Journal of Membrane Science 514 (2016) 518526

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Journal of Membrane Science

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

Graphene oxide functionalized polyethersulfone membrane to reduce

organic fouling
Efosa Igbinigun a, Yaolin Fennell b, Ramamoorthy Malaisamy b, Kimberly L. Jones b,n,
Vernon Morris a
a
b

Department of Chemistry, Howard University, Washington, DC 20059, USA

Department of Civil and Environmental Engineering, Howard University, Washington, DC 20059, USA

art ic l e i nf o

a b s t r a c t

Article history:
Received 1 February 2016
Received in revised form
11 May 2016
Accepted 12 May 2016
Available online 16 May 2016

Graphene-oxide can be used to modify a polymeric membrane surface to render the surface less susceptible to organic fouling. In this study, a three-step method is developed to covalently bind graphene
oxide (GO) nanosheets onto a polyethersulfone (PES) support to create an ultraltration membrane that
is resistant to organic fouling. First, amine functional groups are grafted onto a PES surface by UV-induced graft co-polymerization of allylamine monomer. Next, trimesoyl chloride (TMC, 0.2 wt% in hexane)
and GO nanosheets (2, 4 and 6 wt% in anhydrous acetonitrile) are attached onto the polyallylamine
modied membrane surface by spin coating, allowing covalent binding to take place between TMC and
the amine functional group, and also between TMC and the hydroxyl or carboxylic functional groups of
GO. Covalent bonding was conrmed by the emerging ester or anhydride peaks by attenuated total
reectance Fourier transform infrared spectroscopy (ATR-FTIR). The GO membrane morphology was
observed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The molecular
weight cut offs (MWCO) of the GO (2, 4 and 6 wt%) modied membranes were determined to be 380, 140,
and 75 kDa respectively. The membrane with 4 wt% GO (PES-GO-4) was chosen for further study because
it exhibited higher pure water ux and rejection than the other GO formulations. The PES-GO-4 membrane exhibited 2.6 times greater ux recovery than an unmodied PES-UF membrane of comparable
MWCO. This method is a simple, effective way to create a robust, high ux UF membrane that is resistant
to organic fouling. Such a membrane could be applied in water or wastewater treatment applications,
such as pretreatment for reverse osmosis.
& 2016 Elsevier B.V. All rights reserved.

Keywords:
Graphene oxide
Microltration
Ultraltration
Organic fouling
Surface modication

1. Introduction
Polymeric membranes, such as polysulfone, polyethersulfone,
and cellulosic membranes are commonly used in water and wastewater treatment due to their robust physical, chemical and
mechanical stabilities and effective contaminant rejection [13].
However, their applications in water/wastewater treatment are
limited by their hydrophobic surfaces [46], which encourage the
attachment of hydrophobic organic substances on the membrane
surfaces or inside the membrane pores. One approach to minimizing fouling is to modify the membrane surface by introducing
hydrophilic polymers [1113], nanoparticles [6,14,15], and organic
coatings [16,17], in order to render the surface less susceptible to
organic fouling. Recent studies have shown that carbon nanomaterials, particularly graphene oxide (GO) nanosheets, with their
n

Corresponding author.
E-mail address: kljones@howard.edu (K.L. Jones).

http://dx.doi.org/10.1016/j.memsci.2016.05.024
0376-7388/& 2016 Elsevier B.V. All rights reserved.

unique properties and hydrophilic nature, have drawn great interest in membrane applications [1821]. GO can be incorporated
with a polymeric membrane by membrane surface functionalization [2224] or by embedding into a polymer matrix [25,26], and
can increase permeate ux, improve mechanical strength [27],
increase surface hydrophilicity [28], and reduce both organic and
bio-fouling propensity [22,2933].
Most GO modication techniques employ physical binding for
the attachment of GO to the support polymer [22,23,34]. In those
cases, the loss of GO from the membrane surface may occur over
time, resulting in degraded membrane performance; these prior
studies did not evaluate leaching of GO over time. Chemical attachment of GO nanosheets on the membrane may prove to be a
better method for long term stability of the modied membrane
while still decreasing organic fouling. One study investigated
covalent bonding of GO onto polyamide membranes [33], however
it would be advantageous to study chemical bonding onto a
polyethersulfone (PES) membrane, as this substrate would enable

