicity, anti-
bacterial and antifouling properties.
In the present study, three common antibacterial
(DDBAC, ZnO and GO) functionalized CNC nanocompo-
sites were first synthesized, and their microstructure and
morphology properties were characterized by scanning
electron microscope (SEM), Fourier transform infrared spec-
troscopy (FTIR), and X-ray diffraction (XRD). Then, the
polyvinylidene fluoride (PVDF) hybrid ultrafiltration mem-
branes were fabricated by the non-solvent induced phase
separation (NIPS) method using DDBAC/CNC, ZnO/CNC
and GO/CNC composites as nanofillers. The morphology,
hydrophilicity, permeability, antibacterial activity, antifoul-
ing properties and mechanism of the various PVDF hybrid
membranes were investigated and compared in detail, with
the aim of screening an optimal antibacterial agent that can
concurrently improve the hydrophilicity, antibacterial and
antifouling ability of the membrane, and finally obtain a
superior hybrid membrane for practical membrane filtration
application in the treatment of micro-polluted source water.
MATERIALS AND METHODS
Preparation of ZnO, DDBAC and GO functionalized CNC
nanocomposites
The cellulose nanocrystals were prepared using filter paper
as raw materials according to the previous method (Lv
et al. ). The preparation processes of DDBAC/CNC,
ZnO/CNC and GO/CNC composites are provided in
supplementary material S1 (available with the online
version of this paper).
Preparation of PVDF hybrid membranes
The preparation processes of DDBAC/CNC, ZnO/CNC and
GO/CNC nanocomposite-modified PVDF membranes are
provided in supplementary material S2; all the fabricated
membranes (Figure S1) were preserved in deionized water
prior to characterization and use. (Supplementary material
S1 and Figure S1 are available online.)
Characterization and performance analysis
of membranes
The characterization and analysis methods of membrane
morphology, porous structure, hydrophilicity, permeability,
antibacterial and antifouling performances as well as
 1439 G. Zhang et al. | Hybrid PVDF membrane for micro-polluted source water purification
membrane filtration application are provided in supplemen-
tary material S3–S6 (available online).
RESULTS AND DISCUSSION
Characterization of the functionalized CNC
nanocomposites
The morphologies of the pristine CNC and DDBAC, ZnO
and GO-functionalized CNC nanocomposites are shown
in Figure 1. It can be clearly observed that the pristine
CNC exhibited dense and hierarchical sheet-like structures
due to the aggregation of the nanoscale rod-like CNC. The
SEM images of functionalized CNC composites displayed
three-dimensional loose sheet-like nanostructures, indicat-
ing that the introduction of DDBAC, ZnO and GO
nanofillers notably facilitated CNC dispersion. Especially,
ZnO and GO nanosheets were assembled on the agminated
Figure 1 | SEM images of (a) CNC, (b) DDBAC/CNC, (c) ZnO/CNC, and (d) GO/CNC nanocomposites. The insets in (a) and (b)–(d) show photographs of freeze-dried CNC powders and the
partially amplified SEM images.
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Water Science & Technology | 79.8 | 2019
CNC surface, which is consistent with the fact that ZnO
nanosheets can be synthesized through low-temperature
hydrothermal treatment (Lefatshe et al. ). These loose
and disordered stacking structures of the functionalized
CNC nanocomposites may exert a positive effect on mem-
brane permeability. The similar characteristic bands
corresponding to CNC are also observed in Figure 2(a)–
2(c) for the functionalized CNC composites. In each FTIR
spectrum, the peaks at 3,337–3,423 and 1,380 cm–1 can be
assigned to stretching and bending vibrations of hydroxyl
groups, respectively (Lv et al. , a). The C–O–C
stretching of pyranose and glucose ring skeletal vibration
of CNC was observed at 1,050 cm
1 (Lv et al. a). The
peaks at 2,924, 2,853, 1,625 and 1,462 cm
1 in Figure 2(a)
correspond to –CH3, –CH2, –C ¼ C– and N–C, and C–H
stretching vibration of DDBAC, respectively (Ye et al. ).
