Article

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High-Efficiency Production of Graphene by Supercritical CO2

Exfoliation with Rapid Expansion
Ying Wang,*,† Zhuo Chen,‡ Zhijian Wu,† Yun Li,‡ Wang Yang,‡ and Yongfeng Li*,‡
†
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences,
Changchun 130022, P. R. China
‡
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Changping, Beijing 102249, P. R. China
*
S Supporting Information

ABSTRACT: In this study, direct nonequilibrium molecular

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dynamics simulations based on the density-functional tight-

binding potential were performed to investigate the
mechanism of graphite exfoliation by supercritical CO2 in
the depressurization process. We found that the graphite
peeling rate and the graphene yield depended on the number
of inserted CO2 molecules in our simulations, and the
appropriate pressure or density of CO2 is a prerequisite to
achieve graphite exfoliation. Our theoretical results proposed
that the graphite peeling occurred till the pressure or the
Langmuir 2018.34:7797-7804.

density of CO2 was larger than 12.2 MPa or 0.21 g/cm3. This
is confirmed by the experimental observations. Furthermore, we declared that the essential effect of the pressure or density of
CO2 was attributed to the competition between the van der Waals attraction in the graphite interlayer and repulsion of CO2 and
graphite, which resulted from the steric hinder effect. The current theoretical observations provide potential scientific evidence
to control graphite exfoliation by supercritical CO2.

1. INTRODUCTION regarded as an efficient method to get large amount of

Graphene has been the focus of much scientific research
interest because of its preeminent properties and potential
technological applications since its discovery by Novoselov and
Geim in 2004.1,2 Owing to the outstanding properties of
graphene, it can be used in the fields of sensitive sensors,3
electric power resonators,4 hydrogen storage,5 and so forth. As
a kind of ideal nanomaterial, the application of graphene is
often hindered by the thickness and amount obtained by
different preparation methods. To the best of our knowledge,
the preparation of graphene can be divided into two categories,
top-down and bottom-up. The discovery of graphene by
peeling off the graphite with a scotch tape is one kind of top-
down method leading to single-layer graphene with high
quality.2 The bottom-up method, such as the chemical vapor
deposition (CVD)6 method, is also used to fabricate single- or
few-layer graphene for applying directly. However, the amount
of graphene obtained by the peel-off process or CVD is
unsuitable for commercial applications. Currently, the
industrial method for the mass production of graphene is the
solution exfoliation of graphite oxide (GO) and reduction of
GO.7,8 However, the production process causes lot of
pollution, and the structure of the obtained graphene is
severely damaged. From the perspective of sustainable
development, the loss outweighs the gain.
In the last decades, supercritical fluid (SCF) exfoliation
technology has been in use because of many advantages, such
as the simple setup, less toxic, and mass production. It has been
graphene nanosheets (GNs).9−13 Currently, carbon dioxide
(CO2),12−21 ethanol,10 and N,N-dimethylformamide11 are
commonly used as the SCF media. By far, supercritical CO2
(scCO2) is the most promising SCF in graphene-based
material processing because of its environmentally friendly
nature and easily accessible critical conditions. It has been
reported that CO2 can be diffused easily into graphene layers,
with the molecular size (0.23 nm) similar to the layer distance
(0.34 nm).12,22 The scCO2 exfoliation has been developed,
assisted by several methods such as ultrasonic,14,23 shear
force,21 and ball milling.19,24 The supercritical conversion of
layered graphite to graphene sheet is a multistep process and
can be separated into three stages: (1) pretreatment of
graphite chunk; (2) SCF intercalation, and (3) exfoliation.13
The pretreatment step affects the intercalation degree of SCFs,
and the intercalation degree of SCFs has great impact on the
exfoliation efficiency of the subsequent exfoliation step. In the
exfoliation step, rapid expansion is the common method to
exfoliate graphene sheets from intercalated graphite.
Many studies13,15 have focused on the influences of
temperature, pressure, shock velocity,21 scCO2 density,25
colloid aggregation,26 aqueous solution content ratio, and
ultrasonic power23 during the graphite exfoliation process.
Received: March 30, 2018
Revised: May 14, 2018
Published: June 20, 2018

