Journal of Electroanalytical Chemistry 902 (2021) 115776

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Journal of Electroanalytical Chemistry

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

One-pot green synthesis of graphene oxide/MnO2/polyaniline

nanocomposites applied in aqueous and neutral supercapacitors and sensors
Gabriel Zeplin, Eduardo G.C. Neiva ⇑
Departamento de Química, Universidade Regional de Blumenau (FURB), CEP 89012900, Blumenau, SC, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: Different binary and ternary nanocomposites among graphene oxide (GO), manganese dioxide (MnO2)
Graphene oxide nanoparticles and polyaniline (Pani) were synthesized in aqueous medium and room temperature using
Manganese dioxide KMnO4 as oxidizing agent for aniline and precursor for MnO2 in the presence of GO. The ratio between the
Polyaniline constituents was directly dependent on the HCl concentration and aniline amount used in the synthesis.
Aqueous supercapacitor
Indeed, the lower the acid concentration, the greater the MnO2 ratio (∼65% using 0.01 mol L−1 HCl). The glob-
Hydrogen peroxide sensor
ular morphology of Pani presented higher degrees of polymerization and larger size of spheres according to the
increase of acid concentration. MnO2 nanoparticles exhibited a birnessite structure with a mean size of ∼ 1 nm
well spread throughout the polymer matrix. The multifunctionality of the nanocomposites was evaluated in
neutral aqueous solutions as supercapacitors and electrochemical sensors to H2O2. In both cases, the nanocom-
posites with the highest MnO2 proportion exhibited the best performances, reaching capacitances as high
as ∼ 150 F g−1 with 68.2% of stability under 500 charge–discharge cycles and limit of detection as low as
3.03 ± 0.22 μmol L−1 for the ternary nanocomposites.

1. Introduction accommodate these ions [13,17,18]. In fact, Devaraj et al. evaluated

the effect of the crystallographic structure of MnO2 on its pseudocapac-
Manganese dioxide is a multifunctional material of technological itance properties and concluded that α and δ-MnO2 exhibited the high-
significance in several areas, such as in energy storage [1], sensing est performances due to their largest tunnel size [13]. These open
[2], photocatalysis and adsorption [3,4], electrochromism [5], desalin- structures associated with the high surface area promoted by the nano-
ization [6], water oxidation [7] and oxygen reduction [8]. The great metric size enhance the cation intercalation, causing an increase in the
interest in this semiconductor stands on its high resource abundance, pseudocapacitance [13]. Although MnO2 can be employed in a wide
low cost and toxicity, excellent chemical and electrochemical stability pH range as supercapacitor [1,19], its use in neutral aqueous solution
and high surface area [9–12]. MnO2 nanoparticles can be synthesized would make it safer and more environmentally friendly than the com-
by various methods such as solgel, co-precipitation, solvothermal, mon lithium-ion batteries [1].
thermal decomposition, microemulsion and electrochemical methods, Besides its use in energy storage devices, MnO2 is extensively
leading to different morphologies (i.e. flowers, spheres, rods, cubes, explored as electrochemical sensor for hydrogen peroxide [2], glucose
belts, plates, and so on) [9,13–16]. The chemical and electrochemical [20], dopamine [21], nitrite [21], etc. H2O2 is a common oxidizing
performance of MnO2 nanoparticles is quite dependent on the particle agent and essential for pharmaceutic, clinical, industrial, biochemical
morphology and crystallographic forms, which are known as α, β, γ, δ and environmental fields. Thus, its sensing is fundamental [22–25].
and λ [2]. These polymorphs differ in the way the basic structure units Mn4+ possesses a high electroactivity in neutral pH, which can be
of the MnO6 octahedron are linked [10,15]. The corner, edge or face- tuned by the morphological and structural characteristics of MnO2
linked octahedral lead to 1D (α, β and γ phases), 2D (δ phase) and 3D [2,26]. As observed for supercapacitors, α and δ-MnO2 are preferred
(λ phase) tunnel structures [9,13]. The pseudocapacitance of MnO2 due to their superior electrocatalytic properties that are a result of
involves the Mn4+/Mn3+ electron transfer and as it depends on the facilitated access to their electroactive sites [21].
intercalation/deintercalation of cations from the support electrolyte, Many efforts have been made to increase the conductivity and sta-
the tunnel structure and the interlayer spacing control its ability to bility of MnO2 nanoparticles through the synthesis of nanocomposites

