Article

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Mimicking a Dog’s Nose: Scrolling Graphene

Nanosheets
Zhuo Chen,† Jinrong Wang,† Douxing Pan,§ Yao Wang,*,†,‡ Richard Noetzel,‡ Hao Li,‡ Peng Xie,†
Wenle Pei,† Ahmad Umar,∥ Lei Jiang,*,† Nan Li,⊥ Nicolaas Frans de Rooij,⊥,# and Guofu Zhou*,‡,⊥,#
†
Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry of Education, School of Chemistry, Beihang
University, Beijing 100191, People’s Republic of China
‡
National Center for International Research on Green Optoelectronics, South China Normal University, Guangzhou 510006,
People’s Republic of China
§
Institute of Advanced Manufacturing Technology, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Changzhou
213164, People’s Republic of China
∥
Department of Chemistry, Faculty of Science and Arts and Promising Centre for Sensors and Electronic Devices, Najran University,
Najran 11001, Kingdom of Saudi Arabia
⊥
Shenzhen Guohua Optoelectronics Tech. Co. Ltd., Shenzhen 518110, People’s Republic of China
#
Academy of Shenzhen Guohua Optoelectronics, Shenzhen 518110, People’s Republic of China
*
S Supporting Information

ABSTRACT: Inspired by the densely covered capillary

structure inside a dog’s nose, we report an artificial
nanostructure, i.e., poly(sodium p-styrenesulfonate)-function-
alized reduced graphene oxide nanoscrolls (PGNS), with high
structural perfection and efficient gas sensing applications. A
facile supramolecular assembly is introduced to functionalize
graphene with the functional polymer, combined with the
lyophilization technique to massively transform the planar
graphene-based nanosheets to nanoscrolls. Detailed charac-
terizations reveal that the bioinspired nanoscrolls exhibit a
wide-open tubular morphology with uniform dimensions that
is structurally distinct from the previously reported ones. The
detailed morphologies of the graphene-based nanosheets in
each scrolling stage during lyophilization are monitored by cryo-SEM. This unravels an asymmetric polymer-induced
graphene scrolling mechanism including the corresponding scrolling process, which is directly presented by molecular
dynamics simulations. The fabricated PGNS sensors exhibit superior gas sensing performance with reliable repeatability,
excellent linear sensibility, and, especially, an ultrahigh response (Ra/Rg = 5.39, 10 ppm) toward NO2. The supramolecular
assembly combined with the lyophilization technique to fabricate PGNS provides a strategy to design biomimetic materials
for gas sensors and chemical trace detectors.
KEYWORDS: graphene nanoscrolls, supramolecular assembly, lyophilization, cryo-SEM, gas sensors

he fine sense of smell of dogs, the most familiar

T
macrosmatic animal in nature, is an excellent guide
toward ultrasensitive gas detection.1 In fact, the
ultrasensitive olfaction of dogs originates from the complex
maxilloturbinate covered by dense capillaries inside the dog’s
nose.2,3 The capillaries with large surface area endow dogs with
an ultrahigh response to various odorants even at extremely low
concentrations.4 Inspired by the capillary structure of the dog’s
nose, we demonstrate that the performance of gas sensors can
be significantly improved via preparing capillary-mimicking
artificial nanostructures such as graphene-based nanoscrolls.
Graphene nanoscrolls (GNS), which result from scrolling
planar graphene nanosheets in a continuous and uniform
manner, have been arousing increasing interest as a promising
carbonaceous nanomaterial with one-dimensional topology.5−7
GNS inherit many superior properties from graphene such as
large specific surface area, strong thermostability, high carrier
mobility, and superior mechanical properties.8−10 Moreover,
GNS allow more possibilities to be assembled with various
Received: November 22, 2017
Accepted: February 14, 2018

