Carbon 191 (2022) 563e570

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Shear-induced assembly of high-aspect-ratio graphene nanoribbon

nanosheets in a confined microchannel: Membrane fabrication for
ultrafast organic solvent nanofiltration
Ji Hoon Kim, Yunkyu Choi, Junhyeok Kang, Ju Yeon Kim, Jun Hyuk Bae, Ohchan Kwon,
Dae Woo Kim*
Department of Chemical and Biomolecular Engineering, YONSEI University, Yonsei-ro 50, Seodaemun-gu, Seoul, (03722), Republic of Korea

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

Article history: One-dimensional graphene oxide nanoribbons (GONRs) were self-assembled into two-dimensional (2D)
Received 14 December 2021 nanosheets using the shear and confinement effect during a slot-die coating process. An aqueous GONR
Received in revised form suspension comprising nanostrings made of entangled GONRs at a concentration of 5 mg/mL was used.
5 February 2022
When the GONR suspension was injected into the microchannel of the slot-die coater, the GONR
Accepted 11 February 2022
Available online 16 February 2022
nanostrings self-assembled to form a nanosheet. The thickness of the GONR nanosheet could be
controlled at the nanometer scale by adjusting the injection rate of the GONR suspension into the slot-die
head, and the lateral dimension of the nanosheet was in the range of several tens of micrometers. The
Keywords:
Graphene nanoribbon
GONR nanosheets could be directly and continuously coated on a porous polymer support by the slot-die
Self-assembly coating method. In particular, a 40-nm-thick GONR layer exhibited ultrafast organic solvent nano-
Slot-die coating filtration (OSN) with an isopropyl alcohol permeance of 679 LMH/bar and molecular weight cut-off of
Nanofiltration 961 Da, substantially surpassing the upper limit of the OSN performances of polymeric and 2D-material-
Nanosheet based membranes. Highly efficient diafiltration of mixed organic molecules in an organic solvent is also
feasible using this GONR membrane.
© 2022 Elsevier Ltd. All rights reserved.

1. Introduction multiwalled carbon nanotubes (MWCNTs) in acidic conditions us-

Graphene nanoribbons (GNRs) are one-dimensional (1D) ma-
terials that exhibit the structural properties of both graphene and
carbon nanotubes (CNTs) [1e4]. GNRs can be stacked with a narrow
interlayer spacing owing to their graphene-like basal plane [5e7],
and they can easily form entangled structures because of their high
aspect ratio and narrow widths [8,9]. Because of their unique
chemical, electrical, and physical properties such as a controllable
bandgap, abundant edge density, electrical conductivity, and
chemical stability, GNRs have been used in various applications,
such as in biomedicine, chemical sensors, energy devices, elec-
tronic devices, electrocatalysis, composites, and membranes
[10e13]. In addition, GNRs can be prepared scalably by unzipping
Abbreviations: GONR, Graphene oxide nanoribbon; GO, Graphene oxide; OSN,
Organic solvent nanofiltration; MR, Methyl red; MnB, Methylene blue; BBG, Bril-
liant blue G; EB, Evans blue; RosB, Rose Bengal; MWCO, Molecular weight cut-off.
* Corresponding author.
E-mail address: audw1105@yonsei.ac.kr (D.W. Kim).
ing a strong oxidizing agent (e.g., KMnO4) [14,15]. As the resulting
unzipped nanoribbons of graphene, referred to as graphene oxide
nanoribbons (GONRs), are decorated with oxygen functional
groups, they can be easily dispersed in water and various organic
solvents [16,17].
Most industrial fabrication technologies are based on solution
processing [18]. Therefore, it is critical to understand the dispersion
behavior of GONRs in various solvents for their practical application
and industrial production [17,19]. Recently, we observed the
concentration-dependent self-assembly of GONRs suspended in
aqueous solvents. According to a previous study, aqueous GONR
suspensions exhibit shear-thinning viscoelastic properties, and the
GONRs entangle to form nanostrings, nanoplates, and macroporous
scaffolds as the GONR concentration increases [20]. However,
despite this finding, there is still a lack of understanding of the
GONR structure in solvents with respect to various factors that
affect the dispersion state of graphene oxide (GO), which has a
similar chemical structure [21]. For example, GO exhibits lyotropic
liquid crystal (LC) properties and forms nematic, smectic, and

https://doi.org/10.1016/j.carbon.2022.02.026
0008-6223/© 2022 Elsevier Ltd. All rights reserved.
