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Two-Dimensional CVD-Graphene/Polyaniline Supercapacitors:

Synthesis Strategy and Electrochemical Operation
Michal Bláha, Milan Bouša, Václav Valeš, Otakar Frank, and Martin Kalbác*̌
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ABSTRACT: Nanocomposites of graphene materials and conducting polymers

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have been extensively studied as promising materials for electrodes of

supercapacitors. Here, we present a graphene/polyaniline heterostructure
consisting of a CVD-graphene and polyaniline monolayer and its electro-
chemical operation in a supercapacitor. The synthesis employs functionalization
of graphene by p-phenylene sulfonic groups and oxidative polymerization of
anilinium by ammonium persulfate under reaction conditions, providing no bulk
polyaniline. Scanning electron microscopy, atomic force microscopy, and Raman
spectroscopy showed the selective formation of polyaniline on the graphene. In
situ Raman spectroelectrochemistry and cyclic voltammetry (both in a
microdroplet setup) confirm the reversibility of polyaniline redox transitions
and graphene electrochemical doping. After an increase within the initial 200
cycles due to the formation of benzoquinone−hydroquinone defects in
polyaniline, the specific areal capacitance remained for 2400 cycles with ±1% retention at 21.2 μF cm−2, one order of magnitude
higher than the capacitance of pristine graphene.
KEYWORDS: two-dimensional heterostructure, CVD-graphene, polyaniline monolayer, Raman spectroelectrochemistry, supercapacitor

■ INTRODUCTION
The development of two-dimensional electronics relies on
graphene and polyaniline nanofibers by vacuum filtration of
mixed dispersions of both components; the resulting
designing and developing circuit components and their composite film had a layered structure with polyaniline
incorporation into smart integrated systems. An off-grid nanofibers sandwiched between the graphene layers.20 Finally,
smart integrated system can be designed, consisting of an in 2010, Xu et al. presented hierarchical nanocomposites of
active (working) device, an energy harvesting device, and an polyaniline nanowire arrays on graphene oxide sheets; the
electrical energy storage device. Therefore, the transformation polyaniline nanowire arrays were prepared by a dilute
of bulk supercapacitors into planar micro-supercapacitors and polymerization strategy.9
Since then, various graphene-like materials have been
the design of new two-dimensional supercapacitors are of high
combined with variously nanostructured polyaniline to
interest to the wider scientific community.1−6 Graphene,
produce materials with high specific capacitance and excellent
graphene-like materials, and conducting and redox-active
capacitance retention. The field has been reviewed many times
polymers, particularly polyaniline, have been widely inves-
in the last few years,10−18 reflecting the huge volume of
tigated as materials for supercapacitors.7,8 Unfortunately, the
published work and confirming the importance of the research.
performance of both systems is poor: the graphene-based
While most researchers have combined various graphene and
systems exhibit relatively low capacitances, and the polyaniline-
polyaniline nanostructures, there remains a lack of knowledge
based supercapacitors suffer from a short cycle life.9 However,
of the electrochemical transitions in both components,
the combination of conductive and mechanically stable
including understanding their mutual interactions. This lack
graphene and redox-active polyaniline forms a synergetic
of knowledge is probably caused by the fact that the reported
system: the graphene/polyaniline supercapacitors combine
graphene/polyaniline nanocomposites may not be fully
high specific capacitance with long-life capacitance reten-
tion.10−18
The uniqueness of this synergetic combination has been Received: March 17, 2021
demonstrated by Wang et al. in 2009, who prepared a Accepted: June 21, 2021
freestanding and flexible graphene/polyaniline composite
paper by in situ anodic electropolymerization of aniline on
graphene paper.19 Following that, Wu et al. presented the
synthesis of mechanically stable and flexible composite films of
© XXXX The Authors. Published by
American Chemical Society https://doi.org/10.1021/acsami.1c05054
A ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces
Scheme 1. Reaction of Aniline Hydrochloride with Ammonium Persulfate in an Acidic Aqueous Environment Providing a
Conducting Polymer, Polyaniline
uniform in terms of their composition, distribution, and
structure, making the detailed electrochemical characterization
difficult. A broad, inhomogeneous distribution of components
seems to be unavoidable for systems prepared by physical
mixing and those prepared by chemical oxidative polymer-
ization of aniline physisorbed on graphene. Both graphene
sheet stacking and bulk polyaniline formation can hardly be
excluded. However, for further systematic improvement of the
capacitive properties of various graphene/polyaniline systems,
it is essential to obtain detailed knowledge of the electro-
chemical behavior of well-defined systems. The reduction of
the system dimensionality toward fully two-dimensional
graphene/conducting polymer heterostructures is a promising
option for producing well-defined materials for electrochemical
studies, as shown by Kovařič́ ek et al.21 for poly(3,4-
ethylenedioxythiophene) monolayers on sulfonated graphene.