© XXXX American Chemical Society A DOI: 10.1021/acsnano.7b08294

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Figure 1. Schematic of the supramolecular assembly combined with the lyophilization technique to fabricate PGNS and the comparison of the
nanoscroll morphology of PGNS and GNS. (a) Addition of PSS to a GO aqueous dispersion. (b) Formation of well-dispersed PSS-rGO
nanosheets after the reduction of GO to rGO and the supramolecular assembly of PSS with rGO nanosheets. (c) Fabricated wide-open tubular
PGNS. (d) SEM inspection with low magnification of the attached PGNS, which remain separated. (e) Higher magnified SEM image of the
wide-open tubular and straight PGNS. (f) SEM inspection with high magnification of the end of PGNS, showing a circular and well-opened
orifice. Inset: Suggested mechanism for the formation of the well-opened orifice, where the negatively charged PSS-rGO nanosheets are
prevented from stacking due to electrostatic repulsion. (g) SEM inspection with low magnification of the irregularly entangled GNS
framework. (h) Higher magnified SEM image of the collapsed and bent “ribbon”-like GNS. (i) SEM inspection with high magnification of the
end of the collapsed GNS with no orifice observed. Inset: Suggested mechanism for the tendency of the GO nanosheet to stick together due to
strong π−π interaction during the scrolling in the ice sublimation process, resulting in collapsed GNS.

organic molecules11,12 and inorganic nanoparticles,13−15 realiz-
ing a versatility for wide applications especially in functional
integration as sensors and electronic devices.
GNS can be fabricated by several techniques such as
chemical vapor deposition (CVD),8 low-temperature chemical
exfoliation,16 and templated assembly.14,15,17 However, effective
fabrication technologies are urgently demanded to overcome
high energy consumption, complicated fabrication processes,
and especially the difficulty of upgrading in large-scale
fabrication. In 2014, Gao et al.18 developed a lyophilization
technique to fabricate well-controlled GNS with a facile
fabrication process, promoting a different strategy to transform
planar graphene nanosheets to nanoscrolls. Those GNS were
fabricated based on bare raw materials such as graphene oxide
(GO) or mild reduced graphene oxide (rGO); thus they were
probably not thoroughly reduced due to the irreversible
aggregation of rGO nanosheets. As a result, the obtained
GNS did not exhibit the innate superior electronic properties of
graphene and lacked functionalization, while the GNS were
generally shrivelled and entangled with each other in
nonuniform dimensions.18−22 Obviously, it remains a challenge
B DOI: 10.1021/acsnano.7b08294
to fabricate high-quality graphene-based nanoscrolls with
uniform structure and feasibility of functionalization for
practical application. Beyond that, the distinct scrolling
behavior of GNS during the lyophilization process has not
been visually clarified due to the difficulty in observation
through the ice. Fortunately, the increasingly mature
cryoelectron microscopy technique makes it possible to
distinctly investigate the true nature of graphene-based
nanoscrolls.23−25
In this work, we present the supramolecular assembly
combined with the lyophilization technique to prepare
functionalized graphene-based nanoscrolls with desirable
morphology and uniform dimensions. As expected, the
capillary-like nanoscrolls reveal significant improvement in
NO2 sensing, which is competitive with existing graphene-based
sensing materials. By performing cryo-scanning electron
spectroscopy (SEM), we clearly observe the distinct
morphologies of the graphene-based nanosheets in each
scrolling stage during the lyophilization process and unravel
the corresponding scrolling mechanism, which is proved in
detail by molecular dynamics (MD) simulations.
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Figure 2. Characterization of the dimensions and demonstration of successful assembly of PSS with the nanoscrolls. (a) Length statistics of
the PGNS. (b) Diameter statistics of the PGNS. (c) FTIR spectrum of PGNS, bare rGO, and GO. (d) XPS spectrum of the PGNS and bare
rGO. (e) FESEM image of a typical PGNS structure. (f) Corresponding FESEM-EDS mapping of S Ka1.