E. Igbinigun et al. / Journal of Membrane Science 514 (2016) 518526

519

Fig. 1. Reaction scheme of the membrane surface modication by GO. (a) Amination of PES surface by UV-induced grafting; (b) Reaction between PES-g-NH2 and TMC
(c) Reaction between GO and TMC modied PES membrane surface, and (d) Schematic illustration of GO modied PES membrane.

functionalization under UV treatment without the presence of

photo-initiators [5,35].
In this study, we outline a simple approach to attach GO nanosheets onto PES membrane surfaces using chemical surface
functionalization, which should provide increased stability. Initially amine functional groups were generated on the PES membrane by polymerizing allylamine on the PES membrane surface
via UV induced grafting. The GO was then attached to the allylamine modied PES membrane through a cross-linking reagent,
trimesoyl chloride (TMC). In addition to examining the effect of GO
coating on membrane fouling by humic acid, the stability of the
attached GO on the pretreated PES sheet was also investigated.

2. Materials and methods

2.1. Materials
Unless specied, all chemicals used in this study were used as
received from Sigma-Aldrich (St. Louis, MO). Graphite powder (Bay
Carbon, MI) was used as the starting material for the synthesis of
GO. A 0.1 M pore size PES membrane (Maine manufacturing, ME),
was used as the substrate for the GO modication. Anhydrous
acetonitrile was used for GO dispersion and allylamine was used as
a vinyl monomer for the UV graft co-polymerization of allylamine
on the PES membrane surface, following a similar procedure reported by Malaisamy et al. [37]. TMC dissolved in hexane was
employed as a cross-linker between the polyallylamine and GO.
Dextrans with 25, 50, 80, 150, 270, 410, and 670 kDa molecular
weights were used to characterize the molecular weigh cut off
(MWCO) of the modied and unmodied membranes. A polyethersulfone ultraltration membrane with MWCO of 100 kDa
(Sterlitech, WA) was used in the fouling study [37]. Humic acid
(20 mg/L) solution was used as the organic foulant [38].

2.2. GO synthesis and characterization

Graphene oxide was produced from the chemical oxidation of
graphite powder using the modied Hummers' method [39,40].
Graphite powder (5 g) was rst oxidized by potassium per manganate (15 g) in the presence of concentrated sulfuric acid (98%,
115 mL) and sodium nitrate (2.5 g). During the oxidation, the
temperature of the mixture was kept at 0 C under gentle mixing.
The temperature of the mixture was further raised to 35 C and
stirred for 1 h. The pasty graphite oxide was diluted with Milli-Q
water, and nally heated at 98 C for 1 h. Then about 30 mL of
hydrogen peroxide (30%) was added to the suspension in order to
terminate the reaction. The graphite oxide suspension was ltered,
and the graphite oxide particles were re-suspended in Milli-Q
water. The suspension was centrifuged repeatedly at 8000 rpm
(Thermo scientic, MA) for 1 h to remove unoxidized particles and
then sonicated for 1 h to produce single-layered GO nanosheets.
The product was characterized by ATR FT-IR and Raman spectroscopies to conrm the formation of GO nanosheets.
2.3. Membrane surface modication and characterization
A three-step protocol was used to chemically bind graphene
oxide nanosheets onto polyethersulfone membrane surface. PES
membranes were chosen due to their high mechanical and thermal stabilities, and more importantly, they can be easily functionalized under UV treatment without the presence of photo-initiators [5,35]. The sulfonyl groups in the polymer chain are sensitive to UV light, which create radical sites for polymerization
[36].
First, amine functional groups are introduced to PES membrane
surface through UV induced co-polymerization of allylamine
(Fig. 1a). Next, these amine functional groups react with the acyl
chloride groups of the cross linker, TMC. Lastly, the free acyl
chloride groups on the cross linker react with the hydroxyl or
carboxylic groups of the GO to form an ester or anhydride bond.