© 2018 American Chemical Society 7797 DOI: 10.1021/acs.langmuir.8b01030

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However, until now, the exfoliation mechanism in the
depressurization process of scCO2 has not been well-explored.
It is well-known that the rapid depressurization process can
reduce the pressure of the reaction system from a high to low
in seconds. The volume of the CO2 molecule expanded in the
depressurization process and the distance between layers was
broadened, so that graphite can be exfoliated efficiently.
Therefore, the depressurization process plays a key role for
exfoliating graphite. In this work, molecular dynamics (MD)
simulations were carried out to find out the behaviors of CO2
and graphite in the depressurization process of scCO2 as well
as the interactions between CO2 and graphite layers. Some
fundamental issues, such as the dynamic graphite peeling
process, the effects of CO2 density, and the competition
between the van der Waals (vdW) attraction in the graphite
interlayer and repulsion of CO2 and graphite have been
addressed. We expect these atomic scale simulations to explain
the critical role of supercritical density in the depressurization
process and provide useful information for effective graphite
exfoliation.
2. COMPUTATIONAL AND EXPERIMENTAL SECTION
2.1. Computational Method. 2.1.1. Quantum Chemical MD
(QM/MD) Simulations. All simulations were carried out based on the
self-consistent-charge density functional tight binding (SCC-DFTB)27
method, as implemented in the DFTB+ program. DFTB is a Born−
Oppenheimer MD technique and can bridge the gap between the
classical and first-principles MD simulations because of the balance of
the accuracy and computational time. A finite electronic temperature
(Te = 2000 K) approach28,29 was chosen to improve the convergence
of the DFTB equations. The electronic temperature allows the
occupancy of each molecular orbital to change smoothly from 2 to 0
depending on its energy, and then it could effectively incorporate the
open-shell nature of the system. This method of SCC-DFTB with Te
has been successfully applied to single-wall carbon nanotube growth
and graphene growth.30−34 The vdW correction was included by using
the dispersion term with the universal force field (UFF) method. In
the nonequilibrium MD (QM/MD), the velocity Verlet integrator35
was used to integrate the equations of motion of nuclei with a time
step of 1 fs. MD simulations were performed in the canonical
ensemble (NVT). The nuclear temperature (Tn = 310 K) was
controlled by connecting the Nose−Hoover chain thermostat.36 The
mio-0-1 parameter sets were employed in our study.
To evaluate the reliability of the SCC-DFTB method for our
modeling systems, the interaction energies of graphite, one or two
CO2 molecules with graphite, were calculated by both density
functionary theory (DFT) and SCC-DFTB methods. To save the
computational resources, a double-layer 4 × 4 supercell graphite
consisting of 64 carbon atoms with the size of 9.84 Å × 8.52 Å was
employed. In DFT calculations, Perdew, Burke, and Ernzerhof
(PBE37) was used, and all calculations were implemented by the
Vienna ab initio simulation package.38−41 A kinetic energy cutoff of
400 eV was used with a plane-wave basis set. The integration of the
Brillouin zone was conducted using a 3 × 3 × 1 Monkhorst−Pack
grid.42 All atoms were fully relaxed and optimized until the total
energy was converged to 1.0 × 10−4 eV/atom and the force was
converged to 0.05 eV/Å. A sufficiently large vacuum of 20.0 Å was
taken along the z-axis to avoid image interactions. Spin polarization
and vdW interaction with a semiempirical DFT-D243,44 force-field
