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Research Article

Cite This: ACS Appl. Mater. Interfaces 2018, 10, 16140−16147 www.acsami.org

Robust Covalently Cross-linked Polybenzimidazole/Graphene Oxide

Membranes for High-Flux Organic Solvent Nanofiltration
Fan Fei,†,‡ Levente Cseri,§ Gyorgy Szekely,*,§ and Christopher F. Blanford*,†,‡
†
School of Materials, University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom
‡
Manchester Institute of Biotechnology, University of Manchester, 131 Princess Street, Manchester, M1 7DN, United Kingdom
§
School of Chemical Engineering and Analytical Science, University of Manchester, The Mill, Sackville Street, Manchester, M1 3BB,
United Kingdom
*
S Supporting Information

ABSTRACT: Robust, readily scalable, high-flux graphene

oxide (GO) mixed matrix composite membranes were
developed for organic solvent nanofiltration. Hydroxylated
polybenzimidazole was synthesized by N-benzylation of
Downloaded by 86.134.154.244 at 13:24:46:855 on June 20, 2019

polybenzimidazole with 4-(chloromethyl)benzyl alcohol,

from https://pubs.acs.org/doi/10.1021/acsami.8b03591.

which was confirmed by FTIR and NMR spectroscopy. Flat-

sheet composite membranes comprising of polybenzimida-
zoles and 1 or 2 wt % GO were fabricated via conventional
blade coating and phase inversion. Subsequently, GO was
covalently anchored to the hydroxyl groups of the polymer
using a diisocyanate cross-linking agent. The even distribution
of GO in the membranes was mapped by visible-light microscopy. Hydroxylation and incorporation of GO in the polymer matrix
increased the permeance up to 45.2 ± 1.6 L m−2 h−1 bar−1 in acetone, nearly 5 times higher than the unmodified benchmark
membrane. The enhancement in permeance from the addition of GO did not compromise the solute rejection. The composite
membranes were found to be tight in seven organic solvents, having molecular weight cut-offs (MWCO) as low as 140 g mol−1.
Permeance increased with increasing solvent polarity, while rejection of a 420 g mol−1 pharmaceutical remained over 93%. The
covalent anchoring resulted in robust composite membranes that maintained constant performance over 14 days in a continuous
cross-flow configuration.
KEYWORDS: composite membrane, graphene sieve, mixed matrix membrane, surface modification, cross-linking

1. INTRODUCTION research suggests the potential of advanced materials, such as

Conventional separation processes account for up to 70% of the
total capital and operational cost of chemical plants, and
consequently remain an obstacle to sustainable manufacturing.1
Membrane-based technologies provide more economic and
sustainable alternatives to conventional separation processes.2
Organic solvent nanofiltration (OSN) is a pressure-driven
separation technique that uses semipermeable membranes that
can selectively distinguish solutes between 50 and 2000 g mol−1.3
OSN has found applications mainly in petrochemical and
pharmaceutical industries, being used for solvent exchange and
recycling, product purification and concentration, and catalyst
recovery.
Membrane materials are core parts of any membrane-based
technologies, and consequently the prime focus of the current
membrane research lies in developing new materials to improve
stability, permeance, rejection, and robustness in general. State-
of-the-art OSN membranes provide long-term stability in organic
media, low molecular weight cutoff (MWCO) valuesthe
molecular weight of the compound that is 90% rejectedand a
trade-off between selectivity and ultrahigh permeance to
minimize the processing time and membrane area.4−7 Recent
metal−organic frameworks,8 carbon nanosheets,9 and gra-
phene,10 for the fabrication of more efficient membranes.
Graphene oxide (GO), a chemical derivative of graphite in the
family of graphene nanomaterials, comprises of carbon sheets
decorated with oxygen-containing functionalities on the edges
(hydroxyl, carbonyl, and carboxyl groups) and on the surface
(hydroxyl and epoxide groups). GO is a versatile starting material
because of its ready dispersibility and reactivity in both organic
and aqueous media. GO can be used as a membrane either on its
own as a laminate,11 or mixed with polymers to fabricate mixed
matrix membranes.12 A series of different techniques, such as
vacuum filtration,11 drop casting,13 dip-coating,14 spin-coating,15
spray-evaporation,16 layer-by-layer assembly,17 and shear align-
ment18 have been used to prepare GO membranes.
GO membranes have been mainly developed for desalina-
tion19 and gas separation.20 However, efforts aiming at molecular
separation are emerging with promising results in the field of
Received: March 2, 2018
Accepted: April 19, 2018
Published: April 19, 2018