The band at 1,634 cm
1 in Figure 2(b) is related to hydroxyl
of adsorbed water and another band at around 421 cm
1
belonged to the Zn–O stretching mode, implying the
 1440 G. Zhang et al. | Hybrid PVDF membrane for micro-polluted source water purification
Figure 2 | FTIR spectra and XRD patterns: (A,a) DDBAC/CNC, (B,b) ZnO/CNC and (C,c) GO/CNC nanocomposites.
existence of nanocrystalline ZnO in ZnO/CNC nanocompo-
sites (Lefatshe et al. ). The FTIR spectrum of GO in
Figure 2(c) presents the C ¼ C bonds (1,628 cm
1), C–O
vibrations (1,051 cm
1), and C ¼ O stretching vibration
(1,729 cm
1) (Lv et al. b). A wider peak at around
3,400–3,500 cm
1 was observed in GO/CNC samples, imply-
ing the formation of hydrogen bond interactions between the
hydroxyl groups of CNC and the abundant oxygen-containing
groups of GO sheets (Ouyang et al. ; Lv et al. b).
The crystal structure of the pristine CNC and the functio-
nalized CNC composites was investigated by XRD. As shown
in Figure 2(a)–2(c), the pristine CNC exhibited four distinct
peaks at 2θ ¼ 16.1 , 20.0 , 22.2 and 34.5 , which were attrib-
̄ (110), (200) and (040) planes, respectively, in
uted to (1I0),
accordance with the characteristic diffraction peaks of mono-
clinic cellulose I lattice (Lv et al. b). Many new intensive
peaks at 2θ ¼ 31.8 , 34.6 , 36.2 , 47.6 , 56.5 , 62.8 , and 67.9
were observed in ZnO/CNC nanocomposite, which corre-
spond respectively to (100), (002), (101), (102), (110), (103),
and (112) planes of the hexagonal wurtzite structure of
ZnO (JCPDS No. 36-1451) (Lefatshe et al. ). A slight dif-
fraction peak at 2θ ¼ 11.7 appeared in the XRD pattern of
the GO/CNC composite, which is attributed to the interlayer
spacing between GO nanosheets (d002 ¼ 0.756 nm) (Lv et al.
b), while the (002) reflection peak of GO at 2θ ¼ 26.3
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Water Science & Technology | 79.8 | 2019
disappeared, implying the good exfoliation and dispersion
of GO in the GO/CNC. Of note, the introduction of
DDBAC has not altered the crystal structure of CNC, because
no new peaks nor any peak shift were observed in the XRD
pattern of DDBAC/CNC.
Characterization of PVDF hybrid membranes
The SEM images of the top surfaces, the bottom surfaces,
and the cross-sections of the pristine CNC and the functio-
nalized CNC nanocomposite modified PVDF membranes
are presented in Figure 3. All the membranes’ top surfaces
are smooth and no distinct deformations were observed,
while the bottom surfaces appeared porous. This result
may be related to the strong non-solvent effect during the
NIPS process, which led to the rapid and delayed phase sep-
aration on the top and bottom surfaces, respectively, when
the initial casting films were immersed into the coagulation
water bath (Huang et al. ). The cross-section SEM
images displayed a typical asymmetrical porous structure
with a dense superficial layer, a finger-like intermediate
layer, and a sponge-like bottom support layer. Compared
to the unmodified membrane (Figure S2a) (Figure S2 is
available with the online version of this paper), all the
modified PVDF membranes possessed more finger-like
 1441 G. Zhang et al. | Hybrid PVDF membrane for micro-polluted source water purification
Figure 3 | SEM images of top surface, cross-section and bottom surface of different PVDF hybrid membranes.
macropores that even extended through the entire cross-sec-
tion. This phenomenon can be attributed to the excellent
hydrophilicity of the pristine and functionalized CNC nano-
composites, which significantly altered the thermodynamic
instability of casting solutions during the gelation process
and thus effectively accelerated the inter-diffusion and de-
mixing rate of solvent and non-solvent in the phase inver-
sion process (Zhang et al. a; Lv et al. b). These
results indicated that the functionalized CNC nanocompo-
sites optimized the pore micro-structure, which is
beneficial for improving membrane permeability.