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The steps of the process are outlined as follows:

Step 1. The PES membrane was initially soaked in water for
several hours to remove soluble additives on the surface. The
polymerization reaction was carried out on the PES membrane
surface in a nitrogen-saturated UV chamber, where allylamine
monomer of different concentrations (100, 200, and 300 mM)
were irradiated at different times (10, 20, and 30 min) [5]. The
intensity of the UV radiation for the 300 nm wavelength was
measured to be 28 mW/cm2. At the end of each reaction time, the
membrane was removed and rinsed thoroughly with methanol
and water respectively to remove unreacted monomer and
homopolymer.
The degree of grafting (DG) on the PES membrane was evaluated by measuring the difference between the dried weight of
the PES membrane before and after grafting, and normalized to
the membrane surface area using the equation below:

D. G =

W1W0
A

(1)

W0 is the dried weight of the unmodied PES membrane, W1

is the dried weight of the modied membrane (PES-g-NH2) and A
is the surface area (12.50 cm2). The degree of grafting was expressed in g/cm2 and the weight of the membrane was measured
using a balance with an accuracy of 0.0001 g. FT-IR and X-Ray
Photoelectron spectroscopy (XPS) were also used to characterize
and conrm the success of amine functionalization.
Step 2. A solution of 0.2 wt% TMC dissolved in hexane was
prepared and spin coated onto the PES-polyallylamine membrane
surface in an air-tight environment for one minute, at 2500 rpm.
The TMC spin coated membrane was thoroughly rinsed with
hexane to remove unreacted TMC and spin-dried at 1000 rpm in
an air-tight environment.
Step 3. Three different concentrations (2, 4, and 6 wt%) of GO
were dispersed in anhydrous acetonitrile, after 1 h of sonication.
The GO suspension was immediately spin coated on the TMCmodied membrane at the same spinning conditions. The GOmodied membranes were thoroughly rinsed in Milli-Q water.
The resulting membranes were characterized using ATR-FTIR
spectroscopy. The variation in surface morphology and roughness
of the membranes were evaluated using scanning electron microscope (JSM-7600F, Japan) and atomic force microscope (JSPM5200, Japan), while the surface hydrophilicity of the membranes
was characterized by contact angle measurement (sessile drop
method) using a goniometer (Surface Electro Optics, Korea) following the procedure described by Malaisamy et al. [41]. The zeta
potential was measured using clamping cell of the electro kinetic
analyzer at pH 7 using 1 mM KCl as the electrolyte. A similar
procedure was followed from our group's earlier work [42] and a
correction factor for the polymethylmethacrylate (PMMA) was
used as indicated by one of the early users of the technique [43].
The modied membranes were stored in Milli-Q water for a
minimum of 7 days prior to further testing.
2.4. Membrane ltration performance
The pure water ux (PWF) values of the unmodied PES and
GO modied membranes were evaluated using dead-end ltration. Milli-Q water with resistivity of 18.2 M cm at 25 C was
used as the feed to measure pure water ux at 10 psi for 4 h. All
the membranes were initially compacted with Milli-Q water at
60 psi for at least 2 h or until the ux reached the steady state.
Using the same ltration system and operating pressure
(10 psi), dextran of varying molecular weight values (25, 50, 80,
150, 270, 410, and 670 kDa) at a concentration of 1 wt% were ltered individually through the GO-modied membranes for
10 min, to determine the MWCO. The concentration of dextran

