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A new protocol for the distribution of MnO 2

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electrochemical...

Article in Applied Surface Science · March 2017

DOI: 10.1016/j.apsusc.2016.12.086

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 Applied Surface Science 399 (2017) 95–105

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Full Length Article

A new protocol for the distribution of MnO2 nanoparticles on rGO

sheets and the resulting electrochemical performance
Jitendra Samdani a , Kunda Samdani a , Nam Hoon Kim a , Joong Hee Lee a,b,∗
a
Department of BIN Convergence Technology, Chonbuk National University, Jeonju, Jeonbuk, 561-756, Republic of Korea
b
Center for Carbon Composites Materials, Department of Polymer & Nano Science and Technology, Chonbuk National University, Jeonju, Jeonbuk, 561-756,
Republic of Korea

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

Article history: Herein, reduced graphene oxide (rGO)/MnO2 hybrid materials were prepared via a direct redox reac-
Received 3 June 2016 tion between MnCl2 and KMnO4 on reduced graphene oxide (rGO). A systematic study was carried out
Received in revised form to understand the role of KMnO4 . The morphology and microstructure of the as-prepared composite
18 November 2016
was characterized using field-emission scanning electron microscopy (FESEM), transmission electron
Accepted 11 December 2016
microscopy (TEM), X-ray diffraction (XRD) and Raman Spectroscopy. Results indicate that the concen-
Available online 13 December 2016
trations of KMnO4 have a detrimental effect on the distribution of MnO2 nanoparticles on rGO sheets
and hence on electrochemical properties. The electrochemical capacitive behavior of the as-prepared
Keywords:
rGO/MnO2 composite was investigated using cyclic voltammetry (CV), galvanostatic charge discharge, and electro-
Supercapacitor chemical impedance spectroscopy (EIS) in 1 M Na2 SO4 aqueous electrolyte solution. At the optimum
Biosensor concentration of KMnO4 , the as-prepared rGM-1 composite shows a high specific capacitance of 366 F/g
Dopamine at a scan rate of 10 mV/s. The composite also exhibits good electrocatalytic activity towards the oxidation
of dopamine (DA), exhibiting a low detection limit of 2.3 × 10−7 M with a wide linear range between
2.5 × 10−7 M and 2.30 × 10−4 M. Hence, the use of rGO/MnO2 at an optimized concentration of KMnO4 is
a potential competitive candidate in supercapacitor and biosensor applications.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction als via the introduction of carbonaceous materials and conducting

Manganese oxide are a class of materials that attract great inter-
est as a transition metal oxide because of their high applicability in
various domains. Generally, manganese oxides possess structural
versatility, as well as the numerous attainable oxidation states of
Mn, such as +2, +3, or +4; further, there may be two or three valence
states coexisting in the same crystalline structure [1]. Thus, exten-
sive research on manganese oxides has been carried out in various
fields such as energy storage [2,3], rechargeable Li-ion batteries [4]
electrocatalytic oxygen reduction [5], catalysis [6], electrochemi-
cal and biosensing [7,8]. Despite the various applications, the poor
conductivity of MnO2 (10−5 –10−6 S/cm) restricts its utilization in
various electrochemical applications, and improving its conductiv-
ity remains a significant challenge [9]. The electrical conductivity of
MnO2 is typically improved via the incorporation of noble metals
into MnO2 compounds [10] and the synthesis of hybrid materi-
∗ Corresponding author at: Department of BIN Convergence Technology, Chonbuk
National University, Jeonju, Jeonbuk, 561-756, Republic of Korea.
E-mail address: jhl@chonbuk.ac.kr (J.H. Lee).
polymers [11,12]. Recently, many efforts have focused on devel-
oping nanocomposites of carbonaceous/MnO2 hybrid materials;
among these, a graphene/MnO2 hybrid material has been exten-
sively synthesized and utilized in electrochemical applications such
as supercapacitors and biosensors [13,14].
The supercapacitor or electrochemical capacitor (EC) is one of
the most promising energy storage devices due to its high power
density, high energy density, fast charge-discharge cycles, and
high stability [15–17]. Depending on the charge storage mech-
anism, supercapacitors are classified into two groups: electrical
double-layer capacitors (EDLCs) and pseudocapacitors. The electric
double-layer capacitor mechanism works on the adsorption-
desorption phenomenon, and is based on charge separation at
the electrode-electrolyte interface. Pseudocapacitors are based on
the (faradic) redox reactions occurring in the electrode material.
Chen et al. produced ␣–MnO2 /graphene sheet composites using
excessive amounts of GO and a specific amount of KMnO4 in
a hydrothermal reactor at 200 ◦ C with a specific capacitance of
116 F/g at 1 mA [18]. Further, Li et al. synthesized hydrothermally-
reduced graphene (HRG), which was then used for the deposition
of MnO2 via the use of a KMnO4 and K2 SO4 mixture for vari-