J.H. Kim, Y. Choi, J. Kang et al.
cholesteric phases according to the GO concentration and dopant
type [22,23]. Furthermore, the alignment of GO-based LCs can be
controlled using shear and magnetic/electric forces [24,25], which
is useful for improving the performance of GO-based devices such
as battery, supercapacitors, membranes, and fibers that require
highly ordered graphene structures [26e29].
Inspired by the assembly of GO, herein, we demonstrate that the
self-assembly of GONRs into a nanosheet is feasible using the shear
force generated during a slot-die coating process. A slot-die head
with a micro-gap was used to prepare the GONR nanosheet, and the
as-prepared suspension containing the GONR nanosheet was
directly loaded onto a porous polymer support using the slot-die
coater. The fabricated GONR membranes were tested for organic
solvent nanofiltration (OSN) and organic molecule diafiltration. In
particular, we discuss the effects of the slot-die coating conditions
on the structure of the GONR nanosheet and its coating
characteristics.
2. Experimental
2.1. Preparation of a GONR suspension for slot-die coating
GONR was prepared by unzipping the MWCNTs in acidic con-
ditions using KMnO4 as an oxidizer [14,15] and experimental details
can be found in our previous work [20]. Briefly, 2 g of MWCNT was
mixed in 130 mL of H2SO4. And then, 10 g of KMnO4 was slowly
added in the mixture while stirring the solution in an ice bath. After
cooling the mixture, the solution was stirred at 35
C. Then 150 mL
DI water and 40 mL H2O2 were added sequentially in an ice bath.
The resulting solution was centrifuged to remove the acidic solu-
tion and redispersed in DI water several times. The as-prepared
GONR slurry was diluted with DI water to a concentration of
5 mg/mL. To verify the GONR concentration, 2 mL of the GONR
suspension was dried in a vacuum oven at 50
C for 10 h. Then, the
weight of the GONR powder was determined using an electronic
balance. Importantly, ethanol was added to the GONR suspension
to achieve an ethanol concentration of 8 wt%, which is required for
improving the coating quality and decreasing the thickness of the
GONR layer. Typically, 20 mL of the 5 mg/mL GONR suspension was
used in a single coating process; it was directly injected into the
head of the slot-die coater.
2.2. GONR membrane fabrication through slot-die coating
A lab-scale slot-die coater (DCN: Development Creation Nano-
technology, YSU-LSCDC-190801) was used in this study. The slot-
die coater consists of three parts: an ink injection (feeding)
pump, a slot-die, and a moving stage. The GONR suspension was
filled into a feed syringe tank, which was directly connected to the
slot-die head of the coater. Then, a porous polymer support (PES:
0.03 mm of pore size, the diameter of 9 cm or 4.8 cm; GVS North
America Sandford, ME 04073-USA) was placed on the slot-die
coating stage. The gap between the slot-die head and substrate
was fixed at 0.5 mm. The gap between the slot dies was 80 mm. The
coating was generally performed at a feed injection speed of 1.1 mL
min1 with a coating stage moving rate of 40 mm s1. The slot-die-
coated GONR membrane was further dried in a vacuum oven at
50
C overnight to obtain a well-stacked and stable GONR layer on
the PES support.
2.3. Shear-induced assembly of GONR in the slot-die head
A GONR suspension with a concentration of 5 mg/mL was
injected into the slot-die head. The injection rate was increased
from 0.5 to 3.0 mL/min to understand its effect on the GONR self-
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Carbon 191 (2022) 563e570
assembly. The GONR suspension that penetrated through the
80 mm gap of the slot dies was collected and frozen using liquid
nitrogen. It was then freeze-dried for 12 h, and the obtained
powder was imaged by SEM.