was estimated using a TOC analyzer (Dohrmann Phoenix 8000) by

the persulfate method. The MWCO of the membrane was determined at 90% rejection.
2.5. Fouling experiments
The fouling behavior of the GO-modied membrane was analyzed using humic acid solution as the foulant in a cross-ow ltration system. Humic acid was chosen as a surrogate for the
natural organic matter (NOM) which was chosen due to its prevalence in natural water; their complexity in fouling mechanisms
[79]; and resistance to cleaning [10]. A feed solution containing
100 mM NaCl, 1 mM CaCl2, and of 20 mg/L humic acid buffered at
pH 7 was ltered through the GO-modied membranes (2, 4,
6 wt%) and unmodied PES-UF membrane in direct fouling condition for 4 h. The fouling experiments were repeated three times;
at a cross-ow velocity of 1 L/min and adjusted trans-membrane
pressure to maintain the same initial permeate ux. The permeate
was continuously recycled into the feed tank and the permeate
ow rate was monitored and recorded by an in-situ digital ow
meter.
In order to investigate the membrane recovery performance on
a long term organic fouling, the humic acid feed was ltered across
the GO-4 and the PES-UF membranes for 8 h, at the same operating conditions as the short term fouling experiment. PES-UF
membrane with 100 kDa MWCO was chosen as a control for this
study based on the comparable MWCO of the GO-4-modied
membrane, and approximately the same water permeability. After
every two hours of fouling, the membranes were hydraulically
cleaned for 30 min, at the same cross-ow velocity of 3 L/min and
a pressure of 50 psi. At the end of the long term fouling (8 h), MilliQ water was ltered across the fouled membrane surface for
30 min, at a cross-ow velocity of 3 L/min and a pressure of 50 psi,
and the pure water ux recovery was measured compared to the
water ux before fouling.
2.6. Stability of the GO-modied membrane
The amount of GO nanosheets attached on the TMC-modied PES
surface was determined indirectly by quantifying the GO concentration in Milli-Q water. The stability of the chemically attached GO nanosheets on the PES surface was investigated in an agitated water
bath. The GO membrane was submerged in a 250 mL beaker containing Milli-Q water and placed on a shaker. The water bath was
agitated at 800 rpm at room temperature for 7 days and at the end of
every 24 h, the water was exchanged with fresh Milli-Q water, with
the same GO-modied membrane submerged in it. The agitation
created hydrodynamic shear stress on the GO membrane surface, thus
leaching out physically adsorbed GO nanosheets. The leached out GO
present in the 250 mL water collected every 24 h was concentrated to
50 mL, through evaporation in an oil bath, and the nal GO concentration was analyzed using UV-Visible spectroscopy at a wavelength of 232 nm. GO concentrations of 0.4, 0.3, 0.2, 0.1, and 0.05 wt%,
were prepared and a calibration curve (R2 0.997) was obtained. The
percentage of GO leached during agitation was calculated relative to
the amount of GO attached on the membrane after rinsing, and subsequent amount left after each day of agitation. The experiment was
conducted in triplicate.

3. Results and discussion

3.1. Synthesis and characterization of graphene oxide
The FT-IR spectrum of the synthesized GO is shown in Fig. 2a.
The peak at 1618 cm  1 corresponds to the presence of un-oxidized

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521

Fig. 2. (a) FT-IR spectra of graphene oxide nano sheets and graphite powder (both in solid state) and (b) Raman spectrum of graphene oxide nanosheet.