http://dx.doi.org/10.1016/j.apsusc.2016.12.086
0169-4332/© 2016 Elsevier B.V. All rights reserved.
96 J. Samdani et al. / Applied Surface Science 399 (2017) 95–105
ous periods of time at room temperature; the capacitance value
was 211.5 F/g at 2 mV/s [19]. Deng et al. studied various concen-
trations of KMnO4 while synthesizing MnO2 nanorods/graphene
composites and found that the amount of KMnO4 alters the aspect
ratios of MnO2, which in turn affects the specific capacitance of the
MnO2 /graphene composite [20].
Electrochemical techniques have been widely used for the
detection of electroactive species such as biomolecules. Sev-
eral methods have been developed for the determination of
biomolecules, including high performance liquid chromatogra-
phy [21], chemiluminescence [22], and gas chromatography–mass
spectrometry [23]. However, electrochemical sensors are a pre-
ferred alternative method because of their simple operation, fast
response time, low cost, high sensitivity, excellent selectivity and
real-time detection [24]. Dopamine (DA) is an important neuro-
transmitter molecule of catecholamine, its deficiency leads to brain
disorders such Parkinson disease, and an excess of DA can lead to
schizophrenia [25–27]. The electrochemical behavior of dopamine
plays important roles in its physiological functions and is a key
factor in the diagnosis of some diseases in clinical medicine [28].
Owing to the strong electrochemical activity of DA, the determina-
tion of DA at a sub-micro molar concentration has gained immense
attention among researchers. Fooladsaz et al. [29] modified carbon
paste with ZnO nanoparticles and Peik-see et al. [30] developed the
Fe3 O4 /rGO/GCE electrode for the detection of DA. Further, Huang
et al. fabricated MnO2 nanowires/chitosan-modified gold (Au)
electrodes for the amperometric determination of DA [31]. Yang
et al. proposed that three-dimensional (3D) ternary Pt nanoden-
drite/reduced graphene oxide/MnO2 nanoflowers (Pt/RGO/MnO2 )
modified as glassy carbon electrodes can be used for the selective
and sensitive determination of DA [14]. Recently, Guo et al. reported
the use of 3D porous CNT/MnO2 for biosensors and supercapacitors
[32].
The present study focuses on the synthesis of a reduced
graphene oxide (rGO)/MnO2 nanocomposite with various com-
posite ratios, as well as its application in supercapacitors and DA
biosensors. Herein, MnO2 was prepared via the redox reaction
between MnCl2 and KMnO4 on reduced graphene oxide (rGO).
In this respect, it is highly probable that due to the various con-
centrations of KMnO4 , the deposition of MnO2 onto rGO will
produce a significant change in the carbon bonding structure and
consequently the electrochemical properties of the rGO/MnO2
composite. The rGO/MnO2 composite was drop-casted on the Ni-
foam to fabricate the electrode material for supercapacitive study
using cyclic voltammetry (CV) and galvanostatic charge-discharge
(GCD) techniques. The specific capacitance at optimum concentra-
tions of KMnO4 was found to be 366 F/g at a scan rate of 10 mV/s
and 208.3 F/g at a current density of 1 A/g. Further, hybrid materi-
als were drop-casted onto the glassy carbon electrode (GCE) for
the detection of DA via CV, differential pulse voltammetry, and
amperometric i-t curves. The prepared rGO/MnO2 composite was
successfully used for the supercapacitor as well as biosensing appli-
cations.
2. Experimental
2.1. Materials
Graphite powder, manganese chloride tetrahydrate, NaH2 PO4 ,
Na2 HPO4, ascorbic acid (AA), Dopamine, and Glucose were pur-
chased from Sigma-Aldrich (Germany). Other chemicals such as
sodium sulfate and potassium permanganate were purchased from
Samchun Pure Chemical Co. Ltd. (Korea) and Junsei Chemical Co.
Ltd. (Japan), respectively. Aqueous 1 M Na2 SO4 was used as the
supporting electrolyte for the electrochemical measurements. A
buffer solution (PBS, 0.2 M, pH = 7.2) was prepared from NaH2 PO4
and Na2 HPO4 . Millipore water (Milli-Q system) was used for the
preparation of the solutions.
2.2. Synthesis of graphene oxide (GO)
The modified Hummer’s method was employed to prepare
graphene oxide using the graphite powder. Briefly, 2.0 g of graphite
powder were added to 46 mL of concentrated sulphuric acid in an
ice bath, to which 6.0 g of KMnO4 were added slowly over 30 min,
followed by stirring for 2 h at 0–5 ◦ C. The dark-green reaction solu-
tion was then transferred to a preheated oil bath at 35 ◦ C and stirred
for 3 h. Approximately 92 mL of distilled water were added slowly
and stirred for another 1 h. Another 280 mL of distilled water were
added to the above mixture, followed by the addition of 35% hydro-
gen peroxide to remove excess KMnO4 . The color of the dark brown
reaction mixture changed to bright yellow [33]. Finally, the result-
ing product was mixed with 5% HCl and washed repeatedly with
distilled water until the supernatant reached a pH of 7 and was later
dried under vacuum at 50 ◦ C for 72 h.
2.3. Synthesis rGO-MnO2 nanoparticles composite
The rGO-MnO2 nanocomposite was synthesized via a simple