© 2018 American Chemical Society 16140 DOI: 10.1021/acsami.8b03591

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Figure 1. Reaction scheme showing the N-benzylation of polybenzimidazole and the diisocyanate-based (A) cross-linking of hydroxylated
polybenzimidazole chains, (B) anchoring of GO sheets, and (C) cross-linking of GO sheets.

OSN.21−23 Incorporation of GO into a polypyrrole matrix
significantly enhanced solvent permeance without compromis-
ing solvent rejection.21 In contrast, GO-embedded polyethyle-
nimine membranes displayed enhanced solute rejection and
adequate solvent flux.22 These studies were carried out in a
limited number of mild solvents (acetone and alcohols), in a
dead-end configuration with limited volume of test solutions,
hindering long-term performance studies.
The cohesion between the components of a mixed matrix
membrane plays an important role in the performance and long-
term stability.24 Therefore, not only the individual characteristics
but also the interaction of the phases should be considered when
designing mixed matrix membranes. The distribution of GO
flakes in polymer matrices is an important aspect for composite
filtration membranes; the decline in membrane permeance in
previous reports was attributed to aggregation of GO.25
Herein, we report the fabrication, characterization, perform-
ance, and long-term stability of mixed matrix membranes
comprised of polybenzimidazole (PBI) and GO. PBI was
selected as polymer matrix due to its outstanding ability to
withstand extreme thermal, chemical and mechanical con-
ditions.26 PBI-based OSN membranes have been recently
developed by the Livingston group,27,28 and they have been
successfully used for solvent exchange29 and solvent recovery.30
and solvents were used as received without further purification. All
solutions were prepared using water with a resistivity of 18.2 MΩ cm at
25 °C (Milli-Q).
2.2. Synthesis of Hydroxylated Polybenzimidazole. Hydroxy-
lated polybenzimidazole (PBI−OH) was synthesized through N-
benzylation of polybenzimidazole (Figure 1). In a typical synthesis, 26
wt % PBI dope solution (4.46 g) was diluted with DMAc (45 mL) stirred
at room temperature for 0.5 h, followed by the addition of tBuOK (0.886
g, 7.91 mmol, 2.1 eq. per repeating unit). The color of the reaction
mixture turned from brown to red indicating the deprotonation of the
amine groups of the polymer. The mixture was stirred at room
temperature for 3 h to ensure completion of deprotonation. 4-
(Chloromethyl)benzyl alcohol (1.182 g, 7.53 mmol, 2 equiv per
repeating unit) was added in one portion and the reaction was stirred at
room temperature for 3 days. The product was precipitated in 1 L H2O/
ethanol (1:1 v/v) mixture, and then filtered. The filter cake was dialyzed
in water and freeze-dried to obtain the final product as a yellow powder.
2.3. Membrane Fabrication. Dope solutions containing PBI, PBI−
OH, and GO were prepared. The total solid content in all dope solutions
was 20 wt % by adding suitable amount of DMAc as solvent. The
percentage of PBI, PBI−OH, and GO in the solid content for each
membrane is shown in Table 1. Homogeneous dope solutions were
realized by mechanical stirring of the components at 50 rpm and room
temperature for 6 h, followed by degassing under argon in an incubator
shaker at 400 rpm and 30 °C for 12 h. Membranes were cast onto
nonwoven polypropylene support using an Elcometer 4340 film