RESULTS AND DISCUSSION
Aromatic molecules such as benzene, naphthalene, and
anthracene can noncovalently functionalize graphene nano-
sheets via π−π interactions due to the similar π-conjugated
structure, without destroying the intrinsic electronic properties
of graphene.26−28 Here, an aromatic polymer, poly(sodium p-
styrenesulfonate) (PSS), with benzene ring structure is selected
to disperse into a GO aqueous dispersion (Figure 1a). After the
reduction by hydrazine hydrate, most of the oxygen-containing
groups of GO are removed to form rGO. Meanwhile the PSS is
successfully assembled with the rGO nanosheets to form the
starting material (PSS-rGO) through π−π interactions (Figure
1b).29,30 Unlike the aggregated rGO nanosheets, the PSS-rGO
nanosheets are well dispersed in the aqueous phase. The
dispersion remains stable with a homogeneous black appear-
ance for at least a year (Supporting Information, Figure S1e).
Such a phenomenon relies on three facts: (1) the intrinsically
hydrophilic sulfonic groups (−SO3−) of PSS contribute to the
C DOI: 10.1021/acsnano.7b08294
excellent dispersity of the PSS-rGO nanosheets. (2) The
−SO3− groups of PSS with extra negative charges enhance the
interlaminar static-repulsion forces of PSS-rGO and prevent the
aggregation.26,31 (3) In the case of (poly)aromatic molecules,
the PSS molecules have a strong tendency to stack onto
graphene. The supramolecular assembly is governed by the
π−π interactions between the PSS molecules and graphene
sheets. This also implies that the π−π interactions among
graphene sheets (which can cause the restacking of the sheets)
are thermodynamically hindered.32 Hence, the PSS-rGO
nanosheets are well separated from each other in an aqueous
dispersion, revealing a low bending rigidity, thus facilitating the
subsequent shape transformation into graphene-based nano-
scrolls.
Starting from the PSS-rGO dispersion, the lyophilization
process to prepare the PSS-rGO nanoscrolls (PGNS) contains
three steps. First, the dispersion is poured into a glass bottle
and then immersed in liquid nitrogen to become a fast frozen
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Figure 3. Schematic with corresponding cryo-SEM images and MD simulations of the scrolling behavior from PSS-rGO nanosheets to
nanoscrolls at different states in the lyophilization process. (a) Fast freezing to the solid phase by liquid nitrogen; the PSS-rGO nanosheets
vertically align in the ice. (b) Spontaneous scrolling of the PSS-rGO nanosheets along with the sublimation of ice. (c) Transformation from
planar nanosheets to nanoscrolls after the PSS-rGO nanosheets are entirely freed from the ice. The top-view cryo-SEM image of a typical (a1)
PSS-rGO nanosheet that has not yet scrolled, (b1) PSS-rGO nanosheet in the process of scrolling, and (c1) nanoscroll with the edges
overlapped. The thermodynamic scrolling process of the NaPSS-rGO-H2O system and the corresponding energy variation (here Na+ is used
to balance the number of whole electric charges). (d) Initial state of the system with a planar PSS-rGO nanosheet. (e) Variation of the total
energy with time, where three stages are presented: I, dissolution; II-, scrolling; and III, relaxation. (f) Final state of the nanoscroll. See also
the movie in the Supporting Information showing the whole thermodynamic scrolling process.