approach were also considered. The interaction energies at the DFT
and SCC-DFTB levels of theory are listed in Table S1. As can be seen
in Table S1, the SCC-DFTB method can reproduce the first-
principles (PBE) results very well. The absolute errors in the
interaction energies are less than 0.07 eV. Thus, it is fair to say that
direct MD simulations based on the current SCC-DFTB method are
of comparable quality to first-principles MD simulations. Also, we
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believe that SCC-DFTB is a proper method to study the graphite
exfoliation mechanism by CO2.
2.1.2. Model System. In this study, a larger model of double-layer 6
× 6 supercell graphite with an interlayer distance of 0.34 nm was
established (totally, 72 × 2 = 144 carbon atoms). Following that, one,
two, or five CO2 molecules were randomly inserted into one or two
interlayers of graphite, denoted as G-n-0-CO2 or G-n-CO2 (n = 1, 2,
and 5), as shown in Figure 1. The former corresponds to
Figure 1. Illustration of simulation systems. (a) Graphite alternatively
surrounded by one CO2 and zero CO2 molecules (G-1-0-CO2); (b)
graphite surrounded by one CO2 molecule in each interlayer (G-1-
CO2); (c) graphite alternatively surrounded by two CO2 and zero
CO2 molecules (G-2-0-CO2); (d) graphite surrounded by two CO2
molecules in each interlayer (G-2-CO2); and (e) graphite alternatively
surrounded by five CO2 and zero CO2 molecules (G-5-0-CO2). The
atoms of C and O were decorated with cyan and red. a1 and a2 are
the interlayer distances and the sum of a1 and a2 are 6.8 Å.
inhomogeneous intercalation and the latter is related to uniform
insertion. In our MD simulations, we first optimized these five models
and then equilibrated these structures at 310 K for 10 ps. The total
energy plots as a function of the equilibration time are shown in
Figure S1. Second, three structures for each model were randomly
chosen from the NVT equilibration simulations between 5 and 10 ps.
On the basis of these 15 initial structures, the annealing simulations
were carried out until 100 or 10 ps for the systems of G-1-0-CO2, G-
1-CO2, G-2-0-CO2, G-2-CO2, and G-5-0-CO2 at the same nuclear
temperature. The periodical boundary condition (PBC) was
considered. In the optimization and 10 ps equilibrium processes,
the PBC in the z matrix was imposed as 6.8 Å. In the depressurization
process, it was enlarged to 100 Å to promise enough space for
graphite separation. Because PBC is involved, each model can be
imaged in three directions to construct a huge system. Furthermore,
by intercalating one-two-five CO2 molecules, the different density
effects of CO2 could be well considered. Therefore, the current
models are suitable to describe graphite peeling under supercritical
conditions in the depressurization process.
To investigate the effect of CO2 density or pressure, the interaction
energy of CO2 with graphite (Eint) was calculated based on the
following equation
Eint = EG + CO2 − EG − nECO2 (1)
where EG+CO2, EG, and ECO2 are the total energies of graphite with
CO2, graphite, and isolated CO2 and n is the number of CO2
molecules. The positive energy indicates a repulsive interaction.
The vdW of each graphite layer (Ev‑g) was estimated by the
following equation
Ev ‐ g = Ev ‐ dg − 2Ev ‐ sg
(2)
where Ev‑dg and Ev‑sg are the energies of 6 × 6 double-layer graphite
and single-layer graphene with UFF dispersion correction. Here, the
z-direction was set as 100 Å to avoid the interaction of other image
layers.
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2.2. Experimental Method. 2.2.1. Materials. Graphite flakes