Compared to the CNC/PVDF membrane, the functio-
nalized CNC composite-modified PVDF membranes
possessed larger average pore size and superior porosity
(Figure 4(a)), and their hydraulic contact angles decreased,
except DDBAC/CNC/PVDF membrane (Figure 4(b)). The
probable reasons may be that: (i) the more hydrophilic
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Water Science & Technology | 79.8 | 2019
ZnO/CNC and GO/CNC nanocomposites would tend to
migrate to the membrane surface and decrease interface
energy during the phase separation process (Hong & He
; Lv et al. b), (ii) the hydrophobic segment on the
long alkyl chain (C12) of DDBAC/CNC nanocomposites
led to slightly increased contact angle (Zhang et al. a,
b). Apparently, the superior hydrophilic GO/CNC
nanocomposite would more effectively promote the for-
mation of large pore channels and the amorphous nature
of GO/CNC/PVDF membrane is beneficial for water
permeability and antifouling property.
Anti-adhesion and anti-bacterial properties of PVDF
hybrid membranes
Biofilm formation through the irreversible bacterial
adhesion on membrane surface is believed to be the major
 1442 G. Zhang et al. | Hybrid PVDF membrane for micro-polluted source water purification Water Science & Technology | 79.8 | 2019

Figure 4 | Average pore size and porosity (a), contact angle and water content (b) of various PVDF hybrid membranes.

factor in membrane fouling (Meng et al. , ). The
anti-adhesion performance against Escherichia coli. was
firstly assessed for different PVDF hybrid membranes
through SEM observation to investigate the antibacterial abil-
ity. As seen in Figure S2c, large amounts of bacteria with
intact morphology were attached on the PVDF membrane
surface after 12 h incubation in the bacterial media, which
could be ascribed to no antibacterial activity and inherent
hydrophobicity of the original PVDF membrane. However,
the bacterial adhesion on the modified PVDF membranes
decreased significantly (Figure 5(a)–5(d)), and more notably,
the attached E. coli on DDBAC/CNC, ZnO/CNC and GO/
CNC nanocomposite-modified PVDF membranes presented
poor cellular integrity, implying serious destruction of the
bacterial structure. It is reported although both hydrophilic
and electrostatic interactions between bacterial and mem-
brane surface are involved in bacterial adhesion, membrane
hydrophilicity plays a more important role in the bacterial
attachment process (Hou et al. a, b). Compared to
the original PVDF membrane, the substantially improved
hydrophilicity of the modified PVDF membranes can bond
with water molecules, which generate a hydration layer on
the membrane surface and prevent E. coli attachment in
spite of the occurrence of potential electrostatic attraction
between the positively charged ZnO/CNC and DDBAC/
CNC nanocomposites and the negatively charged E. coli.
On the other hand, the attached E. coli on CNC/PVDF main-
tained cell integrity better when compared with the other
three modified PVDF membranes, due to the non-bacteri-
cidal nature of the pristine CNC.

Figure 5 | The SEM images of E.coli adhesion and the results of biocidal efficacy against E. coli on: (A,a) CNC/PVDF, (B,b) DDBAC/CNC/PVDF, (C,c) ZnO/CNC/PVDF, and (D,d) GO/CNC/PVDF
hybrid membranes, respectively.

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 1443 G. Zhang et al. | Hybrid PVDF membrane for micro-polluted source water purification
To gain more insight into the antibacterial activity, the
original and the modified PVDF membranes were also eval-
uated in term of bacteria inactivation and biocidal efficacy
after being cultivated with E. coli through ‘sandwich’
systems (Hou et al. a, b). Figure 5(a)–5(d) show
that in comparison with the original PVDF membrane
(Figure S2d), a significant decline in bacterial colonies was
observed for E. coli eluted from the DDBAC/CNC, ZnO/
CNC and GO/CNC nanocomposite-modified PVDF mem-
branes, while the CNC/PVDF membrane did not exhibit a
dramatic reduction in E. coli colonies within 30 min of
contact, as evidenced by about 2.1%, 73.6%, 80.7% and
92.8% of bacteriostasis rate (BR) for CNC, DDBAC/CNC,
ZnO/CNC and GO/CNC-modified PVDF membranes
(Figure S2e), respectively, indicating the superior antibacter-
ial abilities of DDBAC/CNC, ZnO/CNC and GO/CNC
nanocomposite-modified PVDF membranes. Nevertheless,
the bacteria-killing approach of DDBAC, ZnO and GO
concerns different inactivation mechanisms:
(i) The general antibacterial mechanism of fat ammonium
bactericides with the positively charged quaternary
ammonium groups involves electrostatic binding to
the negatively charged cell wall of E. coli. The long
alkyl chains (C12) of DDBAC provided good compat-
ibility with the bacterial cell wall, which increased
cell membrane permeability and then disrupted the
cytoplasmic membrane and led to bacteria death
(Zhang et al. b).