⇑ Corresponding author.
E-mail address: [email protected] (E.G.C. Neiva).

https://doi.org/10.1016/j.jelechem.2021.115776
Received 23 June 2021; Received in revised form 7 October 2021; Accepted 8 October 2021
Available online 13 October 2021
1572-6657/© 2021 Published by Elsevier B.V.
G. Zeplin, E.G.C. Neiva Journal of Electroanalytical Chemistry 902 (2021) 115776

with graphene and conductive polymers [27–34]. Furthermore, the redispersed in water under ultrasound bath (Ultronique – 37 kHz)
introduction of these conductive components may decrease the charge for 15 min using a concentration of 0.1 mg mL−1.
transfer resistance, minimize the particle aggregation and growth and
improve sensing performance [35–40]. Polyaniline (Pani) is one of the 2.3. Synthesis of binary and ternary nanocomposites
most used conductive polymer for the syntheses of nanocomposites
due to its low cost, ease synthesis and doping, and thermal and chem- The nanocomposites were synthesized as follows: different volumes
ical stabilities [41–44]. Graphene is a bidimensional nanomaterial of aniline (see Table 1) and 1.6 mL of 0.1 mg mL−1 GO dispersion
composed of sp2 hybridized carbons that can be synthesized by many were added into a flat flask containing 20 mL of HCl aqueous solution
routes, such as chemical vapor deposition, organic synthesis, SiC under magnetic stirring (1500 rpm). Next, 38.6 mg of KMnO4 was
graphitization, decomposition by argon plasma, etc [45–48]. How- added to the mixture to guarantee the total polymerization of aniline.
ever, the chemical exfoliation of graphite stands out due to its low cost The solid produced after 22 h was filtered through a polyamide mem-
and high yield [49]. Graphene oxide (GO) is an intermediate material brane (0.2 μm pore size, Filtrilo), washed with 300 mL of water and
produced in this methodology, which is very interesting to the synthe- 20 mL of ethanol and finally dried at 60 °C for 24 h. Different ternary
sis of nanocomposites since it has oxygenated groups that act as nucle- nanocomposites were obtained varying the aniline volume and HCl
ation sites for nanoparticles [50–52]. Although GO presents lower concentration, as described below. Binary nanocomposites were also
conductivity than reduced graphene oxide (rGO) produced by this synthesized in the absence of GO, KMnO4 or aniline. For the synthesis
route, its oxygenated groups may increase the analyte adsorption of the binary nanocomposite without KMnO4, 55.8 mg of ammonium
and enhance the performance of the nanocomposite in several applica- persulfate was used as oxidizing agent, leading to the sample named
tions [53,54]. GO/P60/HCl-0.01. The description of each precursor amount used in
In this work, binary (GO/MnO2 and Pani/MnO2) and ternary (GO/ the synthesis, as well as the abbreviation of each sample, are detailed
MnO2/Pani) nanocomposites were synthesized through an easy, one- in the Table 1. The low mass of GO used (0.16 mg) is due its high sur-
pot and environmentally friendly route. Both MnO2 and Pani were face area.
obtained together in one-step process, in GO aqueous dispersion and
at room temperature in the absence of additional oxidizing or reducing 2.4. Structural characterization
agents. The effect of different synthetic parameters on the nanocom-
posites were evaluated by microscopic, spectroscopic and electro- The X ray diffraction (XRD) patterns were collected in a Shimadzu
chemical characterization tools. Finally, the electrochemical XRD-6000 equipment with CuKα source (λ = 1.5418 Å) operating at
applications of the MnO2-based nanocomposites were investigated in 40 kV and 30 mA.
energy storage and H2O2 sensing in safe neutral aqueous solutions. The thermal gravimetric analyses (TGA) were carried out in a TGA/
SDT Q600 equipment under air atmosphere using a heating rate of 5 °
C min−1.
2. Materials and methods The FT-IR spectra were registered with 20 scans in an attenuated