were obtained from Xinjiang, China. Carbon dioxide, anhydrous
ethanol, and other materials were used as received without further
purification.
2.2.2. Preparation of GNs. The experiment was performed on a
self-developed SCF apparatus consisting of a gas cylinder, chiller,
compressor, pump, and reactor. The typical process is as follows: 10 g
of pristine graphite was directly put into the reactor (250 mL) with a
heating jacket and a temperature controller. The reactor was sealed
and heated to a set temperature (60 °C). CO2 was injected into the
reactor with the pump to a set pressure (16 MPa). After 1 h of
exfoliation, the valve was opened, and the system pressure was
dropped from 16 to 4 MPa in a few seconds. Then, the GN powder
was collected.
2.2.3. Characterization. The morphology and structure of the
samples were obtained by field emission scanning electron
microscopy (SEM, Hitachi SU8010), high-resolution transmission
electron microscopy (TEM, FEI Tecnai G2 F20), and scanasyst-mode
atomic force microscopy (AFM, Bruker Multimode 8). Raman
spectroscopy was performed on a Horiba Xplora Plus microscope
with the laser wavelength of 532 nm.

3. RESULTS AND DISCUSSION

3.1. Graphite Exfoliation Kinetics. It is well-known that
SCFs feature outstanding wetting of surfaces, low interfacial
tension, low viscosity, and high diffusion coefficients, so that it
will easily accomplish penetration and exfoliation.11 In
Figure 2. Time evolution of graphite exfoliation for model G-1-0-
experiments, it has been proved that following 30 min of CO2. (a−c) Correspond to the three trajectories.
immersion in the SCF, scCO2 diffused into the layers of
graphite.12 Also, previous MD studies declared that at a higher
scCO2 fluid density, there are more confined CO2 molecules
within the interpolate regions.25 Therefore, in our current
study, we assume that the solvent intercalation (step 2) within
the layer of graphite is ready under extremely high-pressure
conditions and only consider the effect of CO2 density on the
rate or efficiency for exfoliation during the depressurization
process (step 3). In this study, both inhomogeneous
intercalation (G-n-0-CO2) and uniform insertion (G-n-CO2,
n = 1, 2, and 5, see Figure 1) are considered.
Figures 2−6 depict the snapshots of 15 trajectories at
different densities of interlayer CO2. For the model of G-1-0-
CO2 (inhomogeneous intercalation, Figure 2), the interlayer
distances of three initial structures (0 ps), which were
randomly selected from the 10 ps equilibrium simulations,
were almost same with the value of ∼3.60 Å. This indicated
that our 10 ps MD annealing simulations reached the
equilibrium states, confirmed by the small floating of the
Mermin free energy (Figure S1a) during 5−10 ps. After 100 ps
annealing simulations at 310 K, we found that the inserted
CO2 molecule continually rotated and collated with the carbon
atoms in the graphite layers. The interlayer distances were
enlarged slightly, such as, at 1 ps, the interlayer distances of
graphite were increased by ∼0.3 Å (3.91, 3.98, and 3.87 Å for
three trajectories) compared to the initial structures.
Furthermore, we found that the graphite layers fluctuated Figure 3. Time evolution of graphite exfoliation for model G-1-CO2.
and moved gradually in the lateral direction, which is (a−c) Correspond to the three trajectories.
consistent with the previous observations.10 This kind of
movement consumed the kinetic energy and potential energy
of the system. Thus, the residual energy was not enough to resumed, as shown in Figure 3. No graphite exfoliation was