solid. Afterward, the bottle is immediately transferred into a
lyophilizer for sublimation. The PSS-rGO nanosheets are
scrolling gradually at this stage. Finally, the nanosheets
accomplish the scrolling and transform into PGNS after
complete dehydration (Figure 1c).
The fabricated PGNS exhibit the desirable nanoscroll
structure with a generally straight morphology. Almost all
PSS-rGO nanosheets have been successfully transformed.
Although the nanoscrolls attach to each other due to the
high density, they are not bent or entangled and remain
separated (Figure 1d). To investigate the influence of PSS on
the formation of the PGNS structure, we tried bare rGO and
GO dispersions to fabricate nanoscrolls, performing the same
experimental steps. For the rGO dispersion, aggregation is
unavoidable and, thus, the lyophilized foams are shrunken and
collapsed (Supporting Information, Figure S1d). Stacked rGO
layers are formed instead of nanoscrolls (Supporting
Information, Figure S2c). For the well-dispersed GO nano-
sheets, fluffy foams with ultralow density are formed
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(Supporting Information, Figure S1b) and also verified as
nanoscroll structures after the lyophilization process. However,
the morphology of the GO nanoscrolls differs a lot compared
to that of the PGNS. As revealed in the low-magnification SEM
image (Figure 1g), the majority of the GO nanosheets are
transformed to GNS, while a few planar nanosheets still remain.
In addition, the GNS are irregularly bent and interlaced with
each other to form a netlike framework. Further, we
investigated the differences between PGNS and GNS at the
microscale. For PGNS, a wide-open tubular and straight
nanoscroll structure is observed (Figure 1e). The end of the
PGNS reveals a round and well-opened orifice (Figure 1f). The
highly perfect nanoscroll morphology is attributed to the
supramolecular modification by PSS. The −SO3−-containing
polymers entirely cover the PSS-rGO nanosheets with negative
charges. Thus, the inner walls of the PSS-rGO nanosheets are
prevented from sticking together due to electrostatic repulsion
during the lyophilization process (Figure 1f inset) to form well-
opened nanoscrolls. Moreover, we verified that the fabrication
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of PGNS is sensitive to the ionic strength of the solution. When
increasing the ionic strength by adding NaCl,33 nanoscrolls are
no longer obtained (Supporting Information, Figure S3),
whereas the GNS are more like thin “ribbons” (Figure 1h),
which is clearly verified by the high-magnification SEM image
of the end of the GNS (Figure 1i). There are obvious wrinkles
wrapped over the “ribbon”, but no orifice is observed; thus the
thin “ribbon” is likely a collapsed nanoscroll like the previous
reported ones.19−21 That is because the GO nanosheets have a
tendency to stack together due to the strong π−π interaction
during the scrolling in the ice sublimation process (Figure 1i
inset), and finally the inner GO sheets stack together to form
the collapsed nanoscroll. To sum up, PGNS can be effectively
fabricated in large scale and exhibit a well-opened nanoscroll
structure with a tubular and straight shape. In contrast to GNS,
we confirm that PSS is key to support the aimed at structure.
Further, we evaluated the statistics in length and diameter to
elucidate the regularity of PGNS. As revealed in Figure 2a, the
length peaks in the range of 8−18 μm with a percentage of
82.4% (8−13 μm accounts for 45.9% and 13−18 μm for
36.5%), and the average length is 13.5 μm. The diameter of
around 660 nm contains a large proportion of 88.4% (Figure
2b). Thus, the PGNS are prepared with uniform dimensions,
which can be easily upgraded to large-scale fabrication. The
statistics in length and diameter were conducted based on Leica
images (Supporting Information, Figures S4 and S5).
Several techniques were adopted to verify the successful and
uniform assembly of PSS on the graphene nanoscrolls. Fourier
transform infrared (FTIR) spectroscopy analysis of the PGNS
provides direct evidence of the successful surface modification
with PSS (Figure 2c), showing the characteristic SO
stretching vibration band at 1620 cm−1 and the phenyl ring
absorption peak at 1400 cm−1, along with the 1196−1032 cm−1
C−C vibration of the carbon skeleton of the PSS chain. The
pure PSS FTIR spectrum is shown in Figure S6 in the
Supporting Information. The two characteristic hydroxyl and
carboxyl peaks of the GO at 3410 and 1722 cm−1, respectively,
are attenuated significantly in the spectrum of rGO and PGNS,
indicating that most oxygen-containing functional groups have
vanished due to the effective reduction with hydrazine hydrate.
X-ray photoelectron spectroscopy (XPS) is in accordance with
the FTIR results, revealing an obvious S 2p peak at 168.4 eV
that is assigned to the −SO3− groups, indicating the successful
modification with PSS (Figure 2d). Further, the field emission
scanning electron microscopy (FESEM) image of a typical
PGNS (Figure 2e) and the corresponding energy dispersive X-
ray spectroscopy (EDS) mapping verify the uniform coverage
of the nanoscrolls with PSS (Figure 2f), revealing the excellent
potential of the facile modification of graphene-based materials
using supramolecular assembly.
In order to gain clear knowledge of the spontaneous scrolling
behavior of the PSS-rGO nanosheets, we tracked the
intermediate states during the lyophilization process by cryo-
SEM. In contrast to previous reports,18,22 most PSS-rGO
nanosheets are uniformly distributed in the ice with the basal
plane oriented in the direction perpendicular to the ice
sublimation surface (Figure 3a), which was verified through the
top-view cryo-SEM image (Supporting Information, Figure S7).
A typical nanosheet that has not yet scrolled is shown in Figure
3a1. This phenomenon is explained by the vertical nucleation
and growth of ice crystals.34−36 Behaving as a typical thermal
conductor,37,38 the glass bottle is immersed vertically into the
liquid nitrogen for fast freezing. The bottom of the bottle is at a
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lower temperature than the top, and a vertical temperature
gradient is generated. Therefore, the ice crystals grow vertically
and drive the PSS-rGO nanosheets to turn vertically until the
end of the ice nucleation, and the nanosheets are finally
unidirectionally embedded in the ice. The schematic of the fast
freezing process and the vertical temperature gradient measure-
ment are shown in Figure S8 in the Supporting Information.
On the basis of the vertical orientation of the PSS-rGO
nanosheets, the spontaneous scrolling behavior is clearly
understood. During the layer-by-layer sublimation of ice, the
vertical PSS-rGO nanosheets begin to be exposed gradually,
and sublimation induces the nanosheets to scroll (Figure 3b).
The process was directly observed by cryo-SEM in Figure 3b1.
As the sublimation continues, the vertical PSS-rGO nanosheets
scroll simultaneously until they are entirely freed from the ice
with the edges overlapped (Figure 3c) to transform them from
planar nanosheets to nanoscrolls (Figure 3c1). From the
evidence of the cryo-SEM in each state during the
lyophilization process, we demonstrate that the scrolling
process is triggered during the sublimation to form edge-
overlapping nanoscrolls instead of free scrolling and forming
random scrolls. The intriguing scrolling behavior is directly
visualized during the lyophilization process of graphene-based
nanosheets.
To elucidate the scrolling process of the PSS-rGO nano-
sheets, a systematic MD simulation was carried out. The
models of Coulombically stabilized assemblies39 and the related
studies of graphene self-assembly on droplets, polymers, and
carbon nanotubes (CNTs) inspired us in building the model of
our MD simulations.40,41 It is feasible and reasonable to reveal a
relatively macroscopic phenomenon via simulating at a
microscopic size instead of a macroscopic size;42 thus the
models here were set up at orders of magnitude smaller size
than the experiment, still in good qualitative agreement with
the available experimental data. The computational model is
shown in Figure 3d, consisting of one rGO nanosheet (with a
length of 7 nm and width of 21 nm), three PSS chains (with the
degree of polymerization N = 20), and 5000 H2O molecules.
The detailed simulation procedure is shown in the Supporting
Information. Initially, the whole system is in a frozen state,
which can be viewed as a liquid nitrogen environment. To
simulate the sublimation, a rapid warming process was
conducted, so that the frozen state could be released according
to the minimum energy principle. Such a reviving process is
very quick, and it can reach the minimum point of total energy
at 0.025 ns. The corresponding configuration is presented at
the end of the first stage (I) in Figure 3e. As the temperature
rises, the kinetic energy increases and contributes to the total
energy, while the PSS adhere closely to the rGO under the
adhesive force from van der Waals and electrostatic
interactions. Also, the scrolling energy from the increased
curvature, which is directly produced from the asymmetric
distribution of PSS on the opposite sides of the rGO nanosheet,
contributes to the increased total energy. Due to the one-
dimensional feature of the PSS, the rGO is induced to assemble
into a nanoscroll, as shown in Figure 3e at the end of the
second stage (II). It can be concluded that for the large
multilayered rGO with numerous PSS in the practical
coscrolling process the complex scrolling configuration can be
viewed as the superposition of the PSS-rGO system discussed
above. Moreover, due to the strong hydrophilic interaction of
the PSS, the scrolling behavior of the PSS-rGO nanosheet is
accelerated with the departure of H2O molecules during the
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Figure 4. (a) Digital and SEM images of a typical fabricated PGNS sensor, maintaining the nanoscroll structure on IEs. (b) I−V characteristics
of the PGNS sensors. (c) Response curves of PGNS, PSS-rGO w/o L, rGO w/L, and rGO w/o L sensors toward 10 ppm of NO2. (d)
Successive response curve of PGNS sensors to different NO2 concentrations ranging from 1 to 10 ppm and (e) corresponding linear fit of the
responses as a function of NO2 concentration. Error bars for the data points lie within the symbols themselves. (f) Selective response of the
PGNS sensors toward 10 ppm of NO2 and 1000 ppm of interferential gases, including Cl2, NH3, ethanol, acetone, and methanol. (g) Three-
cycle response curve of PGNS sensors upon exposure to 10 ppm of NO2. (h) Aging test of PGNS sensors toward 10 ppm of NO2 for 6
months. All the gas sensing measurements were conducted at room temperature under 45−65% relative humidity.