2.4. Nanofiltration using a dead-end setup
The nanofiltration test was performed using a customized dead-
end filtration device. The effective area was 4.52 cm2 and the
applied pressure was controlled by controlling the feed amount of
nitrogen gas. The following dyes were tested: methyl red (MR:
electroneutral, 269 Da), methylene blue (MnB; positively charged,
320 Da), brilliant blue G (BBG; negatively charged, 854 Da), Evans
blue (EB; negatively charged, 960 Da), and Rose Bengal (RosB;
negatively charged, 1010 Da). The concentration of the single dye
solution was 10 mg/L. To evaluate the rejection rate and permeance
through the membrane, 30 mL of each dye solution was permeated
under a pressure of 1 bar. The permeance (J in L m2 h1 bar1,
LMH/bar) and rejection rate (R, %) were calculated using the
following equations:
Vp
J¼ (1)
t  A  DP
ðCf  Cp Þ
R¼ *100 (2)
Cf
where Vp (L) is the volume of the permeate solution, t (h) is the
filtration time, A (m2) is the effective area of the membrane, and DP
is the applied pressure. Cf and Cp are the concentrations of the feed
and permeate solutions, respectively, as calculated by UVevis
spectroscopic analysis. To evaluate the mechanical stability of the
GONR membrane with a thickness of 40 nm under high pressure, a
10 mg/L EB solution was used, and the pressure was increased from
6 to 12 bar.
2.5. Cross-flow filtration using the GONR membrane
A long-term filtration test was performed in the cross-flow
filtration mode. The effective membrane area was 7.07 cm2. The
feed solutions with different dyes (MR, EB, MnB, BBG, RosB, and
MR/EB mixture) were prepared in 40 L of isopropyl alcohol (IPA).
The concentration of the single dye solution was 10 mg/L, and the
concentration of the mixed dye solution was 20 mg/L (10 mg/L for
each dye). The feed flow rate was 2 L/min, and filtration was con-
ducted for 56 h at 1 bar using a 40-nm-thick GONR membrane. The
retentate was recycled into the feed tank using a pump. The per-
meance values were recorded using a digital balance. The rejection
rate was evaluated by UVevis spectroscopic analysis. To measure
the pure IPA permeance of the GONR membrane depending on the
thickness of the GONR layer, filtration was conducted for 1 h at
1 bar.
2.6. Characterization
The morphology of the GONRs was characterized by trans-
mission electron microscopy (TEM; JEM-F200, JEOL, Japan). The
contact angles of water, ethanol, and IPA were measured using an
optical tensiometer (DYNE TECHNOLOGY, USA). The functional
groups of the GONRs were characterized by Fourier-transform
infrared spectroscopy (FT-IR, Vertex 70, Bruker ALPHA, Germany).
The surface chemical states of the GONR were characterized by X-
ray photoelectron spectroscopy (XPS, K-alpha, Thermo U.K.). The
surface and cross-sectional morphologies of the membranes and
J.H. Kim, Y. Choi, J. Kang et al.
substrates were imaged by field-emission scanning electron mi-
croscopy (FE-SEM, IT-500 HR JEOL, USA) at a voltage of 10 kV and a
current of 10 mA. The d-spacing of the GONR layer was determined
by conducting X-ray diffraction on a high-resolution X-ray diffrac-
tometer (HR-XRD, SmartLab, Rigaku, Japan).