reflux method. In detail, 50 mg of GO were dispersed into 50 mL of
water via ultrasonication for 30 min. Ammonia (28 wt.% in water)
was added to the dispersion to adjust the pH to approximately 11.
Then, 1 mM MnCl2 ·4H2 O and x mM KMnO4 (x = 0.66, 1 and 2 mM)
were added to the above dispersion and stirred for half an hour.
Next, 0.5 mL hydrated hydrazine was added and refluxed for 12 h at
80 ◦ C. The above as-synthesized materials were washed with water
and dried at 60 ◦ C in an oven for 12 h and denoted as rGM-0.66, rGM-
1, and rGM-2. The synthesized materials were physico-chemically
characterized via X-ray Diffraction (XRD), Raman, FE-SEM, and TEM
analysis.
2.4. Characterization
X-ray diffraction (XRD) patterns were recorded using a
Max 2500V/PC (Rigaku Corporation, Tokyo, Japan). The spectra
were recorded at a scan rate of 2◦ /min with a Cu-Ka target
(␭ = 0.15406 nm) operating at a voltage of 40 kV and a current of
100 mA. Raman spectra were recorded using a Nanofinder 30 sys-
tem (Tokyo Instruments Co., Osaka, Japan). The surface morphology
of the samples was investigated via field emission transmission
electron microscopy (FESEM) (FE-SEM; JEOL JEM-2200 FS, Japan).
The particle sizes and shapes were investigated through TEM anal-
ysis with an H-7650 (Hitachi Ltd., Japan) at KBSI, Jeonju Center.
Electrochemical measurements were carried out using a CHI660D
electrochemical analyzer (CH Instruments, Austin, TX, USA). Cyclic
voltammograms were recorded using a two-compartment three-
electrode cell where materials drop-casted on Ni foam was used as
the working electrode.
2.5. Electrochemical measurement
The fabrication of working electrodes was carried out as fol-
lows. The as-prepared materials, carbon black, and poly (vinylidene
fluoride) (PVDF), were mixed at a mass ratio of 80:10:10 and
dispersed in N-methylpyrrolidone (NMP). The resulting mixture
was then drop-casted onto a nickel foam substrate (1 cm × 1 cm)
and dried in a vacuum oven at 60 ◦ C overnight. The loading mass
of each electrode was ca. 3 mg. To investigate the electrochemi-
cal behavior of the as-prepared samples, cyclic voltammetry (CV),
galvanostatic charge/discharge experiments, and electrochemical
impedance spectroscopy (EIS) measurements were conducted in
 J. Samdani et al. / Applied Surface Science 399 (2017) 95–105
the three-electrode mode using the as-prepared samples, plat-
inum foil, and Ag/AgCl (KCl-saturated) as the working, counter,
and reference electrodes, respectively. The measurements were
carried out in a 1 M Na2 SO4 aqueous electrolyte at room temper-
ature. The CV, galvanostatic charge/discharge characteristics, and
EIS measurements were performed using a CHI 660D electrochemi-
cal workstation. The EIS measurements were recorded under an AC
voltage amplitude of 5 mV in the frequency range of 105 –0.01 Hz
and an open circuit potential.
For the detection of DA, a modified or unmodified glassy carbon
electrode (GCE) (3 mm diameter) was used as a working electrode.
Prior to modification, the GC electrode was polished with a 0.50 mm
alumina slurry and then rinsed thoroughly with water. The elec-
trode was then sonicated in deionized water for 30 min to remove
the adsorbed alumina particles. As prepared rGM composite was
dispersed in 1 mL of 0.1% nafion solution (10 mg/ml). The above
suspensions (20 ␮L) were dropped onto the clean GCE and dried at
room temperature. Three electrodes were then rinsed with twice
deionized water and submitted to binding and selective recogni-
tion experiments. The CV and DPV measurements were carried out
by potential scanning repeatedly between −0.2 to 0.8 V at a scan
rate of 100 mV/s.
3. Results and discussion
3.1. Structure and morphology
In order to demonstrate the effects of KMnO4 , various reactions
with varying concentrations were carried out. It is well known that
the deposition of MnO2 on rGO takes place as follows: [34] Eq. (1)
3MnCl2 + 2KMnO4 + 2H2 O = 5MnO2 + 2K+ + 6Cl− + 2H+
In this redox reaction Mn2+ is oxidized and Mn7+ is reduced to
form Mn4+ . Herein, to the some extent MnO6 octahedral geometry
shares the oxygen atoms from graphene oxide. As a result, the con-
centration of KMnO4 affects the distribution of MnO2 on the surface
of rGO as well as its attachment to rGO, as shown in Scheme 1.
XRD was employed to characterize the crystal phase of the as-
prepared materials. The typical XRD spectra of rGM-0.66, rGM-1,
and rGM-2 are shown in Fig. 1a. It was observed that in the case of
rGM-0.66, all peaks near 18◦ , 32◦ , 37◦ , and 60◦ are indexed to MnO2 ,
whereas a peak can be seen at 24◦ for rGO. This proves that MnO2
did not completely bind with the rGO and loosely adsorbed/bonded
to its surface. This observation was further confirmed using SEM
and TEM. Upon increasing the concentration of KMnO4 , its reactiv-
ity towards MnCl2 and rGO increases and the structure changes
from crystalline to amorphous. At a concentration of 1 mM, the
MnO2 is well attached to the rGO and slightly loses its crystallinity,
as can be seen in Fig. 1a, whereas at a concentration of 2 mM,