total reflection (ATR) mode in a Bruker equipment (4 cm−1 of
2.1. Reagents resolution).
The UV–Vis absorption analyses were realized in a Perkin Elmer
Graphite (Graflake 99580, 99%, Nacional de Grafite SA, and Fis- equipment with scan rate of 8 nm s−1.
cher Chemical), H2SO4 (Nuclear), NaNO3 (Vetec), KMnO4 (Synth), The Raman spectra were obtained in a Renishaw Raman Imaging
HCl (Dinâmica), H2O2 (Vetec e Reatec), ethanol (Reatec), ammonium Microprobe System 3000 using a 514.5 nm (Ar+ laser) excitation line.
persulfate (Vetec), nujol (Mantecorp), Na2SO4 (Vetec), NaH2PO4 anhy- Raman analyses were also conducted using a 632.8 nm (He-Ne laser)
drous (Vetec) and Na2HPO4 anhydrous (Vetec) were used as received. excitation line in a WITec Alpha 300R equipment.
Aniline (Vetec) was distilled under low vacuum three times before The scanning electron microscopy (SEM) analyses were carried out
used. The aqueous solutions and the washing steps were carried out in a Tescan Field Emission Gun (SEM-FEG) equipment operating at
using deionized water. 10 kV using secondary electrons detector. The samples were analyzed
as powder, being adhered to the surface of the Cu adhesive tape, or
deposited as aqueous dispersions and dried over indium tin oxide
2.2. Preparation of GO dispersion (ITO) substrate. Energy dispersive X-ray spectroscopy (EDS) were car-
ried out in the same equipment, under the magnification of 10 kx,
The GO aqueous dispersion was prepared by modifications in our using an Oxford accessory.
previously reported method [49]: 2 g of graphite (Graflake) and 1 g The transmission electron microscopy (TEM) images in both bright
of NaNO3 were added into a 500 mL round flask kept under ice bath. and dark field were registered in a Jeol JEM 120 kV equipment.
Next, 46 mL of concentrated H2SO4 was added to the flask and the Diluted aqueous dispersions of the nanocomposites were dropped onto
mixture was kept under magnetic stirring (1500 rpm) for 45 min. carbon films supported on copper grids and evaporated under room
Afterwards, 6 g of KMnO4 was slowly added to the system and then temperature for the analyses.
the ice bath was removed. After 180 min stirring in this condition,
92 mL of water was slowly added to the flask and then more 2.5. Electrochemical and electroanalytical characterization
280 mL of hot water. Next, 10 mL of H2O2 (30% V V−1 Reatec) was
slowly added to consume the unreacted oxidizing agent. After The electrochemical measurements were carried out in an Autolab
10 min under stirring, the mixture was left to rest until precipitation. potentiostat and Palmsens potentiostat using a three-electrode system
The solid was washed with water until neutral pH, filtered and dried at with a Pt wire as auxiliary electrode (AE) and Ag/AgCl (NaCl satu-
60 °C for 24 h leading to the graphite oxide (Gr-O). 75 mg of Gr-O was rated) as reference electrode (RE). Modified ITO substrates and carbon
added into a round flask containing 25 mL of water and kept 24 h paste electrodes (CPE) were used as working electrode (WE) for the
under magnetic stirring (1500 rpm). Afterwards, the mixture was cen- supercapacitor application. For H2O2 sensing, modified ITO substrates
trifuged for 30 min at 3000 rpm. The supernatant was removed and were used as WE. Aqueous dispersions of the nanocomposites were
centrifuged again in the same conditions to precipitate the non-exfoli- prepared using ultrasound bath for 5 min. In the following, an aliquot
ated Gr-O. Finally, the supernatant was evaporated at 80 °C in a hot of 15 μL was collected and dropped over the ITO electrodes
plate and after that, dried at 60 °C for 24 h. Then, the GO solid was (0.5 × 2.5 cm) in an area of 0.25 cm2 delimited by Parafilm. Next,

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G. Zeplin, E.G.C. Neiva Journal of Electroanalytical Chemistry 902 (2021) 115776

Table 1
Quantities of the precursors used in the synthesis of the nanocomposites.