sublimation process. Once the scrolling is accomplished, the
system comes into the relaxation stage to adjust itself,
accompanied by slight bending, twisting, shrinking, and
expanding due to the thermal motion at a finite environmental
temperature. Thus, the total energy decreases slightly at the
third stage (III) in Figure 3e, and the final configuration
presented in Figure 3f is established. A video of the whole
thermodynamic scrolling process is shown in the Supporting
Information, which can explain our experimental observation
visually.
A drop and dry method was adopted to fabricate the gas
sensors. First, a 20 μL dispersion of each sensing materials was
dropped on the Ag−Pd interdigitated electrodes (IEs), which
are supported by a ceramic substrate. After drying, a thin
sensing film was formed on the IEs, and the gas sensor was
ready for testing. The digital and SEM images of a typical
fabricated PGNS-based sensor are displayed in Figure 4a. It is
obvious that the PGNS uniformly cover the IEs, and the
nanoscroll structure remains. The current versus voltage (I−V)
curve of the PGNS sensor displays excellent linearity between
−1 and 1 V (Figure 4b), revealing good ohmic contact between
the PGNS and the IEs. In other words, the result indicates that
F DOI: 10.1021/acsnano.7b08294
the electrical contact plays a negligible role in the sensing
process.43 Schottky barriers are absent between the PGNS and
IEs,44 ensuring the accuracy of the gas sensing measurement in
our work. The gas sensing system was employed to monitor the
resistance variation of the fabricated sensors. The correspond-
ing response is defined as Response = Ra/Rg, where Ra and Rg
denote the resistance captured in an atmosphere of air and
NO2, respectively. Details about the fabrication of the gas
sensor and the gas sensing tests are described in the Materials
and Methods.
As shown in Figure 4c, the detailed dynamic gas sensing
transients reveal that the PGNS (i.e., PSS-rGO with
lyophilization (PSS-rGO w/L)) sensor exhibits a dramatically
enhanced response (Ra/Rg = 5.37) toward 10 ppm of NO2 gas
compared to other graphene-based materials, i.e., PSS-rGO
without lyophilization (PSS-rGO w/o L), rGO with lyophiliza-
tion (rGO w/L), and rGO without lyophilization (rGO w/o
L). The enhanced response of PGNS is mainly attributed to the
specific nanoscroll structure and the functionalization with PSS
molecules. The mechanism analysis for gas sensing and the
response enhancement of PGNS is discussed in detail in the
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Table 1. Comparison of NO2 Sensing Performance of Typical Graphene-Based Sensors