Various methods for producing polyaniline mono- and
nanolayers have been reported: (1) self-assembly of the
dissolved bulk polyaniline,22−25 (2) electrochemical and
chemical oxidative polymerization of anilinium films on self-
assembled templates bearing sulfonic groups,26,27 (3) synthesis
of polyaniline thin films on substrate surfaces28−30 and
functionalized surfaces,31−36 and (4) synthesis of polyaniline
freestanding films utilizing templates37 or interfaces.38 Few of
the above-mentioned methods work with surface sulfonation
to produce an electrostatically stabilized anilinium monolayer
for subsequent polymerization,26,27 which is a concept easily
transferable into graphene chemistry through graphene
sulfonation.21,39
The development of fully two-dimensional graphene/
polyaniline heterostructures is a logical next step toward
energy storage devices for flexible/stretchable miniaturized
smart integrated systems. In this study, we adopt the chemical
polymerization of a Langmuir layer of anilinium on the
surfaces bearing sulfonic groups,26 and using sulfonated CVD-
graphene, we prepared two-dimensional graphene/polyaniline
heterostructures on Si/SiO2 substrates. We investigate the
electrochemical operation of these structures by Raman
spectroelectrochemistry and cyclic voltammetry. We discuss
the mutual interactions of both components, including the
charge-injection ratio, and explain the polyaniline-altering
process observed during cycling.
■
EXPERIMENTAL SECTION
Chemicals. Sulfanilic acid (puriss, p.a., ≥99.0%; Sigma-Aldrich),
sodium nitrite (puriss, Penta, Czech Republic), aniline hydrochloride
(purum, p.a., ≥99.0%; Sigma-Aldrich), and ammonium persulfate
(p.a., min 98.0%; Penta, Czech Republic) were used as supplied.
Synthesis. CVD-Graphene Synthesis. Graphene was grown on a
copper substrate by chemical vapor deposition (CVD) and transferred
to Si/SiO2 substrates using the nitrocellulose-based technique.21
Graphene Functionalization. CVD-graphene was functionalized
by phenylene sulfonic groups using a diazonium protocol, for which
zwitterionic diazonium was formed by the reaction of sulfanilic acid
and sodium nitrite in water.21 The experimental procedure is as
B https://doi.org/10.1021/acsami.1c05054
www.acsami.org Research Article
follows: in a 50 mL beaker, 75 mg of sulfanilic acid was suspended in
5 mL of deionized water, and subsequently, a solution of 30 mg of
NaNO2 in 5 mL of deionized water was added. The mixture was
vigorously stirred and left at room temperature until the sulfanilic acid
completely dissolved. Subsequently, the graphene on the substrate
was immersed in the reaction mixture, and the functionalization was
allowed to proceed for 30 min at room temperature. Then, the wafer
was removed from the solution, neutralized by soaking in 2% aqueous
hydrochloric acid for 2 min, washed 3× with 5 mL of deionized water
and 5 mL of methanol (HPLC grade), and dried in a stream of argon.
Graphene/Polyaniline Heterostructure Synthesis. Polyaniline was
prepared on the surface of the functionalized graphene by oxidation of
1.00 × 10−3 M aniline hydrochloride with 1.25 × 10−3 M ammonium
persulfate in an aqueous environment at room temperature (Scheme
1). Equal volumes of solutions of aniline hydrochloride (13.0 mg,
0.100 mmol, in 50 mL of deionized water) and ammonium persulfate
(28.5 mg, 0.125 mmol, in 50 mL of deionized water) were mixed in a
beaker and briefly stirred. The wafer with the functionalized graphene
was immediately immersed in this polymerization mixture. After 90
min, the sample was removed from the reaction mixture, repeatedly
washed with methanol (3 × 5 mL), and left to dry under ambient
conditions. Under the applied concentrations of aniline hydrochloride
and ammonium persulfate, the reaction mixture remained colorless for
the first 90 min, indicating that the reaction did not overcome the
induction period of aniline oxidation with ammonium persulfate40
and consequently that the formation of polyaniline did not proceed
quantitatively in the entire volume of the reaction mixture.
A reference bulk polyaniline film was prepared on a separate Si/
SiO2 wafer by oxidation of aniline hydrochloride (0.2 M) with
ammonium persulfate (0.25 M) in deionized water according to the
“standard” aniline polymerization reported by Stejskal and Gilbert.40
Briefly, equal volumes of aqueous solutions of aniline hydrochloride
(0.259 g, 2 mmol, in 5 mL of deionized water) and ammonium
persulfate (0.571 g, 2.5 mmol, in 5 mL of deionized water) were
mixed in a vial and briefly stirred. After mixing the reaction
components, a Si/SiO2 wafer was immersed in the solution and
kept there for 30 min. The prepared, grown in situ bulk polyaniline
film was washed 4× with 5 mL of 0.2 M hydrochloric acid, left to dry
under ambient conditions, and then stored over silica gel in a
desiccator.