3. Results and discussion
3.1. Overall GONR assembly and membrane fabrication process
using a slot-die coater
Fig. 1A schematizes the fabrication procedure of the GONR
membrane using a slot-die coater and the assembly of GONRs
during the coating process. The GONR coating process can be
divided into three parts: (1) the injection of a GONR suspension
from a feed tank to the slot-die head using a syringe pump at a
controlled injection rate, (2) penetration of the GONR suspension
through the micrometer gap of the slot-die head, and (3) deposition
of the extruded GONR suspension onto a target substrate on a
moving stage. For depositing a uniform and ultrathin GONR layer
on a porous polymeric substrate, it is critical to assemble the GONR
into a nanosheet, which can be achieved by controlling several
fabrication parameters such as the concentration of the GONR
suspension, injection rate of the suspension into the slot-die head,
and moving rate of the stage. As shown in the right panel of Fig. 1A,
GONRs obtained by the unzipping of MWCNTs (Fig. S1) could be
dispersed in water at a concentration of 5 mg/mL, and the indi-
vidual GONRs assembled to form nanostrings during the ball-
milling and stirring process used for preparing the GONR suspen-
sion (see details in the experimental section). The well-dispersed
GONR nanostrings assembled into a nanosheet structure as they
passed through the micro-gap in the slot-die head. When the GONR
nanosheets were extruded from the slot-die lip and deposited on a
moving substrate, the thickness of the GONR nanosheet decreased
owing to the shear force induced by the moving stage. The details of
Fig. 1. (A) Schematics of the GONR membrane fabrication using a slot-die coater and GONR assembly during the coating process. (B) Photographs illustrating the slot-die coating
process. (C) Photograph of a GONR membrane. (D) Top-view and (E) cross-sectional SEM images of a GONR membrane. (F) Contact angles of water, ethanol, and IPA on GONR
membranes (right) in comparison with those on GO membranes (left). In the membrane fabrication process, the stage moving rate was set at 14 mm/s and the feeding rate of the
GONR suspension into the slot-die head was set at 1.1 mL/min. (A colour version of this figure can be viewed online.)
565
Carbon 191 (2022) 563e570
this assembly phenomenon are presented in Figs. 2 and 3.
Fig. 1B shows a photograph obtained during the slot-die coating
process and Fig. S2 depicts the whole slot-die setup. In this process,
a 5 mg/mL aqueous GONR suspension was injected into the slot-die
head at the rate of 1.1 mL/min. The moving rate of the coating stage
was typically set to 14 mm/s. The distance between the slot-die lip
and substrate was 0.5 mm, and the width of the micro-gap between
the slot-die heads was 80 mm. A uniform ultrathin layer of the
deposited GONRs is formed in this method as the solvent sponta-
neously dries on the target substrate.
Fig. 1C shows a photograph of the as-prepared GONR-coated
polyethersulfone (PES) filter (Fig. S3: pore size, 0.03 mm; diameter,
9 cm) with a uniform GONR layer. Fig. 1D and E shows the top-view
and cross-sectional scanning electron microscopy (SEM) images of
the GONR membrane. As shown, a uniform 120-nm-thick GONR
layer was obtained successfully. In general, thick carbon nano-
material layers are coated at the micrometer scale using conven-
tional bar-coating or doctor blade methods, which rely on highly
concentrated and viscous carbon nanomaterial suspensions
[25,30]. However, it was possible to obtain a uniform and ultrathin
GONR layer using a GONR suspension of a relatively low concen-
tration (5 mg/mL) because of the advantage of the slot-die coating
method, which allows direct coating of the nanomaterial suspen-
sion on a substrate at a controlled deposition rate [19,31,32].
To investigate the hydrophilic surface properties of the GONR
layer, the surface contact angles of water, ethanol, and IPA were
measured (Fig. 1F). The GONR layer was found to be both hydro-
philic and oleophilic, as reflected by the low contact angles of 40
,
5
, and 3
for water, ethanol, and IPA, respectively. These contact
angles are similar to those on a GO film. While the degree of
oxidation is different between GO and GONR, both these materials
contain oxygen functional groups and sp2 carbon domains (Fig. S4),
which lead to their similar surface properties. In the case of GONRs,
the oxygen functional groups at the edge may contribute to hy-
drophilicity, while the sp2 carbon domains in the basal plane are
J.H. Kim, Y. Choi, J. Kang et al. Carbon 191 (2022) 563e570

Fig. 2. (A) SEM images of a GONR sample obtained by freeze-drying a 5 mg/mL GONR suspension. (B) SEM images of the GONR sample after it penetrated the micro-gap of the slot-
die head. The feeding rate of the GONR suspension was increased from 0.5 to 3 mL/min, and the gap of the slot-die head was fixed at 80 mm. The obtained suspensions were freeze-
dried to maintain the GONR morphologies in the suspension. (C) XRD patterns of different GONR samples. All the GONR samples were freeze-dried except for the sample labeled
“GONR film 1.1”. The numbers in sample labels indicate the feeding rate (mL/min) of the GONR suspension. (D) Schematic of the GONR assembly in the micro-gap of the slot-die
head. (A colour version of this figure can be viewed online.)