2. EXPERIMENTAL SECTION Table 1. Abbreviations and Compositions of Membranesa

2.1. Materials and Reagents. Polybenzimidazole dope solution membrane PBI PBI−OH GO TDI cross-linking
(PBI, 26 wt % in DMAc) was purchased from PBI Performance designation (wt %) (wt %) (wt %) reaction
Products, Inc. (Charlotte, USA). Graphene oxide (flake) was purchased M1 100 0 0 no
from William Blythe Ltd. (Accrington, UK). Potassium tert-butoxide M2 90 10 0 no
(tBuOK) and analytical grade organic solvents were purchased from
M3 90 10 0 yes
Fisher Scientific. 4-(Chloromethyl)benzyl alcohol, toluene 2,4-
M4 89 10 1 no
diisocyanate (TDI), methylstyrene dimer, and mepenzolate bromide
(N,N-dimethyl-3-piperidiniobenzylate bromide) were purchased from M5 89 10 1 yes
Sigma-Aldrich. Novatexx 2471 polypropylene nonwoven backing was M6 88 10 2 no
purchased from Freudenberg Filtration Technologies (Crewe, UK). M7 88 10 2 yes
Polystyrene markers for solute rejection evaluation were purchased from
a
Agilent Technologies. Microscope slides and dialysis tubing (SnakeSkin The total solid content in all dope solutions were 20 wt %. The table
10 kDa MWCO 35 mm diameter) were purchased from Thermo shows the percentage of PBI, PBI−OH, and GO in the solid content.
Scientific. Si/SiOx (silicon surface with a silica layer of approximately Composite membranes having 3 wt % GO were prepared but were
290 nm) wafer was purchased from IDB Technologies Ltd. All materials found to be unsuitable for testing because of their brittleness.

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applicator with a casting knife set to a thickness of 250 μm and casting ⎛ Cp ⎞