Characterization. Scanning Electron Microscopy. Scanning
electron microscopy (SEM) images were acquired using a Hitachi
S4800 scanning electron microscope at an acceleration voltage of 1
kV.
Atomic Force Microscopy. Atomic force microscopy (AFM)
images were measured using a Bruker Dimension Icon with
ScanAsyst-air silicon nitride probes. Measurements were performed
in the PeakForce tapping mode with a peak force setpoint of
approximately 1 nN.
Raman Spectroscopy. Raman spectroscopy measurements were
performed at room temperature using a LabRAM HR spectrometer
(Horiba Jobin Yvon) interfaced to an Olympus BX-41 microscope
and equipped with a HeNe laser operating at a wavelength of 633 nm
(Eex = 1.96 eV). Measurements were performed using a 100×
objective, a grating with 600 grooves mm−1, and a typical laser power
of ≈0.8 mW on the sample.
Raman Spectroelectrochemistry, Raman−μSEC. Spectroelectro-
chemical characterization was performed in a three-electrode
electrochemical setup employing a microdroplet method and the
Raman system described above (Raman−μSEC). The microdroplet
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Figure 1. (A) Raman spectra of pristine graphene, sulfonated graphene, the Si/SiO2 substrate exposed to the polymerization mixture, the
graphene/polyaniline heterostructure, and the bulk polyaniline film. (B) Area mapped by Raman spectroscopy (black rectangle), with the
indication of the intensity of the Raman band of polyaniline located at around 1165 cm−1 (proportional to the size of the blue circles), and the
indication of the intensity of the 2D band of graphene (proportional to the size of the red crosses). (C) Raman spectra of the graphene/polyaniline
heterostructure on the Si/SiO2 support (blue line) and of the bare Si/SiO2 support exposed to the polymerization mixture (black line) typical for
the Raman map in panel (B). All spectra were recorded with an excitation wavelength of 633 nm.

Table 1. Positions and Assignment of Raman Bands in the Spectra of the Bulk Polyaniline Film and the Graphene/Polyaniline
Heterostructurea,b
Raman shift (cm−1) band assignment
bulk polyaniline film graphene/polyaniline heterostructure graphene polyaniline
2655 2D
1621 1621 D′ ν(CC)B44−46
1590 1595 G ν(CC)Q44−46
1510 δ(N−H)SQ44−46 + ν(CN)SQ45
1480 ν(CN)Q in emeraldine base44,45
1419 ν(C∼N•+) in polaron pairs47
1333 ν(C∼N•+) in polarons44,45
1328 D possible contribution: ν(C∼N•+) in polarons44,45
1260 ν(C−N)B44−46
1223 ν(C−N)Q44−46
1170 1165 δ(C−H) in SQ44−46
a
Spectra were recorded with λexc = 633 nm. bAbbreviations: ν, stretching; δ, in-plane bending; B, benzenoid ring; Q, quinonoid ring; SQ,
semiquinonoid ring; ∼, a bond intermediate between a single bond and a double bond.

method means that the electrochemistry is conducted in a small
electrolyte solution droplet of the order of few tens of μm in
diameter,41 substituting a classical electrochemical cell. The droplet
and the microcapillary inserted into the droplet contain 6 M aqueous
LiCl (Sigma-Aldrich, 99.9%) electrolyte solution. The sample serves
Cyclic Voltammetry. All measurements were performed with the
electrochemical setup described above for Raman spectroelectro-
chemistry. Cyclic voltammograms were measured for the potential
range from −0.2 to 0.6 or 0.7 V (RE: Ag/AgCl) at scan rates of 50
and 500 mV s−1.

■
as the working electrode after contacting the sample by silver close to
the measurement spot; both the reference (RE: Ag/AgCl) and the RESULTS AND DISCUSSION
counter (CE: Pt) wire electrodes are located in the microcapillary
inserted into the droplet. All spectroelectrochemical experiments were The synthesis of the graphene/polyaniline heterostructure was
performed using an Autolab 30 potentiostat (Metrohm) equipped designed as a two-step process. First, CVD-graphene on a Si/
with a low-current module working at a current range down to 10 pA. SiO2 wafer is functionalized by p-phenylene sulfonic groups
C https://doi.org/10.1021/acsami.1c05054
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Figure 2. SEM micrographs of (A) graphene/polyaniline heterostructure and (B) pristine graphene, both on Si/SiO2 supports. (C) Comparison of
the thicknesses of the graphene/polyaniline heterostructure and pristine graphene measured by AFM. The height and the RMS roughness of both
samples are depicted as a red line and a gray shaded area, respectively. Topography images of (D) the graphene/polyaniline heterostructure on the
Si/SiO2 substrate and (E) pristine graphene on the Si/SiO2 substrate. Green lines in (D) and (E) indicate where the thicknesses were evaluated.
We intentionally selected areas with a hole to demonstrate the thickness of investigated layers.