the MnO2 nanoparticles bonded well with rGO and became highly
amorphous.
Fig. 1b shows the Raman spectra of rGM-0.66, rGM-1, and rGM-
2. Raman spectroscopy provides information on the structural
properties of the carbonaceous materials, including the amounts
of disorder, defects, and imperfections in the structures. All of the
Raman spectra are dominated by the two well-understood G and
D peaks found in all graphene-like systems. It is known that the G
band corresponds to the first-order scattering of the E2g phonon
of the sp2 carbon domains in a two-dimensional hexagonal lat-
tice, whereas the D band comes from the disorder-induced mode
associated with structural defects and imperfections. Therefore, the
intensity ratio I(D)/I(G) has been generally used as a standard to
evaluate the quality of graphitic structures [35,36]. The calculated
I(D)/I(G) ratios of rGM-0.66, rGM-1, and rGM-2 were 1.16, 1.14, and
1.14, respectively. This ratio indicates that the defects and imper-
97
fections are almost the same for all composites, since the hydrazine
quantity added is the same in all composites. As the synthesized
composites rGM-0.66 and rGM-2 exhibit D peaks at 1349.67 cm−1 ,
the D peak of rGM-1 cm−1 can be seen at 1343.30; this may be due
to the different interactions between KMnO4 and MnCl2 on the
surface of rGO. The G-peaks of rGM-0.66, rGM-1, and rGM-2 can
be observed at 1583.32, 1580.63, and 1590.19 cm−1 , respectively.
The G peak position in rGM-2 was shifted by 7 and 10 cm−1 when
compared to rGM-0.66 and rGM-1. This shift is attributed to the
presence of MnO2 in the interlayer of rGO in the rGM-2 composite
material. In the prepared composite, rGM-0.66 and rGM-2, a Raman
band can be observed at 639 cm−1 , which is due to the symmetric
stretching vibration (Mn O) of the MnO6 groups [37]. In case of
rGM-1, the Raman band at 628 cm−1 which shows the slightly dif-
ferent spectra resulting from rGM-0.66, and rGM-2. This variation is
further confirmed via the morphological study of prepared hybrid
materials.
The morphologies of the as-prepared composites were exam-
ined using FESEM and TEM, as shown in Fig. 2. The FESEM images
clearly show the effects of KMnO4 on the density and attachment
of MnO2 to rGO. As the concentration of KMnO4 is increased, both
the density of MnO2 and the interlayer distance in the graphene
sheet increases, which is in accordance with the XRD spectrum.
Hence, the concentration of KMnO4 plays a crucial role during the
synthesis of MnO2 , and it is embedded into the graphene layer. The
morphology of rGM-0.66 shows a simple superficial attachment of
MnO2 to rGO, whereas in rGM-1 graphene and the MnO2 nanopar-
ticles were interconnected and formed a 3D network structure. At
very high concentrations of KMnO4 (rGM-2), the MnO2 nanoparti-
cles were deeply embedded into rGO via breaking of the graphene
sheet, as shown in Fig. 2c. TEM was carried out to further exam-
(1) ine the architecture of the obtained rGM-0.66, rGM-1, and rGM-2
materials. Fig. 2d shows that the MnO2 particles are superficially
attached to the graphene, whereas the MnO2 particles in rGM-1
are distributed throughout the graphene layers (Fig. 2e), similar to
SEM. The inset of Fig. 2e at high resolution clearly shows graphene
layers in the rGM-1 material, whereas in rGM-2, the MnO2 parti-
cles are deeply embedded in the graphene sheet via the breaking
of graphene layers (Fig. 2f).
3.2. Electrochemical properties
3.2.1. Supercapacitor
The capacitive performance of the materials used in this
study were investigated via cyclic voltammetry (CV), galvanostatic
charge-discharge, and electrochemical impedance spectroscopy in
a 1 M Na2 SO4 solution. Fig. 3a shows the CV-curves of the as-
prepared composite based on a three-electrode configuration at
a scan rate of 10 mV/s in the potential range between −0.2 to
0.8 V (vs. Ag/AgCl). As shown in Fig. 3a, the CV curve of rGM-0.66
reveals a nearly symmetrical rectangular shape without obvious
redox peaks, whereas rGM-2 shows a slightly distorted symmetri-
cal rectangular shape. The CV-curve of rGM-1 exhibits a distorted
rectangular shape. To verify the rectangular shape, CV was carried
out at scan rates of 5, 10, 25, 50, 75, and 100 mV/s for all materi-
als (Fig. 3b–d, respectively). In Fig. 3b, the symmetrical rectangular
shape of rGM-0.66 results in the current increasing with an increas-
ing scan rate, maintaining its symmetrical rectangular shape at low
as well as high scan rates. This shows the pseudocapacitance of
MnO2 via surface adsorption reaction (Eq. (2)) [38] and the intrinsic
electrical double-layer capacitance of rGO. The symmetrical rectan-
gular shape at lower and higher scan rates also indicates the ideal
capacitive behavior of the supercapacitor [39]. The rGM-1 com-
posite exhibited a distorted rectangular shape at low scan rates
and changed with increasing scan rates to a distorted symmetrical
rectangular shape (Fig. 3c), indicating that the pseudocapacitance
98 J. Samdani et al. / Applied Surface Science 399 (2017) 95–105