speed of 5 cm s−1. The membranes were formed by the precipitation of R[%] = ⎜1 − ⎟ × 100
⎝ Cf ⎠ (2)
the film in a coagulation bath containing deionized water (15.0 MΩ cm)
at 20 °C. The A4-size membrane sheets were cut into 9 cm diameter
discs. The membranes were washed and soaked in acetonitrile prior to 3. RESULTS AND DISCUSSION
cross-linking to remove the water. The GO sheets were anchored to the
polymer matrix and the polymer chains were simultaneously cross-
3.1. Polymer and Membrane Characterization. The N-
linked using TDI (Figure 1), which was previously reported for cross- benzylation of PBI was confirmed by IR and 1H NMR
linking Pebax membranes.31 Cross-linking was performed by immersing spectroscopy. In the IR spectrum (Figure 2A), PBI−OH exhibits
the membrane discs in 2 wt % TDI in acetonitrile for 30 min followed by
washing with 3 × 40 mL acetonitrile. Covalent cross-linking is often used
to lower the MWCO and improve the stability of membranes. In this
particular work, the GO is also cross-linked to the polymer matrix to
prevent it leaching out of the membrane over time.
2.4. Characterization. NMR analyses were performed on a B500
Bruker Avance II+ 500 MHz instrument using DMSO-d6 as a solvent.
The solvent peak was used as an internal chemical shift reference. Solid
state NMR spectra were recorded on a Bruker Avance III 400 MHz solid
state NMR spectrometer with cross-polarization (CP) pulse and magic
angle spinning (MAS) using adamantane as an external 13C chemical
shift reference.
Attenuated total reflection Fourier-transform infrared spectroscopy
(ATR-FTIR) spectra of powder and membrane samples were acquired
using a Bruker Alpha-P run in air, mounting on a zinc−selenium/
diamond plate. The spectra were recorded at a resolution of 4 cm−1 as an
average of 16 scans. Raman analysis of the PBI-containing materials was
not possible because of the intrinsic fluorescence of the polymer.
Optical microscope images were obtained by Keyence VHX-5000
digital microscope. Samples were prepared by sticking the dried
membranes on glass slides using double-sided tape.
Membrane surface and cross-sectional microstructure was deter-
mined by scanning electron microscopy (SEM) using a Hitachi S-
3000N with a tungsten hairpin filament emission gun at an accelerating
voltage of 5 kV. Samples were prepared by sticking the membranes on a
conductive carbon tab and sputter coated with gold/palladium under an
argon atmosphere using a Quorum Q150TES in order to make the
samples conductive.
Atomic force microscopy (AFM) images were acquired in tapping
Figure 2. (A) ATR-FTIR spectra of PBI and PBI−OH powders. The
mode in air using a Digital Instruments Dimension 3100 with Bruker additional C−H and C−O peaks in the PBI−OH spectrum arise from
TESPA-V2 probe with a nominal spring constant of 37 N m−1 and a the presence of hydroxymethyl groups. (B) 1H NMR spectra of PBI and
nominal tip apex radius of 7 nm. Samples were prepared by sticking the PBI−OH. In the spectrum of PBI−OH, the five new peaks between 7.5
membranes on a glass slide using double-sided tape. For roughness and 4.0 ppm, and the change of the signal structure in the aromatic
calculations, three membranes of each type with an area of 25 μm2 were region confirm the N-benzylation.
scanned and analyzed with the NanoScope Analysis software.
Thermogravimetric analysis (TGA) was determined using a TA
Instruments Q500 in N2 atmosphere with the ramp rate of 10 °C min−1.
two additional peaks compared to PBI, which can be assigned to
2.5. Membrane Performance Tests. Membrane performance was
tested in a typical stainless steel cross-flow nanofiltration apparatus at 10
alkane C−H stretch bonds of methylene (2867 cm−1) and
bar (Figure S9). Two independently prepared membrane discs of each alcohol C−O stretch bonds (1015 cm−1). The N-benzylation
type were tested, and the reported results are the mean values of these causes two red shifts in the spectrum: CN stretching vibrations
measurements. The effective area (A) of each membrane was 52.8 cm2. shifted from 1612 to 1619 cm−1 due to the electronic effects of N-
The permeance was calculated as given in eq 1. substitution, and the out-of-plane bending of C−H groups in the
imidazole ring shifted from 687 to 700 cm−1.34
permeance [L m−2 h−1 bar −1] =
J
=
V The 1H NMR spectrum (Figure 2B) is also in good agreement
ΔP ΔPAt (1) with the expectations. In the case of PBI−OH, five additional
signals were observed compared with PBI. Two significant peaks
The permeance of each membrane was calculated by dividing the in the upfield aromatic region, at 7.21 and 7.02 ppm, are
solvent flux through the membrane (J) by the transmembrane pressure attributed to the protons of the para-substituted benzene ring.
(ΔP). The flux was obtained by measuring the volume of solvent (V) Two peaks of methylene protons were identified at 5.69 ppm