using the diazonium protocol as previously reported.21 In the
second step, an anilinium monolayer formed on the surface of
the sulfonated graphene is oxidized by ammonium persulfate;
this process is analogous to the synthesis of polyaniline
monolayers from anilinium Langmuir−Blodgett films.26 The
results of both synthetic steps are reflected by the Raman
spectra of the nanomaterials (Figure 1A). While the Raman
spectrum of pristine graphene (Figure 1A) exhibits only the
typical features, namely, the G mode at 1599 cm−1, the 2D
mode at 2650 cm−1, and the defect-induced D mode at 1328
cm−1 at a negligible intensity,42,43 the functionalization of
graphene results in a strong increase in the intensity of the D
mode. This observation is in accordance with previous work21
and corresponds to a change in the hybridization of carbon
atoms from sp2 to sp3. After the exposure of the functionalized
graphene to the polymerization mixture, a set of new Raman
bands appears (see Figure 1A) at the positions partially
corresponding to the Raman bands of a bulk polyaniline film,
the spectrum of which is presented for comparison (Figure
1A) and corresponds well to previously published polyaniline
spectra.44−46 As a result of graphene functionalization and its
interaction with the polyaniline monolayer, the G mode subtly
changes position from 1599 to 1595 cm−1. We note that the G
mode overlaps with the Raman bands of polyaniline, which
also contributes to its line shape.
The polyaniline bands in the Raman spectrum of the
graphene/polyaniline heterostructure are only in partial
accordance with those in the spectrum of a reference bulk
polyaniline film (see Figure 1A and Table 1). In the spectrum
of the bulk polyaniline film (Figure 1A), we observe the band
of in-plane C−H deformation vibrations at 1170 cm−1, the
band of the C−N stretching vibrations in benzenoid units at
1260 cm−1, the band of C∼N•+ vibrations in polaronic
structures (∼ indicates an order of bond between a single bond
and a double bond) at 1333 cm−1, the band typical of
polyaniline emeraldine salt at 1510 cm−1, the band of CC
stretching vibrations in quinonoid units at 1590 cm−1, and the
band of C∼C stretching vibrations in benzenoid units at 1621
cm−1.44−46 In the spectrum of the graphene/polyaniline
heterostructure (Figure 1A), the following differences are
D https://doi.org/10.1021/acsami.1c05054
present: the band of in-plane C−H deformation vibrations is
shifted from 1170 to 1165 cm−1, a new band of C−N
stretching vibrations in quinonoid units at 1223 cm−1 is
observed instead of the band at 1260 cm−1, the band of C∼N•+
polaronic vibrations is not visible due to overlap with the D
mode of graphene at 1328 cm−1, a new band appears at 1419
cm−1 and can be assigned to the C∼N•+ stretching vibrations
in polaron pairs,47 a new band of CN stretching vibrations in
quinonoid unitstypical of a polyaniline emeraldine
base44−46appears at 1480 cm−1, the band typical of
polyaniline salt at 1513 cm−1 is reduced to a shoulder, the
band of quinonoid rings at 1585 cm−1 is overlapped by the G
mode of graphene 1595 cm−1, and the band of benzenoid rings
at 1621 cm−1 coincides with the D′ mode of graphene. The
observed differences indicate the increased content of
nonprotonated quinonoid rings; the spectrum thus corre-
sponds to a partially protonated polyaniline instead of the
expected fully protonated polyaniline. We note that the
graphene bands were observed without polyaniline bands for
short acquisition times. Increasing the acquisition time resulted
in the appearance of polyaniline bands, the intensity of which
was proportional to the cumulative time of laser irradiation for
the series of repeated measurements (see Figure S1). We thus
expect that the 633 nm laser wavelength slightly heats the
sample and causes the release of the doping hydrochloric acid.
As a result, the bands of the polyaniline base start to appear
due to the resonance enhancement of polyaniline emeraldine
base by the 633 nm excitation line. In summary, Raman
spectroscopy of the graphene/polyaniline heterostructure
confirms the formation of a polyaniline layer but does not
provide information on the polyaniline protonation state; the
sample structure is altered during measurements.
No observation of polyaniline Raman signature outside the
sulfonated graphene area (see Figure 1A) is consistent with the
expectation coming from setting the reaction conditions for
aniline polymerization, namely, that the polyaniline formation
proceeds selectively on the acidic sulfonated surface under
conditions applied.26 This conclusion on no formation of
polyaniline outside the graphene area is also supported by the
Raman maps (Figure 1B) showing the simultaneous absence
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Figure 3. (A) Raman spectroelectrochemistry (Raman−μSEC) of the graphene/polyaniline heterostructure on the Si/SiO2 support with an
excitation wavelength of 633 nm. Spectra recorded for the potential range −0.4 to +0.5 V (RE: Ag/AgCl). (B) Detailed comparison of the spectra
recorded at the potentials of −0.4 and +0.5 V (RE: Ag/AgCl) at different locations. (C) Redox and protonation states of a regular polyaniline
chain. (D) Vector analysis of the G and 2D Raman mode positions of graphene in the graphene/polyaniline heterostructure (blue line, −0.4 to +0.4
V). Data recorded for the pristine graphene monolayer under similar conditions are shown for comparison (black line, 0 to +0.4 V).