Scheme 1. Schematic representation of the formation of rGO-MnO2 composite at various concentrations of KMnO4 .

Fig. 1. (a) XRD patterns (b) Raman Spectrum of the rGM-0.66, rGM-1, and rGM-2.

of MnO2 follows the redox intercalation-deintercalation reaction of
electrolyte into the MnO2 (Eq. (3)) [40]. However, at high scan rates,
the electrical double layer capacitance of rGO also contributes and
a distorted symmetrical rectangular shape was obtained. The dis-
torted symmetrical rectangularity of rGM-2 (Fig. 3d) was preserved
through low and high scan rates, suggesting the pseudocapacitance
of MnO2 via the intercalation-deintercalation of electrolyte ions
and the electrical double layer capacitance of rGO.
(MnO2 )surface + Na+ + e−  (MnOONa)surface
MnO2 + Na+ + e−  MnOONa
The specific capacitance (Cs ) of the as-prepared composite was
calculated from the CV-curve using Eq. (4) [41]:

IdV
Cs = (4)
m ×  × V
where I represents the response current (A), V is the potential
window (V),  is the scan rate (V/s), and m is the mass of active
material in the electrode (g). The specific capacitance values of the
(2) as-prepared composites rGM-0.66, rGM-1, and rGM-2 are 245.7,
366, and 275 F/g, respectively, at a scan rate of 10 mV/s. rGM-1
(3) exhibits superior specific capacitance when compared to the other
 J. Samdani et al. / Applied Surface Science 399 (2017) 95–105
Fig. 2. FE-SEM images of (a) rGM-0.66, (b) rGM-1, and (c) rGM-2, and TEM images of (d) rGM-0.66, (e) rGM-1, and (f) rGM-2.
two electrodes, which is attributed to the uniform morphology and
distribution of MnO2 nanoparticles on rGO.
Further, galvanostatic charge-discharge measurements were
conducted for all materials at a current density of 1 A/g. Fig. 4a
shows that during the charging and discharging steps, and the
charge curve of rGM-0.66 was symmetric to its corresponding dis-
charge counterpart; in the case of rGM-2, the charge curve was
nearly symmetric with its discharge counterpart with a slight cur-
vature, pointing to the high reversibility of the hybrid materials
[42]. However, the charge curve of rGM-1 was symmetric with its
discharge counterpart with a curvature; this is in good agreement
with the CV-curves of rGM-1 in Fig. 3a and c. Due to the superior
response of rGM-1, it was thoroughly studied by varying the current
density to 0.5, 1, 2, 3, 4, and 5 A/g (Fig. 4b). It was observed that as
the current density increased, the time required for charging and
discharging decreased (Fig. 4b and inset). This may be a result of
the electrolyte ions not being able to enter the internal structure of
the MnO2 at a high current density and following the surface redox
reaction. The specific capacitances (Cs ) were calculated from the
charge-discharge curve according to Eq. (5) [41]:
I × t
Cs =
m × V
where I represents the applied current (A), t is the discharge time
(s), m is the mass of the material (g), and V is the potential win-
dow (V) used for the charge-discharge. The specific capacitances of
the as prepared rGM-0.66, rGM-1, and rGM-2 composites are 133.3,
208.3, and 138.8 F/g respectively, and these are in good agreement
with Cs values from the CV-curve. The as-prepared rGM-1 compos-
99
ite possess a higher pseudocapacitance behavior (according to Eq.
(3)) than that of rGM-2 and rGM-0.66; this may due to the even
distribution of MnO2 particles on the rGO.
The relationship between the specific capacitance and current
density of the as prepared composites is shown in Fig. 5a. The
obvious decay of specific capacitance was observed at higher cur-
rent densities, whereas a low current density contributes to the
relatively slow current accumulating process. This facilitates full
access of active sites on the electrode, thereby resulting in high spe-
cific capacitance, which was also confirmed from the relationship
between specific capacitance and scan rate, as shown in Fig. 5b.
Electrochemical impedance spectroscopy (EIS) measurements
were carried out at an open circuit potential with an AC volt-
age amplitude of 5 mV and a frequency range of 100 kHz–0.01 Hz.
The impedance plot shows a semicircle at high frequency and a
nearly vertical line at low frequency. The intercept at the real axis
represents the internal resistance (Rs ), and the diameter of the
semicircle indicates the charge transfer resistance (Rct ) [43]. MnO2
was deposited in the interlayer of rGO in the rGM-2 composite,
therefore Rs and Rct were smaller than those of the rGM-0.66 and
rGM-1 composites, as shown in Fig. 5c. This also supports that the
specific capacitance value of rGM-1 will be higher. Similar obser-
(5)
vations can be drawn from the impedance spectra of rGM-0.66.
Determining the cycling stability of an electrode material via
galvanostatic charge-discharge is a significant factor in the study
of supercapacitors; hence, measurements of the cycle stability of
as-synthesized hybrid materials were carried out by galvanostatic
charge-discharge tests at a current density of 5 A/g for 1000 cycles
(Fig. 5d). The 100% retention observed in the rGM-0.66 compos-
100 J. Samdani et al. / Applied Surface Science 399 (2017) 95–105