materials and structure method NO2 (ppm) responsea operating temperature
2D graphene/MoS2 heterostructure 49
photolithography and ion etching 5 7% 150 °C
3D mesoporous rGO/SnO250 hydrothermal and lyophilization 100 12% 55 °C
MoS2/graphene hybrid aerogel51 freeze-drying and annealing 3 15% 200 °C
3D scaffold rGO/polymer52 electrospinning 4.5 18% 100 °C
N and Si co-doped graphene nanosheets53 high-temperature annealing 21 26% RTb
rGO network covered 3D micropillar54 photoetching 5 28% RT
single-layer graphene channel55 CVD 10 28% 100−165 °C
RGO/porous PEDOT56 in situ polymerization deposition 10 33% RT
flexible Ag-S-RGO45 gravure print 10 45% RT
In2O3 cubes/rGO composites57 microwave-assisted hydrothermal method 10 50% RT
holey rGO nanosheets58 hydrothermal reduction 12.5 54% RT
sulfonated rGO44 chemical modification 10 58% RT
graphene/polymer nanofibers59 self-assembly 5 61% RT
3D SiO2@graphene frameworks60 electrostatic self-assembly 50 69% RT
rGO/In-SnO2 nanohybrids61 one-pot aqueous method 10 75% RT
PGNS (this work) supramolecular assembly and lyophilization 5 75% RT
10 81% RT
a ΔR |R a − R g|
For convenience of comparison, the evaluation of response is converted as Response = Ra
= Ra
(%). bRT represents room temperature.