(on the Si/SiO2 wafer) and presence (on the graphene) of the
Raman band of polyaniline located at ∼1165 cm−1 and the 2D
mode of graphene.
The morphology of the graphene/polyaniline heterostruc-
ture was investigated using scanning electron microscopy;
Figure 2A,B shows the morphologies of the graphene/
polyaniline heterostructure with pristine graphene for refer-
ence. Starting with the latter, Figure 2B shows that the
monolayer of CVD-graphene, which covers almost the entire
image, is accompanied by various features typical of graphene,
such as folds or wrinkles, a second graphene layer, and
impurities: nanoparticles trapped between graphene and the
support. The observation is comparable for the graphene/
polyaniline heterostructure (Figure 2A); the graphene features
are partially covered by the conducting polymer layer but
remain easy to distinguish. The presence of the polyaniline
monolayer results in a different texture, visible as a contrast
variation caused by heterogeneous charging during the
measurement. A sandlike subtexture can be observed in the
polyaniline monolayer itself (Figure 2A), indicating the
uniform coverage of entire functionalized graphene. A detailed
investigation into the crack openings in the graphene layer of
the graphene/polyaniline heterostructure (see Figure S2)
shows that the polymer does not cover areas where graphene
is missing, which is consistent with our conclusion on selective
polymer formation on the surface of functionalized graphene,
based on our Raman results. Scanning electron microscopy did
not indicate any polyaniline macroscopic objects, consistently
with optical microscopy observations.
The thicknesses of pristine graphene and the graphene/
polyaniline heterostructure were examined by atomic force
microscopy (AFM) in peak force tapping mode; the height
profiles are presented in Figure 2C. The pristine graphene has
a height of approximately 2.1 nm and a root-mean-square
E https://doi.org/10.1021/acsami.1c05054
(RMS) roughness of 0.2 nm, which is in line with the
literature.48,49 For the graphene/polyaniline heterostructure, a
height of 4.0 nm and an RMS roughness of 0.8 nm are
observed. These data give a value of approximately 1.9 nm for
the thickness of the polyaniline layer of the graphene/
polyaniline heterostructure, which is within the range of data
reported for polyaniline monolayers.24,28,29,36 Zhang et al.24
prepared mono- and multilayered films of polyaniline/DBSA
and characterized it by AFM; they determined the thickness of
the four-layer film of polyaniline to be 12.5 ± 0.5 nm, which
provides a mean thickness value of 3.1 nm per layer. Vega-Rios
et al.29 used anilinium dodecylsulphate as the surfactant to
assist expanded graphite exfoliation, and then as the monomer
to synthesize the conductive polyaniline; they obtained
polyaniline/graphene flakes with an average thickness of 3.5
nm as determined by AFM. Tang et al.28 synthesized 2D
polyaniline/TiO2 nanosheets and reported their total AFM-
determined thickness as 2.7 nm. Oren et al.36 prepared a
polyaniline monolayer by the oxidative polymerization of the
anilinium Langmuir−Blodgett film, and by variable angle
spectroscopic ellipsometry, they determined its thickness as 0.7
± 0.2 nm.
The total thickness of the graphene/polyaniline hetero-
structure is two times larger than the thickness of the pristine
graphene monolayer used as a reference. Based on the data
shown in Figure 2C and previous results from the
literature,24,28,29,36 we conclude that the synthetic strategy we
employed produces a graphene/polyaniline heterostructure
consisting of a polyaniline monolayer on a functionalized
graphene monolayer.