sp2 C C bond in the graphitic lattice structure, while the peak at

1044 cm  1 corresponds to the presence of C-O stretching vibration [32]. The intense peak at 1721 cm  1 corresponds to the
stretching vibration of C O bond from the carboxylic group and
the broad peak at 3318 cm  1 corresponds to the stretching vibration of OH bond from the synthesized graphene oxide [44].
The Raman spectrum in Fig. 2b indicates the G peak at
1591 cm  1 and D peak at 1355 cm  1. The G peak represents the
sp2 hybridization of the graphitic carbon. The D peak signies the
carbon lattice distortion as a result of the introduction of oxygenic
functional groups (epoxy, hydroxyl, and carboxyl) on the basal
plane and edges of the graphitic carbon during oxidation [44].
3.2. UV-induced amination on PES membrane surface
The mass of allylamine grafted on the active surface of the PES
membrane is a function of the monomer concentrations and UV irradiation time (Fig. 3). At 10 min irradiation time, the average degree
of grafting (1172 g/cm2) was statistically the same for the 100 and
200 mM allylamine monomer concentrations, while the D.G slightly
increased to 1375 g/cm2 for the 300 mM allylamine monomer
concentration. However, at 20 min, the DG increased signicantly
from 6474 to 8876 g/cm2 between the 100 and 300 mM monomer concentrations. The highest DG was observed at 30 min irradiation time, where the DG increased from 9375 to 133710 g/cm2
between 100 and 300 mM allylamine monomer concentrations.
The membranes modied with 300 mM at 30 min irradiation
time have more than 80% lower water ux relative to the unmodied PES membrane (Fig. 4). At long UV exposure times, it is
likely that the grafted polyallylamine partially blocks the pores of
the PES membrane, lowering the water ux. In order to increase
the reactivity between the acyl chloride from the cross-linker and
the amine groups on the PES-g-NH2 membrane surface, while still
maintaining relatively high water ux, the conditions of 100 mM
at 20 min were chosen for subsequent GO modication
experiments.
The membrane surface was interrogated by XPS to more directly conrm the grafting of amine functional groups onto the
membrane surface. The elemental compositions and atomic ratios
are shown in Table 1. The increase in nitrogen content from 2.96 to
7.46% and increase in the atomic nitrogen in N/C and N/O ratios,
conrm the grafting of allylamine on the membrane. The nitrogen
content in the unmodied PES membrane may have come from
undissolved additives (such as polyvinylpyrrolidone) added during
the fabrication of the PES membrane.

Fig. 3. The degree of allylamine grafting onto PES membranes surfaces with different allylamine concentrations (100, 200, and 300 mM) and reaction times (10,
20, and 30 min).

Fig. 4. Effects of allylamine concentration and UV irradiation time on pure water

ux of PES-g-NH2 membranes.

3.3. Characterization of the GO membrane surface

3.3.1. Surface functionality
The IR spectra (Fig. 5) of the modied PES with 100 mM

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E. Igbinigun et al. / Journal of Membrane Science 514 (2016) 518526

Table 1
The elemental and atomic compositions in PES-Polyamine membrane (PES-g-NH2).
Membranes

PES
PES-g-NH2

Elemental Composition (%)

Atomic Ratios

O/C

N/C

N/O

S/N

75.01
78.32

17.85
12.63

2.96
7.46

4.18
1.59

0.24
0.16

0.04
0.10

0.17
0.60

1.41
0.21

Fig. 5. FT-IR spectra of (a) unmodied PES membrane; (b) Amine functionalized
PES membrane (PES-g-NH2); (c) PES-g-NH2 membrane reacted with TMC (0.2 wt%); and (d) PES-g-NH2-TMC membrane covalently bonding with GO.

allylamine after 20 min irradiation time, revealed vibrational

peaks at 1634 cm  1 corresponding to NH bending [45,46], peak
at 1034 cm  1 corresponding to the -C-N stretching [7]. In the
second step of the modication, the free acyl chloride groups from
the cross-linker, reacted with the terminal amine groups of the
PES-g-NH2 membrane, and the peaks at 1802 and 1797 cm  1
correspond to the symmetric and asymmetric free acyl chloride
stretching. The peaks at 1800 and 1755 cm  1 indicate the presence of carbonyl stretching in the anhydride bond formed between the acyl chloride and the carboxylic group on the GO nanosheets. The intense peak at 1722 cm  1 may correspond to the
carbonyl stretching from the carboxylic group of the GO nanosheets or from an ester bond formed between the free acyl
chloride and the hydroxyl group on the GO nanosheets.
3.3.2. Surface morphology and hydrophilicity
The changes in the surface morphology before and after GO
modication were examined by SEM in Fig. 6(ad). The pore size of
the PES membrane became smaller then indiscernible after modication with polyallylamine and GO respectively. The GO nanosheets completely covered the modied PES surface, as indicated by the SEM image in Fig. 6c. AFM images (Fig. 7) showed
that the GO-modied membrane has a lower RMS roughness
(8.8 nm) when compared to the unmodied PES membrane
(37.2 nm) and commercial PES-UF membrane (18.3 nm). The GO
membrane showed an average contact angle of 5575 indicating
a higher hydrophilicity than the unmodied PES and commercial
PES-UF membranes, which had contact angles of 7775 and
76 74 respectively.