Supporting Information together with a mathematic model
analysis.
In practical gas sensing applications, linearity of response as a
function of gas concentration is also of important significance.
Figure 4d exhibits the successive dynamic-sensing response
(Ra/Rg) of the PGNS sensor toward 1−10 ppm of NO2. It is
clear that the response amplitude increases monotonically with
the rising of NO2 concentration. A simple linear regression fit is
applied to find that the PGNS sensor reveals an excellent linear
detection range from 1 to 10 ppm with the corresponding
response (Ra/Rg) measured from 2.25 to 5.48 (Figure 4e).
The PGNS sensor also exhibits excellent selectivity to NO2
gas, as shown in Figure 4f. For convenience of comparison,
here the evaluation of the response is converted as
|R a − R g |
ΔR
Response = Ra
= Ra
(%). The PGNS sensor exhibits a
much higher response toward NO2 (ΔR/Ra = 81%, 10 ppm)
than other interferential gases including Cl2 (ΔR/Ra = 21%,
1000 ppm), NH3 (ΔR/Ra = 17%, 1000 ppm), ethanol (ΔR/Ra
= 14%, 1000 ppm), acetone (ΔR/Ra = 8%, 1000 ppm), and
methanol (ΔR/Ra = 7%, 1000 ppm), even though the NO2
concentration is 100 times lower than the others. The results
indicate that the PGNS sensors are extremely sensitive to NO2.
Similar to the previously reported mechanism,29,44,45 the high
selectivity of the PGNS sensor probably results from two facts:
(1) The −SO3− groups of PSS possess a strong adsorption
capacity especially for NO2 gas molecules. (2) NO2 is a typical
strong electron-withdrawing gas, while the interferential gases
exhibit weak electron-withdrawing properties or -donating
capacity and are, thus, unable to cause a significant resistance
change. Therefore, the selectivity of the PGNS sensors for NO2
gas detection is high.
To investigate the repeatability and stability of our sensing
device, the PGNS sensor was exposed to 10 ppm of NO2 for
three successive cycles. An average response (Ra/Rg = 5.39)
with a small standard deviation of 8% is measured (Figure 4g),
verifying the reliable repeatability of the PGNS sensor.
Moreover, an aging test was carried out monthly for half a
year (Figure 4h). The sensor reveals a high stable response
toward 10 ppm of NO2 within an 11% standard deviation of its
average value (Ra/Rg = 5.37) over the whole period of time.
Notably, no distinct degradation of the response is observed,
and the response/recovery times also remain stable, proving the
high stability of the PGNS sensor. In fact, the high response
toward NO2 of the PGNS sensor is competitive with the
existing graphene-based gas sensors as summarized in Table 1.
Here, it is noteworthy that the PGNS sensor operates at room
temperature with an ultrahigh response, which makes it more
versatile for practical gas detection with low energy
consumption.46−48
CONCLUSIONS
In summary, inspired by the capillary structure inside a dog’s
nose, functionalized graphene-based nanoscrolls, i.e., PGNS,
were fabricated for application as highly sensitive gas sensors.
An effective supramolecular assembly combined with the
lyophilization technique was developed to massively transform
the planar PSS-rGO nanosheets to uniform PGNS of high
quality. By performing cryo-SEM, we revealed the distinct
morphological changes in each scrolling stage during the
lyophilization process and clarified the corresponding scrolling
mechanism supported by MD simulations. Due to the
important role of the functional PSS molecules, the PGNS
exhibited a wide-open tubular morphology with uniform
dimensions. The as-prepared PGNS gas sensors revealed an
ultrahigh response, superior selectivity and sensing linearity,
reliable repeatability, and stability. The supramolecular
assembly combined with the lyophilization establishes an
effective processing technique to prepare graphene-based
nanoscrolls with the potential for large-scale production.
MATERIALS AND METHODS
Preparation of GO Dispersion. GO flakes (purchased from
XianFeng NANO Co., Ltd.) were ultrasoniated in deionized (DI)
water for an hour and then mildly sonicated for 40 min to prepare a
0.2 mg/mL GO dispersion.
Preparation of rGO Dispersion. A 75 μL amount of ammonia
(30%) was added to 20 mL of GO dispersion (0.2 mg/mL) to regulate
the pH to 12.5. Then 10 mL of hydrazine hydrate (1 μL/mL) was
used to chemically reduce the GO dispersion in an oil bath for 1 h at
95 °C with gentle stirring. After cooling to ambient temperature, the
dispersion was dried by vacuum filtration and then redispersed into 20