overcome the vdW interaction between the graphite layers, and achieved. Also, we found that the CO2 in the upper layer flew
the graphite failed to be exfoliated. At 100 ps, the interlayer away immediately, once the vertical direction (z-matrix) was
distances of graphite were still ∼3.88, 3.69, and 3.81 Å, enlarged to 100 Å from 6.80 Å during the pressure releasing
respectively. process. Compared with G-1-0-CO2, the initial interlayer
For the model of G-1-CO2 (uniform insertion), similar distance was shortened to be ∼3.40 Å in G-1-CO2, which is
situations were observed. The graphite expanded first and then close to the interlayer distance of perfect graphite because of
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Figure 4. Time evolution of graphite exfoliation for model G-2-0-
CO2. (a−c) Correspond to the three trajectories.
Figure 5. Time evolution of graphite exfoliation for model G-2-CO2.
(a−c) Correspond to the three trajectories.
the uniform distribution of CO2 in each interlayer (see Figure
1b). When the z-direction was expanded, the interlayer
distance of graphite was enlarged more significantly in G-1-
CO2, such as, at 1 ps, the interlayer distances were 5.64, 4.73,
and 5.99 Å, which were larger than the ones in G-0-1-CO2 by
∼1.5 Å, indicating that uniform insertion of CO2 (here, each
layer one CO2) could more effectively weaken the interactions
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Figure 6. Time evolution of graphite exfoliation for model G-5-0-
CO2. (a−c) Correspond to the three trajectories.
of the graphite layer. Meanwhile, the lateral movement and the
fluctuation of graphite as well as the rotation and collation of
CO2 in G-1-CO2 was also more substantial than in G-1-CO2.
Therefore, more redundant energies were exhausted and
resulted in graphite peeling failure. At 100 ps, the interlayer
distance of graphite returned to 3.80−3.90 Å.
With the number of intercalated CO2 increasing, graphite
peeling occurred, as shown in Figures 4−6. Figures 4 and 6
correspond to CO2 inhomogeneous intercalation (G-0-2-CO2
and G-0-5-CO2), where CO2 was alternatively inserted into
graphite interlayers (the upper layer without CO2 and the
lower layer with n CO2, see Figure 1c,e). Figure 5 is related to
the uniformed two CO2 insertions (G-2-CO2, see Figure 1d).
From Figures 4 and 6, we can see that the initial interlayer
distances of the lower layer in the models G-2-0-CO2 and G-5-
0-CO2 (a1 = ∼3.70 and ∼3.98 Å) were larger than the one in
model G-1-0-CO2 by 0.10 and 0.38 Å, respectively. This is
attributed to the larger steric hindrance effect by more CO2
insertion. At the same time, the distance in the upper layer (a2,
without CO2) decreased to ∼3.10 and ∼2.82 Å as the total
distance was restricted as 6.8 Å (a1 + a2 = 6.8 Å, see Figure 1).
These results showed that the CO2 molecules played a “wedge”
role in the exfoliation process, which is in good agreement with
the previous observations.17 Furthermore, the gradually
reduced space with the increasing number of CO2 led to a
stronger repulsive interaction, which further resulted in rapid
graphite peeling25,26 during the depressurization process. At 1
ps, the exfoliation has already occurred for the models G-2-0-
CO2 and G-5-0-CO2, and the averaged interlayer distances
from the three trajectories were 8.93 and 12.98 Å, respectively.
At 10 ps, graphite was fully exfoliated with an extremely larger
expanded interlayer distance of 30−40 Å.
In addition, for G-2-CO2, in which four CO2 molecules were
randomly filled into the two interlayers, the calculated
interlayer distance was comparable to that of G-1-CO2 as