Fig. 3. (a) Comparison of CV curves of rGM-0.66, rGM-1, and rGM-2 at a constant scan rate of 10 mV/s. (b) CV curves of rGM-0.66, (c) rGM-1, and (d) rGM-2 at various scan
rates of 5, 10, 25, 50, 75, and 100 mV/s.

Fig. 4. (a) Galvanostatic charge-discharge for rGM-0.66, rGM-1, and rGM-2 at 1 A/g, and (b) rGM-1 at various current densities of 0.5, 1, 2, 3, 4, and 5 A/g (the inset shows
galvanostatic charge-discharge in the range of 2–5 A/g).
 J. Samdani et al. / Applied Surface Science 399 (2017) 95–105 101

Fig. 5. (a) The relationship between specific capacitance and current density, (b) relationship between specific capacitance and scan rate, (c) Nyquist plots in the frequency
range from 0.01 Hz to 105 Hz with an amplitude of 5 mV, and the (d) cycle-performance of various composites over 1000 cycles at a current density of 5 A/g.

ite was attributed to the pseudocapacitance of MnO2 followed by a
surface redox reaction and the electrical double layer of rGO. The as-
synthesized rGM-1 and rGM-2 hybrid materials show retentions of
75.8% and 89.3%, respectively, which suggests that the supercapac-
itor behavior is due to the faradaic reaction of MnO2 through the
intercalation-deintercalation of electrolyte ions. It is well known
that rGO-MnO2 materials exhibit good stability but have a low spe-
cific capacitance due to the carbonceous material. Our results are in
good agreement with results reported in relevant literature; there-
fore, optimization between a high specific capacitance and longer
cycling life is an important parameter for practical applications
of supercapacitors. It is worth comparing the specific capacitance
and cycle stability of as-synthesized rGO/MnO2 composites with
previously reported materials (Table S1).
3.2.2. Biosensors
The electrocatalytic performance of the bare GCE and various
rGM/GC electrodes toward the oxidation of DA was investigated
using cyclic voltammetry. Fig. 6a shows the CV responses of 100 ␮M
DA in PBS (pH 7.2) at bare GCE, rGM-1/GC, rGM-2/GC, and rGM-
0.66/GC, respectively. No peaks were observed in the absence of
DA at modified electrodes (inset of Fig. 6a), whereas upon the addi-
tion of DA, a couple of small oxidative and reductive peaks were
obtained at all rGM/GC electrodes. A significant enhancement was
observed in the DA oxidation current at the rGM-1/GC (17.76 ␮A)
when compared to that of rGM-2/GC (11.14 ␮A), rGM-0.66/GC
(13.62 ␮A), and bare GCE (1.81 ␮A), respectively. The observed
improvement in the oxidation current and lowering of over poten-
tial could be attributed to the larger electro-active area and higher
catalytic efficiency of rGM-1. The superior electrochemical perfor-
mance of the rGM-1/GC could be attributed to the even distribution
of MnO2 on rGO, which was not observed in the case of rGM-2/GC
and rGM-0.66/GC. These results are in good agreement with super-
capacitor behavior (Section 3.2.1). As illustrated in Section 3.1, the
rGM-1 composite could provide a larger electrochemically active
surface area than those of rGM-2 or rGM-0.66. Furthermore, with
bare GCE the oxidation of DA is observed at 0.33 V, alternatively,
with the modified electrode (rGM-1/GC) the oxidation of DA is
observed at 0.28 V in the presence of 100 ␮M DA. A 50 mV shift
in the negative direction was observed and is due to the MnO2 ,
which acts not only as an electron mediate but also as a cata-
lyst [44]. Experimental results show reproducible and well-defined
anodic and cathodic peaks with an Epa, Epc, and E◦ of 0.28, 0.21,
and 0.245 V, respectively. The observed peak separation potential,
Ep = (Epa − Epc) of 70 mV, was greater than the value of 59/n mV
expected for a reversible system [45], suggesting that the redox
couple of DA in rGM-1/GC has a quasi-reversible behavior in an
aqueous medium. It was also confirmed that the peaks in the CV
curve were assigned to the oxidation of DA and not to the oxi-
dation of Mn [46,47]. Good synergistic effects emerged between
the MnO2 and graphene sheets, enhancing the conductive area and
electron transfer rate between DA and the electrode surface. When
102 J. Samdani et al. / Applied Surface Science 399 (2017) 95–105