In situ Raman spectroelectrochemistry is an efficient tool to
study the effects of an injected charge on the electronic
structure of various conducting polymers47,50−53 and their
composites with carbon nanostructures.21,54−56 In this study, a
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Table 2. Positions and Assignment of the Raman Bands of the Graphene/Polyaniline Heterostructure: A Comparison of the
Prepared Form with the Raman Spectroelectrochemical Study at Potential Ranges −0.4 to −0.1, 0.0 to +0.3, and +0.4 to +0.5
V (RE: Ag/AgCl)a,b
Raman shift (cm−1) band assignment
prepared −0.4 to +0.4 to
form −0.1 V 0.0 to +0.3 V +0.5 V graphene polyaniline
2650 (m) 2650 (m) 2650−55 (m) 2655 (m) 2D
1621 (sh) 1621 (m) 1622 (m) 1622 (m) D′ ν(C∼C)B44−46
1600 (vs) G
1595 (s) 1587−91 (s) 1588−97 (vs) G ν(CC)Q44−46
1586 (vs) ν(CC)Q44−46
1564 (w) 1569 (sh) 1564 (sh) ν(C−C)Q in pernigraniline units44
1513 (sh) 1513 (vw) 1513 (w) δ(N−H)SQ44−46 + ν(CN)SQ45
1480 (m) 1480 (m) for +0.3 V ν(CN)Q in emeraldine base44,45
1474 (sh) 1474 (vs) ν(CN)Q in emeraldine base44,45 or in the bipolaronic structure of
pernigraniline salt62
1419 (m) 1419 (m) ν(C∼N•+) in polaron pairs47
1383 (sh) 1383 (w) ν(C∼N•+) in highly localized polarons45,63
1352 (sh) ν(C∼N•+)44,45
1328 (vs) 1328 (vs) 1328−30 (vs) 1330 (vs) D possible contribution: ν(C∼N•+) in polarons44,45 and delocalized polarons44−46
1264 (vw) 1264 (w) 1264 (vw) 1264 (w) ν(C−N)B44−46
1223 (w) 1223 (w) 1223 (s) ν(C−N)Q44−46
1180 (sh) 1180 (m) 1174 (vw/m) δ(C−H) in leucoemeraldine base units64
1165 (m) 1165 (w) 1165 (w/m) 1165 (s) δ(C−H) in SQ44−46
1144 (w) sulfuric acid47
a
Spectra recorded with λexc = 633 nm. bAbbreviations: vs, very strong; s, strong; m, medium; w, weak; vw, very weak; sh, shoulder; ν, stretching; δ,
in-plane bending; B, benzenoid ring; Q, quinonoid ring; SQ, semiquinonoid ring; ∼, a bond intermediate between a single bond and a double
bond.

microdroplet in situ Raman spectroelectrochemistry (Ram-
an−μSEC; for details, see the Experimental Section) was used
to investigate electrochemically induced changes in the
graphene/polyaniline heterostructure in the potential range
−0.4 to +0.5 V (RE: Ag/AgCl; Figure 3A) and to compare
them with those observed for pristine graphene. Changes in
the electrochemical potential are reflected by the shifts and
changes in the intensities of the graphene G and 2D bands of
the graphene/polyaniline heterostructure. Simultaneously, the
appearance and disappearance of various Raman bands
indicate polyaniline reduction and oxidation, respectively.
For graphene, it is known that electrochemical doping causes
the injection of charge carriers into its structure and shifts the
Fermi level.57 Using vector analysis58,59 of the G and 2D mode
positions, the contribution of doping and strain can be
disentangled. In our spectroelectrochemical experiments, we
compared the G and 2D band positions for the pristine
graphene and the graphene/polyaniline heterostructure using
spectral sets recorded under similar experimental conditions.
For both samples, the slopes of the linear fits in the G/2D
vector analysis diagram (Figure 3D) are similar within a range
of approximately 0.5−0.6, which is in good agreement with refs
58, 59 and indicates graphene hole doping for the potential
increase from −0.2 to +0.5 V.60,61 Using a simplified formula
for the dependence of the G mode position on doping,
ΔPos(G) = −0.986n2 + 9.847n (where n is the charge carrier
concentration in 1013 cm−2),60 the change in the potential from
0 to +0.4 V results in the change of the charge carrier
concentration: Δn ≈ 1.29 × 1013 cm−2 for the graphene layer
of the graphene/polyaniline heterostructure and Δn ≈ 1.64 ×
1013 cm−2 for the pristine graphene used as a reference sample.
These values indicate that comparable amounts of charge are
injected into the pristine graphene and the graphene layer of
F https://doi.org/10.1021/acsami.1c05054
the graphene/polyaniline heterostructure. The observed differ-
ence between the Δn values is within the variation of Δn
calculated for the G band position variation obtained by
Raman mapping of the graphene/polyaniline heterostructure.