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well as to that of perfect graphite, owing to the uniformly
distributed CO2 and the space restriction of 6.8 Å along the z-
direction. Similar to G-1-CO2, in the depressurization process,
that is, when the PBC box was expanded to 100 Å in the z-
direction, the two CO2 molecules in the upper layer were
quickly released to the larger vacuum. On the other hand, the
lower layer graphite was separated by the pressure relieved
CO2. For example, at 1 and 10 ps, the interlayer distances have
already been ∼10.8 and 51 Å, indicating that graphite is fully
exfoliated, as shown in Figure 5.
3.2. Pressure Effect. It is well-known that pressure is a
crucial parameter for the exfoliation of graphite into graphene.
In this study, the influence of pressure on the graphene yield
was investigated by changing the number (or density) of CO2
molecules in between graphite layers.
First, we analyzed the graphite separation time for each
model, as listed in Table 1. Here, the interlayer distance being
Table 1. Exfoliation Time (in ps) for Graphite by CO2a
Tra1 Tra2 Tra3 averaged
G-1-0-CO2    
G-1-CO2    
G-2-0-CO2 0.55 0.60 0.65 0.60
G-2-CO2 0.45 0.45 0.45 0.45
G-5-0-CO2 0.25 0.30 0.30 0.28
a
Noted that the distance between two layers being larger than 7 Å is
denoted as graphite separation. “” indicates that graphite is not
separated.
larger than 7.0 Å was regarded as graphite exfoliation. From
Table 1, we can see that for G-1-0-CO2 and G-1-CO2, the
graphite failed to peel, so there is no exfoliation time available.
As for G-2-0-CO2, G-2-CO2, and G-5-0-CO2, the averaged
exfoliation time from three trajectories was 0.60, 0.45, and 0.28
ps, respectively, indicating the exfoliation speed increasing with
the increasing number of intercalated CO2. Furthermore, we
did not find the restacking of separated graphene sheets,
suggesting that the aggregation was obstructed by the confined
CO2 molecules with an efficient exfoliation. This agrees well
with the previous experimental and theoretical results.20,45
To see the pressure effect more clearly, we also plot the
averaged (averaged from 3 trajectories) interlayer distance as a
function of time for the five models, as shown in Figure 7. The
same plots for the individual trajectories are shown in Figure
S2. From the inset figure, we can see that during the first 20 ps,
the distance of the graphite interlayer constantly fluctuated for
the models G-1-0-CO2 and G-1-CO2, and G-1-CO2 fluctuated
Figure 7. Averaged interlayer distance for the five models. The inset is
the enlarged figure of distance vs time for the models of G-1-O-CO2
and G-1-CO2. Averaged from three trajectories.
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more seriously than G-1-0-CO2. This can also be reflected by
the snapshots in Figures 2 and 3. For G-2-0-CO2, G-2-CO2,
and G-5-0-CO2, with the number of CO2 molecules increasing,
the interlayer distance increases faster and faster. The
increasing rates (slopes) for G-2-0-CO2, G-2-CO2, and G-5-
0-CO2 are 3.49, 5.16, and 7.53 Å/ps. This suggested that a
higher density of CO2 would lead to an easier and faster
formation of graphene sheets, which is consistent with the
previous results.25 Furthermore, if we added more pressure to
the system, CO2 molecules could be inserted and accumulated
more in the interlayers of graphite because of good
compressibility of scCO2. Thus they would generate a much
stronger repulsive energy and further expand the spaces
between the interlayers. Therefore, higher pressure can
increase the speed and efficiency of peeling and is beneficial
to graphite exploitation under scCO2 conditions.
3.3. Essence of Graphite Exfoliation by scCO2. As we