likely responsible for their high affinity for organic solvents [14,33].
The high affinity of the GONR for organic solvents is beneficial for
achieving ultrafast organic solvent permeance through a GONR-
coated membrane [34], as discussed later.
3.2. Assembly of a GONR nanosheet in a confined micro-gap
In our previous work, we studied the assembly of GONRs
depending on their concentration in aqueous suspensions and
observed the development of relatively thick strings and scaffolds
with increasing GONR concentration [20]. Therefore, a thick GONR
layer was expected for the coating layer obtained with a 5 mg/mL
suspension in this study. However, an ultrathin GONR layer with a
thickness of ~100 nm was obtained, as shown in Fig. 1E. To un-
derstand the origin of this ultrathin layer, the variation in the GONR
morphology was observed before and after the injection of the
GONR suspension into the slot-die head (Fig. 2A and B). Fig. 2A
shows the SEM images of a GONR sample obtained by freeze-drying
a 5 mg/mL GONR suspension before slot-die injection. Thick
bundle-like GONR strings were formed, as reported previously [20].
Fig. 2B shows the SEM images of freeze-dried GONR samples after
injection into the slot die-head at different feeding rates in the
range of 0.5e3.0 mL/min. As the injection rate increased, the thick
bundle-like GONR strings reorganized to form wider and thinner
nanosheets. In particular, the thickness of the nanosheets
decreased to 150 nm and the lateral size ranged up to 100 mm,
resulting in an aspect ratio of ~670. In the magnified SEM images in
Fig. 2B, no defects or cracks are observed in the basal plane of the
nanosheets, indicating the formation of a dense 2D structure
composed of entangled GONRs.
The influence of the feeding rate on the interlayer spacing of the
nanosheet was investigated by the X-ray diffraction (XRD) analysis
of the freeze-dried samples (Fig. 2C). All the GONR powders yielded
a diffraction peak at a 2q of ~10.2
(8.7 Å); the peak position was
slightly shifted to a lower angle compared to that of the GONR film
(8.0 Å) prepared by slot-die coating. The results suggest that the

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J.H. Kim, Y. Choi, J. Kang et al.
Fig. 3. (A) Photographs of GONR membranes obtained at different stage moving rates. (B) Corresponding top-view and (C) cross-sectional SEM images of the GONR membranes. A
thinner GONR layer was formed at a higher stage moving rate. The concentration of the GONR suspension used for slot-die coating was 5 mg/mL, and the feeding rate of the
suspension into the slot-die head was fixed at 1.1 mL/min. (A colour version of this figure can be viewed online.)
injection rate of the GONR suspension into the slot-die head does
not change the interlayer structure but significantly modifies the
assembled GONR morphology and aspect ratio. The slightly wider
interlayer spacing of the GONR powder compared to that of the
GONR film can be attributed to the freeze-drying process, which
hinders the regular stacking of GONRs during solvent drying.
Considering the above results, we conclude that the morphology
control of the GONR strings to nanosheets is induced by the micro-
gap between the slot-die heads. Fig. 2D shows a schematic of the
GONR assembly in the micro-gap of the slot-die head. Because the
size of the GONR strings, ~10 mm, is much smaller than the width of
the micro-gap, 80 mm, the physical extrusion effect on the GONR
assembly is not significant, while the slit may guide their shaping
into a nanosheet as per the dimensions of the slit gap. This aspect is
confirmed by the SEM images depicted in Fig. S5, which shows the
effects of the slit gap size on the alignment of the GONR nanosheets
prepared with a higher concentration solution (50 mg/ml). The
nanosheet thickness is drastically decreased as the slit size is
reduced due to the higher guiding shear force. We note that,
although the concentration is increased tenfold, the general
alignment is well achieved, indicating the feasibility of the slot-die
coater towards high viscosity GONR solutions. Finally, a high in-
jection rate decreases the thickness of the GONR nanosheet;
therefore, the shear force generated in the micro-gap is expected to
be the main driving force for transforming the GONRs into a
nanosheet. In our previous study, the GONR solution was coated by
the bar-coating technique, which has a wider gap, and the applied
shear force is relatively reduced [20]. As such, nanosheet formation
was not observed using the bar-coating method. Conversely, the
slot-die head has a narrower, confined gap that induces a stronger
shear force, which allows the formation of 2D structures.