Fig. 6. Top surface SEM images of PES membrane (a) before modication (b) after amine modication (c) after GO-4 modication and (d) commercial PES-UF membrane for
fouling studies.

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523

Fig. 7. AFM Surface roughness of (a) PES membrane (b) commercial PES-UF membrane, and (c) GO modied membrane, PES-GO-4.

3.3.3. Zeta potential

The zeta potential (ZP) of the GO-modied membrane is
23.3 7 2.4 mV at pH 7, 10  3 M KCl. This value can be compared
to the ZP of the unmodied PES microltration membrane,
15.7 72.8 mV and the PES ultraltration membrane surface,
0.3 70.8 mV. The higher negative ZP of the GO membrane is due
to the anionic functional groups OH and COOH. A more negative
zeta potential is desirable, as it reduces organic fouling by electrostatic repulsion between the negatively charged membrane
surface and the organic foulant (humic acid), which is negatively
charged at pH values common in water bodies and water treatment (pH 69).
3.4. Pure water ux and dextran rejection of the membranes
As shown in Fig. 7a, the pure water ux (PWF) for the PES
membrane is 1407 4.8 L/(m2 h), which decreased to 84 72.5,
767 1.6 and 55 77 L/(m2 h) after being modied with 2, 4, and

6 wt% GO respectively. The membrane coated with 4 wt% GO exhibited a decrease in pure water ux by approximately 46% and
15% relative to the water ux of the PES and PES-g-NH2 membranes respectively. The pure water ux of the 6 wt% GO modied
membrane was more than 50% lower than the PES membrane
water ux. The decrease in pure water ux may be due to additional lm thickness caused by the GO nanosheets, thus offering
additional membrane resistance to water ux [47].
The PES-GO-4 membrane has a MWCO of 140 kDa, while the
6 and 2 wt% GO-modied membranes have a MWCO of 80 and
370 kDa respectively, as seen in Fig. 8b. The PES-GO-6 has the
highest solute rejection but it is limited by its low pure water ux.
The 4 wt% GO modied membrane with MWCO in the ultraltration range, was selected for fouling studies due to its combination of higher pure water ux (relative to the PES-GO-6
membrane) and lower MWCO value (relative to PES-GO-2
membrane).

Fig. 8. (a) The pure water ux for PES, PES-g-NH2 and GO modied membranes (2, 4, 6 wt%) in a dead-end membrane ltration (b) Dextran rejection characteristics of the
GO modied and pristine PES membranes at 10 psi.

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Fig. 9. Normalized permeate ux during humic acid (20 mg/L) fouling of commercial PES-UF and the GO-modied membranes (2, 4, and 6 wt%) in a cross-ow
ltration system.

3.5. Fouling and cleaning studies

3.5.1. Short-term humic acid fouling study
During the 4 h of fouling (Fig. 9), the GO- modied membranes
exhibited higher ux compared to the commercial PES-UF membrane. The commercial PES-UF membrane showed the highest ux
decline, likely due to increased rate of fouling caused by interactions between the hydrophobic groups of the humic acid [49,50]
and the hydrophobic surfaces of the commercial PES-UF membrane surface. These interactions increased the rate of humic acid
adsorption on the membrane surface and pores, and resulted in a
signicant permeate ux decline [51]. The hydrophilic and relative
smooth surface of the GO membranes may play a role in reducing
the attachment of humic acid foulant onto the GO modied
membrane surfaces.
3.5.2. Effects of hydraulic cleaning for long-term humic acid fouling
study
Humic acid solution was ltered through the commercial PESUF and GO-modied membranes for 8 h (under the same operating parameters as the short term fouling), with regular hydraulic
cleaning every 2 h. In addition to the comparable MWCO, the pure
water permeability of PES-GO-4 (8.28 L/m2 h psi) and commercial
PES-UF (7.81 L/m2 h psi) membranes were similar at a transmembrane pressure of 50 psi.
The normalized permeate ux results are shown in Fig. 10.
After three cycles of fouling with hydraulic cleaning, 70% of the
original pure water ux was recovered for the GO-4 membrane,
while 28% of the pure water ux was recovered for the commercial
PES-UF membrane.
The zeta potential of the GO-4 modied membrane is more
negative ( 23.3 mV) compared to the PES-UF membrane, which is
almost neutral at pH 7. This difference in surface charge results in a
strong repulsion between the humic acid and GO-modied
membrane surface that inhibits adsorption and aids in the removal
of loosely adsorbed humic acid from the GO-modied surface
during hydraulic cleaning [15,48]. This behavior may be due to the
formation of more hydrated layers between the oxygenic functional groups of the GO-membrane and water during the repeated
hydraulic cleaning [52]. As expected, for the commercial PES-UF
membrane, fouling becomes more severe at longer ltration times.
After the initial deposition, a gel layer forms on the surface,
blocking the pores, thus, increasing the rate of pure water ux
decline [53,54].