In situ Raman spectroelectrochemical measurements also
provide information on the reduction and oxidation processes
in polyaniline.47,50−52 Polyaniline exhibits three distinctive
oxidation states (Figure 3C). (1) Leucoemeraldine is the
reduced form of polyaniline and consists only of −amino−p-
phenylene− units. (2) Emeraldine base is formed by two-
electron oxidation of the tetra(−amino−p-phenylene−)
subchain of leucoemeraldine. Due to oxidation, each fourth
diamino phenylene unit changes to a diimino quinone unit,
meaning that every fourth benzenoid ring changes to a
quinonoid ring. (3) Pernigraniline base is formed by a two-
electron oxidation process of an emeraldine base tetramer;
diimino quinone units and benzenoid rings regularly repeat in
the structure of the pernigraniline base. Furthermore, the
diimino units of the emeraldine base and the pernigraniline
base can act as two-proton acceptors, which results in the
formation of emeraldine salt and pernigraniline salt,
respectively. The protonation of diimino quinone units
provides −NH+•−phenylene−NH+•− units. An increase of
conductivity by 8 orders of magnitude is observed due to the
formation of polarons in emeraldine salt.40 (All redox and
acid−base transitions of polyaniline are presented in Figure
3C.) The described polyaniline states differ in their UV−visible
absorption spectra; resonance effects thus play an important
role in the Raman spectroscopy of polyaniline.50,51
Our Raman−μSEC experiment (Figure 3A) shows reduc-
tion and oxidation of the polyaniline monolayer of the
graphene/polyaniline heterostructure consistent with the
previous studies on bulk polyaniline films.47,50−52 The intensity
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces www.acsami.org Research Article

Figure 4. (A) Cyclic voltammograms (CV) of the graphene/polyaniline heterostructure and pristine graphene (on the Si/SiO2 support) recorded
at a scan rate of 50 mV s−1. (B) Specific areal capacitance of the graphene/polyaniline heterostructure during the first 2650 CV cycles at a scan rate
of 500 mV s−1 (potential window −0.2 to +0.6 V; every fifth value is plotted), recorded for a different sample. (B, inset) Raman spectra recorded at
+0.4 V before and after 200 cycles. (C) Specific areal capacitance of pristine graphene during the first 1200 CV cycles at a scan rate of 500 mV s−1
(potential window −0.2 to +0.6 V; every fifth value is plotted). (D) Typical CV of the graphene/polyaniline heterostructure and a pristine
graphene sample after the initial capacitance increase in (B) and (C).

ratio of the polyaniline and graphene bands differs for various
applied electrochemical potentials. Whereas the graphene
bands dominate in the spectra recorded at −0.4 to 0.0 V
(RE: Ag/AgCl), for +0.4 and +0.5 V, the most intense
polyaniline bands are of intensity comparable to that of the
graphene bands (see Figure 3A,B). The 633 nm excitation laser
line resonantly enhances the modes of the oxidized units of
polyaniline, whose increasing content results in an intensity
increase for all polyaniline bands. Further investigation of the
spectral set shows three different polyaniline spectral patterns,
for −0.4 to −0.1 V, 0.0 to +0.3 V, and +0.4 to +0.5 V (RE: Ag/
AgCl). A tentative assignment for each spectral pattern is
provided in Table 2. We note that the spectrum of the as-
prepared graphene/polyaniline heterostructure is in the best
accordance with the spectrum recorded at +0.4 V (RE: Ag/
AgCl), which confirms that the polyaniline monolayer is
formed in the emeraldine oxidation state.47
Cyclic voltammetry measurements proved the reversibility of
the graphene electrochemical doping and the redox transitions
in polyaniline. The shape of the cyclic voltammograms is
dependent on the scan rate. For the low scan rate of 50 mV s−1
(Figure 4A), the pristine graphene exhibits an almost
rectangular shape,65 whereas the graphene/polyaniline hetero-
structure shows prominent redox peaks with redox transitions
located at around +0.25 and +0.40 V (RE: Ag/AgCl) for
oxidation and at around +0.15 V for reduction, specifically the
reduction of emeraldine to leucoemeraldine (see Figure 3C).
This observation is in line with previously reported
G https://doi.org/10.1021/acsami.1c05054
voltammetry data on polyaniline monolayers.26,27,34 For the
high scan rate of 500 mV s−1, the pristine graphene
voltammograms remained almost rectangular (Figure S3),
while the graphene/polyaniline heterostructure exhibited less
well-resolved redox peaks and a significant increase in current
values (Figure S3).
The capacitance stability of the graphene/polyaniline
heterostructure at a scan rate of 500 mV s−1 was determined
by cyclic voltammetry in the range −0.2 to +0.6 V (RE: Ag/
AgCl) using a similarly prepared sample. For this purpose,
2650 cycles were recorded, and the cyclic voltammograms
were integrated according to ref 66 in the range −0.2 to +0.6 V
(RE: Ag/AgCl). In Figure 4B, there is a continuous increase in
the specific areal capacitance to 21.2 μF cm−2 within the first
approximately 200 cycles. The capacitance then remains stable
for at least 2400 cycles with ±1% retention. Figure 4D shows
the shape of the typical cyclic voltammogram of the graphene/
polyaniline heterostructure for the cycles following an increase
in the capacitance, corresponding to a power density of 13.1
μF cm−2 s−1. A similar experiment was carried out for pristine
graphene, the cyclic voltammograms of which were qual-
itatively similar during cycling. The specific areal capacitance
obtained by the integration of the cyclic voltammograms in the
range −0.2 to +0.6 V (RE: Ag/AgCl) slightly increases with
the number of cycles from the initial value of 1.8 μF cm−2 to
the value around 2.1 μF cm−2 (Figure 4C) after approximately
400 cycles. The graphene capacitance obtained is qualitatively
in accordance with the reported capacitance of CVD-
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces
graphene,65 ∼4 μF cm−2. To understand the initial capacitance
increase of the graphene/polyaniline heterostructure, Raman
spectra were collected at +0.4 V (RE: Ag/AgCl) before cycling
and after 200 cycles in a similar experiment (see the inset in
Figure 4B). A comparison of these Raman spectra shows a new
shoulder at around 1640 cm−1, which indicates structural
changes in the polyaniline layer: the formation of oxygen-
containing p-benzoquinone-like structural defects,44,67 known
as the group that causes the “middle oxidation peak” of
polyaniline.47 We thus expect that the observed capacitance
increase (Figure 4B) is connected with the formation of
hydroquinone/benzoquinone moieties.