that permeates through the membrane per membrane area (A) per time
(N−CH2−φ) and 4.40 ppm (φ−CH2−O) while the peak at 5.13
(t). The model system for the MWCO curve determination composed
of a mixture of 1 g L−1 PS580 and PS1300 polystyrene markers and 0.1 g ppm belongs to OH protons. The relative peak areas of these five
L−1 of divinylbenzene (130 g mol−1) and 0.1 g L−1 methylstyrene dimer signals are 2:2:2:2:1 in agreement with the expected structure. A
(236 g mol−1) solutions.3,32,33 Because of its versatile solubility, peak at 13.24 ppm in the spectrum of PBI−OH, identified as NH
mepenzolate bromide (420 g mol−1) at 0.1 g L−1 was used for solute protons, shows that the N-benzylation was not complete. The
rejection determinations in various solvents. The rejection (R) of solutes degree of benzylation was calculated to be 70% based on the ratio
was determined as the ratio of its measured concentration in the between aromatic backbone protons and the methylene protons
permeate (Cp) and the feed (Cf) as defined in eq 2. found at 4.40 ppm. The incomplete N-benzylation can be
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attributed to the steric crowding around the polymeric backbone.
Furthermore, a significant change can be observed in the
structure of aromatic protons compared with PBI. The
phenylene protons at 9.19 and 8.36 ppm significantly down-
shifted due to the extra shielding provided by the introduced
benzyl groups. Moreover, their signals are split up as a result of
the incomplete modification.
Membranes were characterized by FTIR and TGA analysis.
The cross-linking was verified by two characteristic signals of
urethane bond in the IR spectrum (Figure 3). In the cross-linked
Figure 3. FTIR spectra of GO flake and membranes of different
compositions. The cross-linked membranes exhibit two characteristic
peaks which confirm the presence of the urethane groups formed during
the cross-linking. GO peaks could not be identified in the membrane
spectra due to the low GO content.
membranes, the peaks of the CO stretch (1665 cm−1) and C−
N stretch (1225 cm−1) were observed. Owing to the small GO
content (1−2 wt %), it has no characteristic peak in the FTIR
spectra.
The chemical composition of membranes was characterized by
suspension and solid-state 13C NMR spectroscopy (Figure 4).
Both techniques provided similar results; however the solid-state
NMR showed higher sensitivity, while the suspension NMR had
higher resolution. The PBI signals were the most prominent in
the spectra with aromatic signals between 110−140 ppm, and the
imidazole carbon at 151 ppm (δ). Weak signals of benzyl carbons
originating from PBI−OH (β and γ) were identified in the solid
state spectra of M6 and M7. The spectra of M7 contain the
characteristic methyl carbon of the cross-linker at 17 ppm (α).
Furthermore, the two additional aromatic signals of the cross-
linker can be observed in the suspension NMR spectra at 130 and
138 ppm. The appearance of urethane carbons at 153 ppm (ε)
indicated successful diisocyanate cross-linking, which was also
confirmed with TGA analysis (Figure S12).
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Figure 4. 13C NMR analysis of polymers PBI and PBI−OH, and
membranes M6 and M7. Characteristic signals are indicated by Greek
letters, and they are assigned to carbons showed in Figure 1. An asterisk
(*) is used to mark the solvent (DMSO-d6) in liquid state spectra. ls:
Liquid-state NMR (homogeneous). ls-s: Liquid-state NMR (suspen-
sion). ss: CP-MAS solid-state NMR.
Membrane morphology was characterized by optical micros-
copy, SEM, and AFM. None of the techniques revealed any
difference between non-cross-linked membranes and their cross-
linked counterparts. The images of cross-linked membranes
(M3, M5, and M7) can be found in the Supporting Information.
Visible-light images of the membranes are shown in Figure 5A.
Images of GO containing membranes (M4 and M6) revealed
shiny flakes which are similar in shape and size to the pristine GO
(Figure S1). The flakes were evenly distributed on the membrane
surfaces. ImageJ analysis (Figure S8) revealed the mean apparent
area of GO flakes in the top layers of M4 and M6 to be 0.39 and
0.37 μm2, and their coverage to be 1.5% and 2.0%, respectively.
SEM surface and cross-sectional images of the membranes are
shown in Figure 5B and 5C, respectively. All the membranes
show typical structure of integrally skinned asymmetric polymer
membranes formed via phase inversion, with dense top layers,
spongy support structures in the middle of the membrane and
macroscopic voids at the bottom of the membranes. AFM height
images (Figure 5D) revealed similar surface morphology with
cavities in a few micrometers for all membranes. The
incorporation of PBI−OH reduces the root-mean-square