(ii) The general antibacterial mechanism of ZnO is mainly
related to the photo-generated and/or non-photo-gener-
ated superoxides (O2
), hydroxyl radicals (•OH) and
hydrogen peroxide (H2O2) (Lefatshe et al. ; Zhao
et al. ), which damage cell membranes/proteins
and cause bacterial death. The CNC promotes the good
dispersion of ZnO nanosheets and provides a larger sur-
face area, thus leading to generation of more reactive
oxygen species and higher antibacterial activity.
(iii) The antibacterial mechanism of GO nanosheets
involves the combined effect of physical membrane
stress including wrapping, insertion and perforation/
incision as well as induction of oxidative stress (Liu
et al. ; Feng et al. ). The electrostatic repulsion
between the negatively charged GO/CNC and E. coli
can effectively prevent the initial attachment, growth
and spreading of E. coli onto the membrane surface.
Additionally, the wrinkled GO nanosheets with sharp
edges and defect sites on the basal plane could cause
membrane stress and oxidative stress, which can destroy
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Water Science & Technology | 79.8 | 2019
the bacteria cell integrity and effectively oxidize the thiol
groups (–SH) of glutathione in bacteria to disulfide bond
(–S–S–), resulting in irreversible damage to the bacterial
cells (Feng et al. ). Therefore, the excellent hydrophi-
licity, cytotoxicity, and electronegativity of GO/CNC
nanocomposites endowed the GO/CNC/PVDF mem-
brane with outstanding antibacterial ability, which is
favorable for preventing biofouling formation.
Antifouling performance of membranes
Three-stage dynamic filtration was carried out to explore the
antifouling performances. As seen in Figure 6(a), the initial
pure water flux of CNC/PVDF was around 75.0 L M–2 h–1
bar–1, while the DDBAC/CNC, ZnO/CNC and GO/CNC
modified PVDF membranes presented higher fluxes of
about 130, 175 and 230 L M–2 h–1bar–1, which are around
1.73, 2.33 and 3.07 times that of the CNC/PVDF membrane.
When pure water was substituted by HA solution, an
obvious decline in permeation flux was observed for all
membranes due to the formation of a fouling layer caused
by HA molecules’ adsorption/deposition on the membrane
surface/pore wall, which decreased the effective filtration
area (Liu et al. ; Lv et al. b). The recuperative pure
water flux of all membranes exhibited an apparent upswing,
but did not recover to the initial levels owing to the entrap-
ment of HA molecules within the pores. Clearly, the
tendency of pure water permeability and HA rejection
(Figure 6(b)) agreed well with SEM images; that is, blending
the functionalized CNC nanocomposites’ optimized pore
micro-structure, porosity, hydrophilicity and electronegativ-
ity of the PVDF hybrid membrane greatly.
Generally, the antifouling ability of the membranes was
associated with surface roughness. The three-dimensional
AFM images in Figure 6(c)-(f) show that compared to the
CNC/PVDF membrane, the other three hybrid membranes
displayed a prominent texture structure with more ridges
and valleys, and thus presented higher roughness par-
ameters (Ra). Previous studies (Zhang et al. a, b;
Wu et al. ) confirmed that a higher surface roughness
will not impose a negative effect on the separation perform-
ance of a hydrophilic membrane. On the contrary, it can
effectively resist contaminants’ adhesion and improves the
membrane’s permeating flux and antifouling ability, because
the higher roughness produces more flow obstacles, which
would effectively increase the hydraulic shear stress and
mass transport through micro-turbulence and more cavities
generated at the fluid/membrane interface, leading to a
 1444 G. Zhang et al. | Hybrid PVDF membrane for micro-polluted source water purification Water Science & Technology | 79.8 | 2019

Figure 6 | (a) Permeation flux change during three-step ultrafiltration of HA solution and (b) time-dependent rejection rate of HA solution for different PVDF hybrid membranes; AFM
images of (c) CNC, (d) DDBAC/CNC, (e) ZnO/CNC and (f) GO/CNC modified PVDF hybrid membranes.

positive effect on permeation flux and fouling mitigation
(Izák et al. ; Pourbozorg et al. ).