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mL of DI water under mild sonication to prepare a 0.2 mg/mL rGO
dispersion.
Preparation of PSS-rGO Dispersion. An 80 mg amount of PSS
(Purchased from Alfa Aesar) was added into 20 mL of a GO
dispersion (0.2 mg/mL). After 5 min of mild sonication, 10 mL of
hydrazine hydrate (1 μL/mL) was added dropwise under gentle
stirring, and the dispersion was then kept at 80 °C for 1 h in an oil
bath. After cooling to ambient temperature, the resultant dispersion
was rinsed three times by vacuum filtration with DI water and finally
redispersed into 20 mL of DI water under mild sonication to get a
homogeneous PSS-rGO dispersion (0.2 mg/mL).
Lyophilization of GO, rGO, and PSS-rGO Dispersion. The as-
prepared GO, rGO, and PSS-rGO aqueous dispersions were poured
into glass bottles (10 mL) and vertically immersed into liquid nitrogen
for 5 min to be solid frozen. The samples were immediately transferred
into the hanging bottle of a lyophilizer and kept at around −10 °C
under 20 Pa for 48 h to be completely dehydrated.
Fabrication of Gas Sensors. A drop and dry method was applied
in the gas sensor fabrication. First, the lyophilized rGO powders and
PGNS were redispersed into DI water with the same concentration
(0.2 mg/mL) of rGO w/o L and PSS-rGO w/o L. Afterward, 20 μL of
each dispersion was dropped on the surface of the IEs, which were
fabricated by jetting Ag−Pd paste on ceramic substrates through a
metal-jetting system (Supporting Information, Figure S9). Then the
IEs were dried on a heating holder in air at 50 °C for 2 min. Finally,
the gas sensors were available for the subsequent tests.
Gas Sensing Tests. All the gas sensing tests were performed by a
gas sensing system that was designed to monitor the resistance
changes of the fabricated gas sensors under a dc bias voltage of 4.5 V.
Prior to the sensor measurements, pure air gas was inflated into the gas
chamber to create a stable air environment; then quantitative NO2
(Cl2) with testing concentration was injected as the test started, and
the gas chamber was opened when the test ended. For the injection of
volatile gases including ammonia, ethanol, acetone, and methanol,
their vapor streams can be generated by heating the corresponding
volatile compounds in a crucible inside the chamber. All the gas
sensing tests were performed at room temperature (25 °C) in the
range of 45−65% relative humidity, and the final data were obtained
based on five measurements.
Characterizations. The general morphology of GNS and PGNS
was examined by SEM (Quanta 250 FEG, FEI, Czechia). The
morphology of the scrolling PSS-rGO nanosheets embedded in ice was
characterized by cryo-SEM (Helios NanoLab G3 UC, Czechia). The
length and diameter of the PGNS were measured by confocal optical
microscopy (Leica DCM8, Germany). The surface elemental
composition and characteristic functional groups of the samples
were analyzed by XPS (ESCALAB 250 photoelectron spectrometer,
Thermo Fisher Scientific, USA) and FTIR (Thermo Scientific Nicolet
iN10, USA). FESEM (JSM-7500F, JEOL, Japan) in combination with
EDS mapping (Oxford Instruments, UK) was performed to verify the
uniform coverage of PSS on the nanoscrolls. I−V characteristic curves
were measured by an SA6101 electrical analysis system (Sinoagg Co.,
Ltd., China). The applied voltage was varied from dc −1 to 1 V in
steps of 0.05 V. All the gas sensing measurements were performed by
the Intelligent Gas Sensing Analysis System (CGS-1TP, ELITE
TECH. Beijing).
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsnano.7b08294.
Digital images of GO, rGO, PSS-rGO dispersions, and
corresponding lyophilized foams; SEM images of PGNS,
rGO w/o L, rGO w/L, and PSS-rGO w/o L; SEM
images of PGNS under enhanced ionic strength; Leica
images of PGNS; Leica image of PGNS; FTIR spectrum
of PSS powders; top-view cryo-SEM image of vertically
distributed PSS-rGO nanosheets; schematic of fast
H DOI: 10.1021/acsnano.7b08294
Article
freezing process and temperature gradient measurement;
metal-jetting system and interdigitated electrode fab-
rication process; MD simulation methods; mechanism
analysis for gas sensing and response enhancement of
PGNS (PDF)
Video of the whole thermodynamic scrolling process
(AVI)
AUTHOR INFORMATION
Corresponding Authors
*E-mail: yao@buaa.edu.cn.
*E-mail: jianglei@buaa.edu.cn.
*E-mail: guofu.zhou@m.scnu.edu.cn.
ORCID
Yao Wang: 0000-0002-0713-5018
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was supported by National Natural Science
Foundation of China (Grant Nos. 51673007, 51773069,
51561135014), National Key Basic Research Program of
China (2014CB931800), Startup Foundation from SCNU
(No. 8S0134), Guangdong Innovative Research Team Program
(No. 2013C102), Guangdong Provincial Key Laboratory of
Optical Information Materials and Technology (Grant No.
2017B030301007), MOE International Laboratory for Optical
Information Technologies, and the 111 Project.
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J DOI: 10.1021/acsnano.7b08294
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