(RMS) roughness. However, there is no trend for the influence
of the incorporation of GO and cross-linking toward surface
roughness (Table S1).
3.2. Membrane Performance. As shown in Figure 6A, the
10 wt % addition of PBI−OH (M2) increased the initial
permeance by almost two and half times compared to the pristine
PBI membrane (M1), which could be attributed to the
hydrophilicity (Figure S11),35 and lower packing density of
PBI−OH.36 Nonetheless, the M2 membrane showed consid-
erable compaction over time, which resulted in a 33% permeance
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ACS Applied Materials & Interfaces
Figure 5. Images of membranes cast from pure PBI (M1), PBI + 10 wt % PBI−OH (M2), PBI + 10 wt % PBI−OH and 1 wt % GO (M4), and PBI + 10
wt % PBI−OH and 2 wt % GO. (A) Visible-light microscope reflection images (frame size = 100 μm × 100 μm), (B) surface and (C) cross-sectional
SEM images (Scale bar = 10 μm; see Figure S6 for active layer thickness), and (D) AFM height images (scan size = 25 μm × 25 μm) of membranes.
decline in 14 days. Having cross-linked the membrane (M3), the
decline in permeance was found to be only 11%, which is less
prominent than for the non-cross-linked membrane (M2). The
incorporation of GO increased both the permeance and the long-
term stability of the membranes (M4−M7). The decrease of
membrane top layer thickness (Figure S6) can contribute to the
increase of the permeance. Moreover, it is speculated that the
presence of GO inhibits compaction of the polymer matrix,
subsequently the permeance is maintained over 14 days of
continuous operation. The highest flux of 45.2 ± 1.6 L m−2 h−1
bar−1 was demonstrated by M6, which is around 18 times higher
than commercial OSN membranes (2.5 L m−2 h−1 bar−1).3,37
The increase from 1 wt % to 2 wt % GO content improved the
permeance, but further increase to 3 wt % GO resulted in a fragile
membrane not suitable for filtration.
The benchmark M1 membrane showed the highest MWCO of
485 g mol−1 (Figure 6B). On the basis of the cutoff curves, the
rest of the membranes formed two distinguished clusters. Cluster
1 consists of the non-cross-linked membranes (M2, M4, M6)
with MWCO of about 277 ± 7 g mol−1, and cluster 2 consists of
the cross-linked membranes (M3, M5, M7) with MWCO of
about 137 ± 15 g mol−1. The results show that the TDI cross-
linking tightened the membranes via decreasing the permeance
(Figure 6A) and increasing the solute rejection and the MWCO
values (Figure 6B). Interestingly, the GO-induced increase in
permeance does not compromise the cutoff profile.
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The reported OSN performances of GO-based membranes are
compared with this work in Table 2. The MWCO values for
M4−M7 show comparable, or even tighter membranes than
previously reported GO/polymer mixed matrix membranes.21,22
Moreover, the permeance obtained for M6 is 1 order of
magnitude higher than the others. Our work outperforms the
GO laminate membrane38 in permeance, although the latter has
an unprecedented ultrasharp sieving cutoff. Such improvement
comes with the requirement for excessive GO quantity as 100%
GO is used for the membrane fabrication, which hinders scale-up
due to currently limited GO availability and high cost.
M6 and M7 were tested in a series of common solvents with
different polarity such as toluene, tetrahydrofuran, dichloro-
methane, acetonitrile, methanol, and water, through continuous
operation over 14 days in cross-flow configuration (Figure 6C
and 6D). The cross-linked M7 showed lower permeance but
higher rejection in all the solvents. The permeance increased with
the dielectric constant of the solvent, and reached a plateau in
highly polar solvents (Figure 6C), which can be explained by the
higher affinity of polar solvents for the hydrophilic membrane
surface.39,40 This result is in agreement with the reported trend
for GO laminates.11 Rejection values were obtained for
mepenzolate (420 g mol−1), an active pharmaceutical ingredient,
which has a versatile solubility covering both polar and nonpolar
solvents. Both membranes showed high rejection (93−100%) in
all solvents, but no correlations between rejection and
permeance or rejection and solvent polarity were observed
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Figure 6. Comparison of membrane performance in acetone: (A) permeance of acetone over time and (B) solute rejection. Error bars represent
standard deviations derived from two independently prepared membranes cast from separately prepared dope solutions. The effect of solvent on
membrane performance: (C) permeance of various solvents, and (D) rejection values for mepenzolate (420 g mol−1). Error bars represent standard
deviations derived from two experiments using independently prepared membranes.