Comparing the specific areal capacitance values for the scan
rate of 500 mV s−1 shows that the graphene/polyaniline
heterostructure capacitance value is about ten times higher
than that of pristine graphene (see the graphical comparison of
CV in Figure 4D). As the G/2D vector analysis indicates a
comparable amount of charge carriers in the graphene in both
cases (see Δn discussed above), we conclude that the
polyaniline monolayer and the graphene monolayer act in
synergy, and an asymmetry of charge distribution can be
expected. Our data indirectly indicate that the polyaniline layer
accommodates one order of magnitude more charge per
geometrical area than the graphene layer of the graphene/
polyaniline heterostructure.
■
CONCLUSIONS
In summary, we have prepared a two-dimensional hetero-
structure consisting of a CVD-graphene monolayer and a
polyaniline monolayer by a two-step synthetic strategy.
Graphene was functionalized by p-phenylene sulfonic groups
using the diazonium protocol. Subsequently, a polyaniline
monolayer was prepared by the oxidation of aniline hydro-
chloride with ammonium persulfate on a functionalized
graphene surface under reaction conditions reported for the
interfacial polymerization of anilinium in Langmuir mono-
layers. The formation of the graphene/polyaniline hetero-
structure has been proven by Raman spectroscopy: in addition
to the Raman bands of functionalized graphene, the bands
indicating the polyaniline emeraldine form were observed.
Polyaniline synthesis proceeded selectively on the surface of
the functionalized graphene, and no polyaniline was detected
by Raman spectroscopy on a neat Si/SiO2 wafer. This
selectivity is due to a combination of the higher local acidity
of the functionalized surfaces, the reaction concentrations, and
reaction time under which no polyaniline is formed in the
entire volume of the reaction mixture. Atomic force
microscopy indicated that the graphene/polyaniline hetero-
structure is approximately two times thicker than the pristine
graphene used as a reference. Scanning electron micrographs
showed a change of surface texture after the formation of a
polymer layer and thus confirmed the synthesis of the
graphene/polyaniline heterostructure. We have investigated
and described the reversible electrochemical operation of both
components of the graphene/polyaniline heterostructure by
Raman−μSEC for the potentials −0.4 to 0.5 V (RE: Ag/
AgCl): polyaniline exhibits reversible redox transitions, and
graphene is electrochemically doped both by positive and
negative charges. Finally, cyclic voltammetry measurements at
500 mV s−1 showed that the specific areal capacitance of the
graphene/polyaniline heterostructure increased during the first
200 cycles to 21.2 μF cm−2 and remained stable at this value
for 2400 cycles with ±1% retention. Our data indirectly
H https://doi.org/10.1021/acsami.1c05054
www.acsami.org Research Article
indicated that the polyaniline layer accommodates about one
order of magnitude more charge than the graphene layer.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.1c05054.
In situ deprotonation of the graphene/polyaniline
heterostructure during Raman measurements; SEM
micrograph of the graphene/polyaniline heterostructure
showing an area with a crack; and cyclic voltammograms
of the graphene/polyaniline heterostructure, sulfonated
graphene, and pristine graphene recorded at the scan
rate of 500 mV s−1 (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Martin Kalbáč − J. Heyrovský Institute of Physical Chemistry,
Czech Academy of Sciences, CZ-182 23 Prague 8, Czech
Republic; orcid.org/0000-0001-9574-4368;
Email: martin.kalbac@jh-inst.cas.cz
Authors
Michal Bláha − J. Heyrovský Institute of Physical Chemistry,
Czech Academy of Sciences, CZ-182 23 Prague 8, Czech
Republic; orcid.org/0000-0003-3664-0037
Milan Bouša − J. Heyrovský Institute of Physical Chemistry,
Czech Academy of Sciences, CZ-182 23 Prague 8, Czech
Republic; orcid.org/0000-0002-1073-7386
Václav Valeš − J. Heyrovský Institute of Physical Chemistry,
Czech Academy of Sciences, CZ-182 23 Prague 8, Czech
Republic
Otakar Frank − J. Heyrovský Institute of Physical Chemistry,
Czech Academy of Sciences, CZ-182 23 Prague 8, Czech
Republic; orcid.org/0000-0002-9661-6250
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.1c05054
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors acknowledge financial support from the Czech
Science Foundation (project no. 20-08633X). The synthesis of
graphene by O. Volochanskyi and Dr. K. Drogowska-Horná is
gratefully acknowledged.
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