Fig. 6. (a) Electrochemical detection of 100 ␮M DA in 0.2 M PBS (pH = 7.2) at a scan rate of 100 mV/s, inset: CV curves of rGM-1, rGM-2, and rGM-0.66 in 0.2 M PBS without
DA, (b) effect of the scan rate from 10 mV/s to 500 mV/s, in 0.2 M PBS (pH = 7.2), (c) the plot of the peak current vs. , (d) the plot of Ep vs. log , (e) the plot of Epa and Epc vs.
log , (f) DPV curve for various concentrations of DA (2.5–475 ␮M) on the rGM-1/GC, (inset represents a calibration curve of DPV analysis).

a potential is applied to the electrode, DA is easily oxidized to form The effects of the potential scan rate on the electrochemical
dopamine-o-quinone (DAQ) after an exchange of 2 electrons and properties of the rGM-1/GC were also studied via CV in 0.2 M PBS
2 protons (Scheme 2). These electrons are later donated to the at pH = 7.2. The results show an increase in the both anodic and
electrode and produce a faradaic current [48,49]. cathodic peak currents (Ip) with an increase in scan rate () in
 J. Samdani et al. / Applied Surface Science 399 (2017) 95–105
Scheme 2. Plausible oxidation mechanism of dopamine at the rGM/GC modified electrode.
Fig. 7. (a) Amperometric i–t curve for the determination of DA at the rGM-1/GC in a 0.2 M PB solution (pH 7.2) with concentration ranges between 0.25 ␮M to 230 ␮M at
intervals of 50 s and at a potential of 0.23 V. Inset (a): plot of the concentration of DA vs. current. (b) Amperometric response of the rGM-1/GC composite to the addition of
DA in the presence of interfering compounds (10 fold of UA and Glu).
the range of 10–500 mV/s (Fig. 6b and c), with the linear regres-
sion equation Ip (␮A) = 0.2811x (mV/s) + 9.2633, R2 = 0.9951 (for
oxidation peak current) and Ip (␮A) = −0.2815x (mV/s) − 7.2404,
R2 = 0.9939 (for reduction peak current). This indicates that the
redox process of DA at the modified electrode is diffusionless in
nature. The kinetic parameters of ␣ and ks can be calculated using
Laviron’s model [50]:
◦ RT ␣c
Epc =E + ln
␣c nF m
◦ RT ␣a
Epa = E + ln
␣a nF m
 RT 
logks = ␣ log (1 − ˛) + (1 − ˛) log ␣ − log − ␣ (1 − ˛)
nFϑ
nFEp
2.3RT
where m = (RT/F)(ks /n␣), ks is the apparent charge transfer rate
constant, ␣ is the charge transfer coefficient, n is the number
of electrons transferred in the rate-determining reaction, Ep is
the peak potential separation, R, T, and F have their usual mean-
ings (R = 8.314 J/mol/K, T = 298 K, F = 96,483 C/mol), and  is the
scan rate. It was observed from Fig. 6d that for higher scan rates,
the values of Ep were proportional to log . The plot of Ep = f
(log ) (Fig. 6e) yields two straight lines with slopes equal to
−2.3RT/␣c nF and 2.3RT/␣a nF for the cathodic and anodic peaks,
respectively. Hence the value of ␣ can be calculated using the
above mentioned slopes. Based on Eq. (8), an average value of ks
was determined to be 0.612 cm/s. This value is higher than the
value reported by Huang et al. [48] (9.1 × 10−4 cm/s), indicating that
the rGM-1/GC modified electrode exhibited a fast electron trans-
103
fer rate towards the electrochemical oxidation of DA compared to
the MnO2 nanowires/chitosan-modified electrode. For a reversible
surface reaction, the peak current is given in Eq. (9) [51]:
n2 F2 ϑAc
Ip = (9)
4RT
The surface concentration of the electroactive species (c) can
be estimated from the slope of peak currents vs. the scan rate plot
(6)
(Fig. 6c). Here,  is the sweep rate, A is the surface area of the mod-
ified electrode, and the other variables have their usual meanings.
(7) From the slope of the cathodic peak currents vs. scan rate, the calcu-
lated surface concentration of DA is 2.49 × 10−6 mol/cm2 . DPV was
used for the determination of DA at the modified electrode for its
higher current sensitivity and better resolution when compared to