know, the interlayer distance of graphite is about 3.4 Å, which
is larger than the size of the CO2 molecule (2.3 Å) by 1.2 Å.
Therefore, there is enough space for the CO2 molecule to
diffuse into the interlayers of graphite, especially at higher
pressure. Following CO2 molecules intercalation, we system-
atically investigated the exfoliation process during depressuri-
zation. We found that the entered CO2 molecules not only
expanded the interlayer distance because of the steric
hindrance effect but also produced a repulsive energy between
graphite and CO2 molecules. Both of them reduce the
attraction of the graphite interlayer and benefit graphite
exfoliation.
In principle, the prerequisite for graphite exfoliation was the
repulsive energy resulting from the molecular insertion being
enough to overcome the vdW interaction between the graphite
interlayers.25,26 Therefore, in this study, we evaluated the
interaction energies (Eint) and vdW contribution of each layer
based on our 6 × 6 double-layer graphite model (Ev‑g), as listed
in Table 2. It shows that all interaction energies (Eint) were
positive due to the space hinder effect, indicating there was a
strong repulsive integration between CO2 and graphite.
Furthermore, to declare the essence of graphite exfoliation,
the averaged repulsive energy in each layer was calculated as
3.10, 3.32, 5.76, 5.94, and 13.47 eV for G-1-0-CO2, G-1-CO2,
G-2-0-CO2, G-2-CO2, and G-5-0-CO2, respectively. It is clearly
seen that Eint‑a in the two former systems was less than the
absolute value (3.97 eV) of Ev‑g, indicating that a small amount
of CO2 was not enough to expand the interlayer spacing; and
thus, no graphite exfoliation was observed. Contrarily, for more
CO2 cases (G-2-0-CO2, G-2-CO2, and G-5-0-CO2), a stronger
repulsive energy (Eint‑a is higher than Ev‑g) resulted in graphite
peeling. Moreover, Eint‑a gradually increased with more and
more CO2 molecules accumulating in the graphite interlayers,
caused by the gradually narrowed interlayer distance in the
optimized structures (d, see Table 2). This suggested that the
higher the CO2 density (or the high pressure), the stronger the
repulsion, and further more quick exfoliation. This revealed the
essence of pressure effect, as discussed in section 3.2.
Furthermore, our simulation results showed that efficient
graphite peeling occurred until the density of CO2 or pressure
was larger than 0.21 g/cm3 or 12.2 MPa (see Table 2);
otherwise, the graphite peeling failed. We hope our theoretical
observation can provide a reference for further experiments or
industrial applications.
3.4. Characterization of GNs. To confirm our prediction,
the experiments was performed at 16 MPa, which is slightly
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Table 2. Density of CO2 (ρ), Pressure of CO2 (P), and the Interlayer Distance (d) in the Optimized Graphite with Different
Number of CO2 Molecules. Here, a1 and a2 (a1 + a2 = 6.8 Å) Are the Interlayer Distances, as Defined in Figure 1. Eint is the
Interaction Energy between CO2 and Graphite, Eint‑a is the Averaged Eint in Each Interlayer, and Ev‑g is the vdW Contribution
in Each Interlayer of Graphitea
ρ P d (a1/a2) Eint Eint‑a Ev‑g
G-1-0-CO2 0.11/0 6.28/0 3.61/3.19 3.10 3.10 −3.97
G-1-CO2 0.11/0.11 6.69/6.65 3.39/3.41 6.65 3.32
G-2-0-CO2 0.21/0 12.2/0 3.72/3.08 5.76 5.76
G-2-CO2 0.23/0.23 13.5/13.2 3.36/3.44 11.88 5.94
G-5-0-CO2 0.49/0 28.5/0 3.97/2.83 13.47 13.47
a
The data before and after slash (/) are for the lower and upper layers. The units of density, pressure, energy, and distance are in g/cm3, MPa, eV,
and Å, respectively.