3.3. Effect of the stage moving rate on the quality and thickness of
the GONR membrane on a PES support (pore size: 0.03 mm)
After investigating the self-assembly behavior of the GONR in
the slot-die head, the influence of the stage moving rate was also
studied by fixing the GONR concentration at 5 mg/mL and the
suspension injection rate at 1.1 mL/min (Fig. 3), which are
567
Carbon 191 (2022) 563e570
conditions for producing a nanosheet with a thickness of 230 nm,
as shown in Fig. 2B. Because the extruded GONR suspension is
directly applied to a moving support, another shear effect due to
stage movement may exist, and the shear force increases as the
stage moving rate increases.
Fig. 3A shows the photographs of the as-prepared GONR layers
on PES supports, and Fig. 3B shows the corresponding SEM images.
When the stage moving rate was lower than 9 mm/s, sustained and
uncoated areas were observed, and a uniform layer was not formed
because the suspension was highly dilute and flowed on the sub-
strate. When the stage moving rate was greater than 14 mm/s, a
pale-colored GONR membrane was formed without any defective
or sustained area. The photographs of samples obtained at stage
moving rates of 20e40 mm/s exhibit some stripes owing to the
local accumulation of the suspension because of the high stage
moving rate; however, the top-view SEM images confirm the for-
mation of a uniform GONR layer without any cracks or defects
(Fig. 3B).
The thickness of the GONR layer was further investigated using
the cross-sectional SEM images of the samples, shown in Fig. 3A. As
shown in Fig. 3C, surprisingly, the thickness was smaller than that
of the parent GONR nanosheet in suspension with a thickness of
230 nm. In addition, the thickness of the GONR layer gradually
decreased from 180 nm to 40 nm with an increase in the stage
moving rate, where a higher speed increases the shear force during
the coating process. The results suggest that further thinning of the
GONR nanosheet occurs owing to the second shear effect due to the
moving stage when the suspension is deposited on the substrate.
Consequently, even if the same suspension is used as a feed for slot-
die coating, the combination of the feed injection rate and stage
moving rate can dramatically modulate the structure of the GONR
nanosheet and deposited layer. Because interlayer spacing is
responsible for the molecular separation performance of stacked
graphene membranes [19,35,36], the stability of the interlayer
spacing of the GONR and coating layer was investigated by
immersing the GONR membrane in water, ethanol, and IPA for 1
day (Fig. S6). XRD analyses revealed a stable interlayer structure of
the GONR membranes in the tested solvents, as reflected by the fact
that the d-spacing of the GONR membrane was the same (~8 Å)
J.H. Kim, Y. Choi, J. Kang et al. Carbon 191 (2022) 563e570

regardless of the solvent type. In addition, the GONR membrane
remained stable during 7 days of immersion in the tested solvents,
while the GO layer was easily delaminated after immersion in
ethanol for 1 h (Fig. S6B).
3.4. OSN and diafiltration performance of GONR membranes
After confirming the stability of the GONR membrane and its
rigid interlayer structure in the tested organic solvents, the per-
formance of the membrane in the nanofiltration of organic solvents
was evaluated (see Fig. 4). First, the permeance of pure IPA was
studied by changing the thickness of the GONR layer (Figs. 4A and
S7). The permeance test was conducted at 1 bar in dead-end and
cross-flow filtration modes to investigate the effect of the filtration
mode on the solvent permeance. In the cross-flow test, the per-
meance was measured under stabilized equilibrium conditions
(Fig. S7).