Table 2. Graphene Oxide Membranes for Molecular Separations in Organic Solventsa

maximum continuous
GO permeance MWCO stability test process
polymer matrix (wt %) (L m−2 h−1 bar−1) (g mol−1) solvents (days) configuration
Ding et al.22 polyethylenimine 1−4 5 (acetone) 200−400 acetone, ethanol dead-end cell
(batch)
21 b
Shao et al. polypyrrole 1 3 (2-propanol) <973 methanol, ethanol, 2-propanol dead-end cell
(batch)
Yang et al.38 N/A 100 18 (hexane) <249c butanol, isopropanol, ethanol, water, butyl dead-end cell
acetate, methanol, tetrahydrofuran, (batch)
acetonitrile, acetone, hexane
this work polybenzimidazole 1−2 45 (acetone) 140−490 acetone, toluene, tetrahydrofuran, 14 cross-flow
dichloromethane, acetonitrile, methanol, (continuous)
water, dimethylformamide
a
Only this work includes GO crosslinking. bReported rejection for rose bengal (973 g mol−1) is 98.5%. cReported rejection for chrysoidine G (249 g
mol−1) is >99.9%.

(Figure 6D). The non-cross-linked M6 was found to be stable in 4. CONCLUSIONS

DMF, which is speculated to be the result of GO stabilizing the
polymer matrix through π−π interactions with the polymer, as
observed in the literature.41,42 The high rejection and water
permeance of M6 suggests potential applications also in aqueous
separations including desalination.
16145
Mixed matrix membranes comprising of graphene oxide and
polybenzimidazoles were developed for nanofiltration in organic
media. The hydrophilic modification of PBI (PBI−OH) was
confirmed by ATR-FTIR and 1H NMR analysis. Membrane
cross-linking and GO anchoring was achieved by diisocyanate
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ACS Applied Materials & Interfaces
treatment of the membranes. The cross-linking was followed by
13
C NMR, ATR-FTIR, and TGA analysis. Since GO flakes are
widely regarded as difficult to be identified by electron
microscopic analyses and AFM, we proposed visible-light
microscopy as a method to map the distribution of GO flakes
in polymer matrices. Incorporation of GO into the polymer
matrix improved the membrane performance. First, the presence
of 2 wt % GO increased the permeance by 2.9 and 2.5 times for
the cross-linked and non-cross-linked membranes, respectively.
The membranes showed superior permeance to OSN mem-
branes composed entirely from GO laminates.38 Second, the
stability of the membranes improved, which was demonstrated
via continuous filtration over 14 days in a cross-flow
configuration. The higher polarity solvents had higher
permeance values, which plateaued at 54 L m−2 h−1 bar−1. The
membranes showed high rejection (>93% for 420 g mol−1) in
both polar and nonpolar solvents. Owing to the high permeance
and rejection, the desalination potential of these membranes will
be further studied.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.8b03591.
Characterization of commercial GO flakes by visible-light
microscopy, SEM, AFM, and Raman spectroscopy;
viscosity values for the dope solutions; AFM, SEM, and
visible-light microscope images of membranes; thermog-
ravimetric and nanoindentation analyses of membranes;
nanofiltration process scheme; permeance and rejection
data in eight solvents; NMR and IR spectra of membranes
(PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*Tel.: +44 161 306 4366. E-mail: gyorgy.szekely@manchester.
ac.uk.
*Tel.: +44 161 306 8915. E-mail: christopher.blanford@
manchester.ac.uk.
ORCID
Fan Fei: 0000-0003-0548-5775
Gyorgy Szekely: 0000-0001-9658-2452
Christopher F. Blanford: 0000-0002-0112-7818
Notes
The authors declare no competing financial interest.
In accordance with the University of Manchester’s guidelines, the
data are openly available from Mendeley Data (DOI: 10.17632/
tnh4sgrspy.1).
■
ACKNOWLEDGMENTS
The authors thank the experimental support from Dr. Ben
Spencer (AFM), Mr. Andrew Forrest (nanoindentation), Mr.
Michael Faulkner (SEM), and Mr. Martin Jennings (TGA). This
work was supported by the UK’s Biotechnology and Biological
Sciences Research Council (BBSRC) and Engineering and
Physical Sciences Research Council (EPSRC) through an award
from the BioProNET Network in Industrial Biotechnology and
Bioenergy (BB/L013770/1). F.F. acknowledges the financial
support from his family for his doctoral studies.
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Research Article
■ ABBREVIATIONS
GO, graphene oxide; MWCO, molecular weight cutoff; OSN,
organic solvent nanofiltration; PBI, polybenzimidazole; PBI−
OH, hydroxylated polybenzimidazole; TDI, toluene 2,4-
diisocyanate; DMAc, N,N-dimethylacetamide; DMF, N,N-
dimethylformamide; THF, tetrahydrofuran; DCM, dichloro-
methane; MeOH, methanol; MeCN, acetonitrile
■
REFERENCES
(1) Adler, S.; Beaver, E.; Bryan, P.; Robinson, S.; Watson, J. Vision
2020:2000 Separations Roadmap; EERE Publication and Product
Library, 2000.
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ACS Appl. Mater. Interfaces 2018, 10, 16140−16147