Flux recovery ratio (FRR) and filtration resistances were
also used to clarify the antifouling mechanism of the PVDF
hybrid membranes. As shown in Figure 7(a), the GO/CNC/
PVDF exhibited the highest FRR value (above 90%) and the
lowest HA adsorption value (ca. 75.3 mg m–2) after the ultra-
filtration-regeneration process, which demonstrated the
excellent antifouling property owing to the enhanced hydro-
philicity and the optimized pore micro-structure after the
introduction of GO/CNC nanocomposites. As seen in
Figure 7(b), the functionalized CNC composite-modified
PVDF membranes displayed significantly reduced filtration
resistance (Rt), membrane resistance (Rm) and fouling resist-
ance (Rf ) values, suggesting a low fouling tendency and high
permeability compared to the CNC/PVDF membrane. Of
note, the GO/CNC/PVDF possessed the lowest filtration
resistance and superior antifouling property, which could
be ascribed to the abundant hydroxyl groups of CNC provid-
ing more binding sites for oxygen-containing functional
groups of GO, and thus promoting the good dispersion of
GO/CNC nanocomposites in PVDF membrane matrices
(Lv et al. , a, b), resulting in the enhanced
pore size, porosity, hydrophilicity and electronegativity of
the GO/CNC/PVDF membrane compared to the CNC/
PVDF membrane. These outstanding properties effectively
decreased the hydrophobic interaction between GO/CNC/
PVDF membranes and HA molecules, which restrained
the accumulation of the cake layer during the membrane fil-
tration process. More importantly, the reversible cake layer

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 1445 G. Zhang et al. | Hybrid PVDF membrane for micro-polluted source water purification
Figure 7 | Antifouling properties of the different PVDF hybrid membranes: (a) water flux recovery ratio and HA adsorption and (b) membrane filtration resistance.
can be facilely removed by hydraulic cleaning, thus the per-
meation flux was recovered to a greater extent, as depicted
in Figure 7(a).
Membrane filtration application for actual micro-
polluted source water
During membrane purification of the micro-polluted source
water, a biofilm generally formed via the deposition/attach-
ment of humic substances and microorganisms onto the
membrane surface, resulting in the decrease in membrane
permeability flux. In this work, the antifouling performances
of different PVDF hybrid membranes were evaluated in a
laboratory-scale membrane filtration system using actual
reservoir water (Table S1, available online). As seen in
Figure 8, the GO/CNC/PVDF membrane displayed a much
more slowly-increasing rate of trans-membrane pressure
Figure 8 | The time-dependent permeation flux and TMP of different PVDF hybrid
membranes during the treatment of the actual reservoir water in a laboratory-
scale membrane filtration system.
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Water Science & Technology | 79.8 | 2019
(TMP) than the other three PVDF hybrid membranes,
which is attributed to the enhanced hydrophilicity, electrone-
gativity, antibacterial activity and the optimized pore
structure, which effectively inhibit bacterial attachment/
growth, alleviating membrane fouling and prolonging
membrane operating time. The result demonstrated that
embedding the hydrophilic and antibacterial GO/CNC nano-
composites into a polymer matrix is an effective strategy to
improve membrane anti-biofouling ability.
CONCLUSION
The DDBAC/CNC, ZnO/CNC and GO/CNC nanocompo-
site-blended PVDF hybrid ultrafiltration membranes were
fabricated, characterized and compared in term of
membrane morphology, pore structure, hydrophilicity,
antibacterial activity, and antifouling performance. Among
these newly-developed hybrid membranes, the GO/CNC/
PVDF exhibited superior antibacterial activity and antifoul-
ing performance, due to the improved pore micro-structure,
surface roughness, hydrophilicity and electronegativity, lead-
ing to the increased filtration area, the decreased adhesion of
bacteria/contaminants, and effective membrane fouling alle-
viation. The outstanding antifouling performance of the GO/
CNC/PVDF membrane during the practical micro-polluted
resource water filtration demonstrated that the hydrophilic
and antibacterial GO/CNC nanocomposite is an effective
additive for the anti-biofouling membrane.
ACKNOWLEDGEMENTS
This work was supported by the National Natural Science
Foundation of China (No. 21437001) and the Program of Intro-
ducing Talents of Discipline to Universities (No. B13012).
 1446 G. Zhang et al. | Hybrid PVDF membrane for micro-polluted source water purification
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