Fig. 10. Effects of GO modication on long-term fouling behavior of commercial

PES-UF and GO-4 modied PES membranes.

3.6. Stability of the GO-modied membrane

Leaching experiments were conducted to conrm the stability
of the covalently bound GO nanosheets onto the PES membrane
coupons with surface area 12.5 cm2. The concentration of GO on
the membrane surface was 1.84 g/cm2 upon initial modication.
After the 7 day leaching study, 0.336 g/cm2 of GO was leached
out of the membrane surface, with the majority of the leaching
(90%) occurring during the rst day. As shown in Fig. 11, the
leaching of the GO nanosheets was not signicant, as approximately 82% of the GO nanosheets remained covalently attached
onto the PES membrane by the cross-linker after 7 days.
Leaching was attributed to the unreacted GO that was physically adsorbed on the membrane surface. There was no signicant
amount of GO detected in the storage solution after day 5; this
indicated that the covalent bonding between the GO sheets and
TMC is stronger than the hydrodynamic shear force created during
agitation. Performance data presented in this study were collected
with GO modied membranes after 7 days of storage.

4. Concluding remarks
This study has demonstrated that UV induced amination of a
polyethersulfone membrane followed by the binding of graphene
oxide nanosheets can be employed as a simple, effective method

Fig. 11. The concentration of GO nanosheets leached into storage solution during
the 7 days of agitation. The initial GO surface concentration was 2.30 wt% before
agitation.

E. Igbinigun et al. / Journal of Membrane Science 514 (2016) 518526

to produce a GO-functionalized UF membrane. The resulting GOfunctionalized membrane had relatively smooth surface that
completely covered the PES substrate and exhibited increased
surface hydrophilicity, increased negative zeta potential, lower
fouling and higher ux recovery when compared to a commercial
PES-UF membrane using a humic acid feed solution.
The process of chemically linking the GO nanosheets to the PES
membrane through the intermediate steps such as amination and
cross-linking results in a stable UF composite membrane under
realistic operating conditions. The GO-modied membranes could
be used as pretreatment for nanoltration or reverse osmosis
applications. This technique is also scalable and should be more
cost effective than comparable modication approaches.

Acknowledgements
This material is based upon work supported by the National
Science Foundation (NSF) and the Environmental Protection
Agency (EPA) under NSF Cooperative Agreement EF-0830093,
Center for the Environmental Implications of NanoTechnology
(CEINT) and the National Oceanic and Atmospheric Administration, Ofce of Education Partnership Program Award. Any opinions, ndings, conclusions or recommendations expressed in this
material are those of the author(s) and do not necessarily reect
the views of the NSF or EPA. This work has not been subjected to
EPA review and no ofcial endorsement should be inferred. Its
contents are solely the responsibility of the award recipient and do
not necessarily represent the ofcial views of the U.S. Department
of Commerce, National Oceanic and Atmospheric Administration.
We acknowledge the help of Mr. James Grifn of the Howard
Nanoscale and Engineering Facility, who conducted the SEM experiments. We also acknowledge Dr. Preethi Chandran and Hashanti Perera komitige of the Department of Chemical Engineering, Howard University for their assistance on AFM analysis and
interpretation of results on our membrane samples.

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