The IPA permeance increased dramatically with a decrease in
the thickness of the GONR layer from 150 nm to 40 nm in both
modes. Surprisingly, the IPA permeance was enhanced in the cross-
flow filtration mode even when identical membranes were tested,
regardless of their thickness, and the permeance of the 40-nm-
thick GONR membrane was ultrafast at 679 LMH/bar. Because de-
fects can increase the solvent permeance, photographs and SEM
images of the GONR membranes were obtained after cross-flow
filtration experiments (Fig. S8), and no defective areas were
observed in the membranes. This observation indicates that the
enhanced permeance under cross-flow is the nature of the GONR
membrane rather than permeation through defective bypaths,
although the related mechanism is not clear at this stage.
Additionally, other organic solvent permeances in GONR
membrane were tested (Fig. S9). The thickness of the used GONR
membrane was 150 nm. The obtained experimental data exhibited
a general trend of increasing permeances with decreasing solvent
viscosity. However, toluene and benzene showed higher per-
meances than acetone and hexane solvents despite having a
slightly higher viscosity, possibly attributed to their planar molec-
ular structures.
Fig. 4B shows the rejection rates of 40-nm-thick GONR mem-
branes for five dyes dissolved in IPA: methyl red (MR, 269 Da
(neutrally charged)), methylene blue (MnB, 320 Da (positively
charged)), brilliant blue G (BBG, 854 Da (negatively charged)),
Evans blue (EB, 961 Da (negatively charged)), and Rose Bengal
(RosB, 1018 Da (positively charged)). The membrane was tested
with a 10 mg/L dye solution in IPA at 1 bar. Both dead and cross-
flow filtration experiments were performed. In dead-end filtra-
tion, the dye rejection rates were 41.3% (MR), 33.3% (MnB), 51.7%
(BBG), 93.1% (EB), and 72.8% (RosB). Further, 150-nm-thick mem-
branes also showed a similar dye rejection rate trend (Fig. S10),
while their solvent permeance decreased because of the thicker
selective layer [25,36]. Moreover, a similar rejection rate trend was
observed in the cross-flow tests, but the dye rejection rates were
slightly different: 10% (MR), 6% (MnB), 25.8% (BBG), 99.9% (EB), and
14.48% (RosB) (see Fig. S11). In particular, the rejection rate of EB
increased under cross-flow filtration, while the rejection rates of
the other dyes decreased. The lower rejection rate of RosB (1018 Da)
than that of EB (961 Da) can be attributed to the shape of the dye
molecule (Fig. S12): RosB with a planar shape can relatively easily
penetrate the nanochannels of the stacked GONRs, as is frequently
observed with graphene-based membranes [37]. The 40-nm-thick
GONR membranes were also tested at higher pressures ranging up
to 12 bar; they showed a high and stable rejection rate (~100%) for
EB (Fig. S13). These results indicate that the ultrathin GONR layer
(thickness, 40 nm) is effective as a molecular sieve in the separation
of subnanometer-sized molecules, and its molecular weight cut-off
(MWCO) is around 961 Da.

Fig. 4. (A) Permeance of pure IPA depending on the thickness of the GONR layer and filtration modes. (B) Rejection rate of a 40 nm thick GONR membrane for dye molecules
dispersed in IPA. Filtration was conducted at 1 bar using a solution with a dye concentration of 10 mg/L. (C) Comparison of the IPA nanofiltration performances. (D) Schematic of the
diafiltration mechanism of the GONR membrane for a mixed dye solution in IPA. (E) EB/MB mixture separation using a 40 nm thick GONR membrane under cross-flow filtration at
1 bar and (F) the corresponding UVevis absorbance spectra of feed and permeates. Insets show photographs of the feed/permeate solutions after 56 h of cross filtration with the
membrane. The dye concentration was 10 mg/L for the single dye solution. A 20 mg/L binary dye solution was tested for diafiltration. (A colour version of this figure can be viewed
online.)

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J.H. Kim, Y. Choi, J. Kang et al.
The IPA nanofiltration performance of the GONR membrane is
compared with those of other 2D-material-based membranes in
Fig. 4C and Table S1 [38e51]. The performances of the GONR
membranes in both dead-end and cross-flow experiments exceed
the upper limits of the performances of other membranes. In
particular, the membrane performance under cross-flow filtration
(679 LMH/bar of IPA permeance, 961 Da of MWCO) far surpasses
those of the previously reported polymeric membranes or gra-
phene membranes, while the MWCO is larger than that of the
nanoporous graphene membrane (nGO) obtained by rapid thermal
activation [45,46].