CV. The DPV measurement was carried out in 0.2 M PBS (pH = 7.2)
via repeated potential scanning between 0.0 and 0.6 V.
(8)
Fig. 6f shows that the DPV peak current responses towards
DA were higher at the modified electrode; this indicates better
immobilization and a superior binding capacity for the template
molecules. The oxidation of DA occurred at 0.23 V, with a well-
defined inverted ‘V’-shaped voltammogram and a stable response.
As shown in the inset of Fig. 6f, the calibration curves for DA detec-
tion via DPV are linear from 2.5 ␮M to 475 ␮M.
Fig. 7a shows the typical amperometric response curve (i-t
curve) towards the oxidation of DA at the rGM-1/GC in 0.2 M PBS
that is obtained by applying a potential of 0.23 V. Sequential addi-
tions of various concentrations of DA to the electrode provoked
dramatic increases in the current, and the time required to reach the
98% steady state response was less than 3 s. Each addition increased
the concentration of DA to 0.25, 0.75, 1.75, 3.25, 5.75, 9.75, 14.75,
22.25, 32.25, 44.75, 59.75, 79.75, 104.75, 129.75, 154.75, 179.75,
104 J. Samdani et al. / Applied Surface Science 399 (2017) 95–105
204.75, and 229.75 ␮M at the rGM-1/GC in a 0.2 M PBS (pH 7.2) at
intervals of 50 s. The inset of Fig. 7a shows that the amperometric
current response increased linearly with increasing DA concentra-
tions between 0.25 ␮M and 230 ␮M, while its sensitivity dropped at
higher DA concentrations (>50 ␮M); this could be attributed to the
limited available electrode surface for electro-chemical reactions
to take place, similar to the previous report [31,52]. The modified
electrode yielded a significantly low detection limit of 2.3 × 10−7 M
at a signal-to-noise ratio of three, compared to data previously
reported in literature (Table S2). To evaluate the selectivity of the
proposed biosensor, possible interfering biomolecules, uric acid
(UA), and glucose (Glu), which normally coexist with DA in real
samples (human blood and urine), were examined [53]. An amper-
ometric response of DA in the presence of 10-fold excess of UA and
Glu was tested in PBS (pH 7.2). No incremental variation in amper-
ometric current was observed at the modified electrode for UA and
Glu at added concentrations (Fig. 7b). These results indicate that
the modified electrode is highly selective for DA.
4. Conclusions
In summary, rGO/MnO2 hybrid materials were successfully pre-
pared via a direct redox reaction between MnCl2 and KMnO4 on
the surface of reduced graphene oxide (rGO). It was observed that
variations in the concentration of KMnO4 significantly affects the
structural, and thereby also the electrochemical, properties of the
composite. The specific capacitance of the rGM-1 hybrid mate-
rial (366 F/g) is higher than that of rGM-0.66 and rGM-2, due to
the pseudocapacitance of MnO2 carried out via the intercalation-
deintercalation of electrolyte ions into MnO2 . Since the rGM-1
composite shows good specific capacitance as well as high stabil-
ity, it was further analyzed for use in biosensor applications. The
rGM-1 composite exhibits a low detection limit of 0.23 ␮M with a
wide liner range between 0.25 ␮M and 230 ␮M, and a high electron
transfer rate constant (0.612 cm/s). This kind of rGO/MnO2 hybrid
material paves the way for the use of KMnO4 in the deposition of
MnO2 and its application in supercapacitors and biosensors.
Acknowledgement
The authors would like to acknowledge support from the
Basic Research Laboratory Program (2014R1A4A1008140)
and the Nano-Material Technology Development Program
(2016M3A7B4900117) through the National Research Foundation
(NRF) funded by the Ministry of Education of Korea.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apsusc.2016.12.
086.
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