larger than our predicted values (12.2 MPa). The morpho-
logical and structural characterizations of pristine graphite and
GNs were performed by SEM, TEM, and Raman (Figure 8).
Raman spectra (Figure 8e,f) after the exfoliation process. This
shows that the GNs have a smaller crystallite size compared
with the pristine graphite and have a little damage to the
crystal.46 A large red shift in the 2D band (from 2720 to 2702
cm−1) is observed, and it proves that graphite has been
successfully exfoliated in scCO2. In addition, the shape of the
2D band becomes more symmetric, which also can confirm the
reduction of the layer number.
AFM is also used to determine the thickness of graphene
sheets (Figure 9). We find that the height is about 1 nm, larger

Figure 9. (a,b) AFM images of graphene sheets on mica substrates,

corresponding height profile along the lines, with height of closing to
1, 3 and 4.4 nm, respectively.

than the theoretical thickness of monolayer graphene.

Figure 8. (a,b) SEM images of graphite and GNs; (c,d) TEM images
of graphite and GNs; and (e,f) Raman spectra of graphite and GNs.
The pristine graphite showed a typical smooth graphite surface
in which graphite layers were stacked densely (Figure 8a).
Wrinkles were clearly observed after the exfoliation process in
the SEM image (Figure 8b), indicating that graphite has been
exfoliated into few-layer GNs. From the TEM images (Figure
8c,d), it can be seen that the layer number before and after the
exfoliation process clearly decreased, which is consistent with
the SEM results. We also found that the D band (around 1351
cm−1) was slightly enhanced and ID/IG was increased in the
7802
Considering the residue of the solvent on graphene, the
product can be defined as monolayer graphene. Moreover, the
heights of the stacked graphene layers are about 3 and 4.4 nm,
indicating the existence of few-layer graphene. To further
confirm the yield of graphene sheets, AFM measurement was
performed on randomly selected 100 GNs, and the histogram
of the layer distribution is shown in Figure 10. From the layer
distribution, we can clearly see that more than 76% of the
graphene sheets have fewer than five layers. All results are
consistent with our theoretical simulations. Compared with
previous reports, the advantages of ours are they are free of
surfactants and organic solvents and does not require post-
treatment. After the exfoliation process, the layers may restack
together without the CO2 intercalation; but the interaction
DOI: 10.1021/acs.langmuir.8b01030
Langmuir 2018, 34, 7797−7804
Langmuir
Figure 10. Histogram of the number of visual observation of flakes as
a function of the number of layers of graphene per sheet made by
AFM.
between layers may not be fixed as close as the vdW attraction
and can be easily broken up.
4. CONCLUSIONS
In this work, we performed nonequilibrium QM/MD
simulations based on the DFTB potential to explore the
mechanism of graphite exfoliation in the presence of scCO2
during the depressurization process. The dynamic process of
graphite peeling was depicted, and the pressure effect was
declared by inserting different numbers of CO2 molecules into
graphite interlayers. The role of CO2 was also predicted. The
simulation results highlighted that the fundamental driving
force for graphite exfoliation is the repulsive interaction
between CO2 and graphite because of the space hinder effect,
attributed to the compressed (or inserted) CO2 molecules. On
the other hand, the vdW interaction between the graphite
interlayers is the major resistance for graphite exfoliation. Our
calculated results showed that if the repulsive energy is not
enough to overcome the vdW interaction, the graphite peeling
will fail. Conversely, once the repulsive energy is larger than
the vdW interaction, graphite exfoliation will occur. Fur-
thermore, the higher the density of CO2, the quicker and more
efficient is the exfoliation. Meanwhile, during the graphite
exfoliation process the graphite could move along both lateral
and vertical directions, fluctuated continually, and the inserted
CO2 rotated and vibrated ceaselessly in between the layers of
graphite. These movements consumed the remainder energy of
the systems. We proposed that the prerequisite of graphite
exfoliation was the pressure or density of CO2 being larger
than 12.2 MPa or 0.21 g/cm3. This is verified by our
experiments. In our experiment, the layer number of GNs has
been obviously reduced and the yield of few-layer GNs has
been enhanced. The current theoretical observation provides
potential scientific evidence to control the graphite exfoliation
by scCO2.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.lang-
muir.8b01030.
Interaction energies, total Mermin free energy, and the
interlayer distance (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: ywang_2012@ciac.ac.cn (Y.W.).
7803
Article
*E-mail: yfli@cup.edu.cn (Y.L.).
ORCID
Zhuo Chen: 0000-0002-0669-0044
Yongfeng Li: 0000-0003-0855-7949
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work is supported by the National Key Research and
Development Program of China (2016YFA0602901), the
National Natural Science Foundation of China (21673220,
21503210, 21521092, 21733004, 21576289, and 21776308),
the Jilin Province N atural S cience Foundation
(20150101012JC), and the Special Program for Applied
Research on Super Computation of the NSFC-Guangdong
Joint Fund (the second phase). Part of the computational time
is supported by the Performance Computing Center of Jilin
University, Changchun Normal University, the High Perform-
ance Computing Center of Jilin Province, the Science
Foundation of China University of Petroleum, Beijing (grant
no. C201603), the Science Foundation Research Funds
Provided to New Recruitments of China University of
Petroleum, Beijing (grant no. 2462014QZDX01), and the
Thousand Talents Program.
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