According to the aforementioned results for membrane filtra-
tion with a single dye solution, GONR membranes have a sharp
MWCO and high IPA permeance under cross-flow filtration, which
can be beneficial for the diafiltration of mixed organic molecules, as
illustrated in Fig. 4D. In this process, the small molecule in the
mixed solution permeates the membrane, whereas the large
molecule accumulates on the membrane feed side [46,52,53].
Fig. 4E shows the diafiltration performance of 40-nm-thick GONR
membranes under cross-flow filtration for an EB/MB mixture. EB
(961 Da) and MR (269 Da) were selected for preparing the mixed
dye solution because the MWCO of the GONR membrane lies be-
tween the sizes of EB and MR. These two dyes were mixed to a total
concentration of 20 mg/mL in IPA; Fig. S14 shows the UVevis
spectrum of this solution. Filtration was conducted at 1 bar for
56 h, and the inset in Fig. 4F shows the photographs of the GONR
membrane before and after filtration. Fig. 4F shows the UVevis
absorbance spectra of the feed and permeate solutions corre-
sponding to Fig. 4E. The permeated solution did not show the
absorbance peak of EB molecules, indicating that EB was selectively
removed by the GONR membrane with a 100% rejection rate.
Interestingly, the intensity of the absorbance peak of MR in the
permeate solution is identical to that of the mixed solution, indi-
cating that MR is highly permeable through the GONR membrane.
A stable separation of the mixture was observed over 56 h, while
the permeance declined slightly from 900 to 280 LMH/bar, possibly
due to compact selective layer, surface fouling, or pore blocking
caused by the adsorbed dye molecules [31,54,55]. Despite the slight
decline in permeance, the GONR membrane maintained ultrafast
IPA/small dye molecule permeation while blocking larger
molecules.
4. Conclusions
We observed the assembly of GONRs into a GONR nanosheet as
a GONR suspension penetrated a narrow microchannel. It is
observed that a thin GONR nanosheet can be formed by decreasing
the gap width of the microchannel, critically below 50 mm. Further,
we used the GONR nanosheet to fabricate high-performance OSN
membranes using a scalable slot-die coating method. In addition
to the shear effect in the microchannel of the slot-die head, the
shear effect of the moving stage with the PES support also changed
the structure of the coated GONR layer, leading to a thinner
deposited layer at a higher stage moving rate. The GONR mem-
brane showed high permeance of 186 LMH/bar for pure IPA in
dead-end filtration and moderate permeance of 679 LMH/bar in
cross-flow filtration with a MWCO of 961 Da. The membrane could
be used in the diafiltration of mixed dyes in organic solutions. Our
observations indicated that the structure of 1D materials such as
GONRs can be further tuned using a physical treatment, such as by
using the shear effect, without performing an additional chemical
treatment. This study provides insights into the scalable fabrica-
tion of 1D-material-based coatings and membranes and enhances
the understanding of the assembly behaviors of 1D materials in
their suspensions.
569
Carbon 191 (2022) 563e570
CRediT authorship contribution statement
Ji Hoon Kim: Conducted the overall experiment, wrote the
manuscript and all experiments were conducted under the super-
vision of D.W. Kim. Yunkyu Choi: characterized the structure of
graphene. Junhyeok Kang: characterized the structure of gra-
phene. Ju Yeon Kim: wrote the manuscript and all experiments
were conducted under the supervision of D.W. Kim. Jun Hyuk Bae:
conducted formal analysis. Ohchan Kwon: conducted formal
analysis. Dae Woo Kim: wrote the manuscript and all experiments
were conducted under the supervision of D.W. Kim.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
This work was supported by a National Research Foundation of
Korea (NRF) grant funded by the Korean government (MSIT) (NRF-
2020R1C1C1003289). This research was also supported by the Basic
Science Research Program through the National Research Founda-
tion of Korea funded by the Ministry of Education (NRF-
2019R1A6A1A11055660).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.carbon.2022.02.026.
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