Nomenclature GO (mL) KMnO4 (mg) Aniline (μL) HCl conc. (mol L−1)

GO/MnO2/HCl-0.01 1.6 38.6 – 0.01

P60/MnO2/HCl-0.01 – 38.6 60 0.01
GO/P60/MnO2/HCl-1 1.6 38.6 60 1
GO/P60/MnO2/HCl-0.1 1.6 38.6 60 0.1
GO/P60/MnO2/HCl-0.05 1.6 38.6 60 0.05
GO/P60/MnO2/HCl-0.01 1.6 38.6 60 0.01
GO/P30/MnO2/HCl-0.01 1.6 38.6 30 0.01
GO/P120/MnO2/HCl-0.01 1.6 38.6 120 0.01
GO/P60/HCl-0.01 1.6 – 60 0.01

the modified ITO was firstly dried at 60 °C for 1 h, then Parafilm was e.g. 0.3 mg for GO/MnO2/HCl-0.01 in comparison to 11.2 mg for
removed and finally, it was dried at 100 °C for 1 h. The mass of GO/ GO/P60/MnO2/HCl-0.01.
MnO2/HCl-0.01, P60/MnO2/HCl-0.01 and GO/P120/MnO2/HCl-0.01 Fig. 1B shows the TGA data of the samples collected under air
over the ITO substrates were 13.44, 28.08 and 22.44 μg cm−2, respec- atmosphere. It is clear to note a direct relation between MnO2 propor-
tively, for the supercapacitors and 13.44 μg cm−2 for the sensors anal- tion in the nanocomposites with the HCl concentration used in the syn-
yses. These masses were calculated using the mass concentration of the thesis. The higher the HCl molar concentration the lower the MnO2
dispersions and the volume deposited over the substrates. The modi- proportion, as indicated by the residue (%). The pH plays a critical role
fied CPE were prepared by mixing the nanocomposites, nujol and gra- in the synthesis of MnO2, once low pH favors the conversion of the
phite (Fischer Chemical) in a mass proportion of 20/20/60, manganese precursor (MnO− 4 ) to Mn
+2
instead of MnO2 (Mn4+) as fol-
respectively, in a mortar and pestle for 20 min. Part of this homoge- lows (equation (1)) [30]:
nous paste was packed into the cavity of a plastic tube (internal diam-
eter of 1.4 mm and depth of 1 mm) using a Cu wire as electric contact MnO4
ðaqÞ + 8Hþ ðaqÞ + 5 !Mn2þ ðaqÞ + 4H2 OðlÞ ð1Þ
previously planned, polished and cleaned. The paste surface was sub-
sequently smoothed on a glossy paper. 0.1 and 1 mol L−1 Na2SO4 The thermograms also indicated different Pani chain structures.
aqueous solutions were used as support electrolyte for the application The nanocomposites obtained at higher acid concentration resulted
as supercapacitors and 0.1 mol L−1 phosphate buffer solution (PBS) in a greater mass loss in the range from 350 to 600 °C, attributed to
pH 7 for the sensing analyses. Cut-off potentials of −0.1 and 0.8 V long chains of Pani. The nanocomposites synthesized at 0.01 mol
and 3 cycles for each charge–discharge current were used for the L−1 HCl presented a higher % of short chains of Pani (range from
charge–discharge analyses, which were carried out after a pre-treat- 120 to 330 °C). This behavior is associated with a better polymeriza-
ment of 100 voltammetric cycles at 50 mV s−1 for both ITO and tion of aniline in lower pH, which also increase the Pani yield [56].
CPE. The same voltammetric pre-treatment was employed to evaluate The initial mass loss from 20 to 140 °C is related to elimination of
the influence of the number of depositions of GO/P120/MnO2/HCl- water and dopant. The oxidation of GO (from 164 to 355 °C) could
0.01 over ITO. The charge–discharge currents densities were calcu- be detected only in the GO/MnO2/HCl-0.01 curve due to the higher
lated using the entire film mass. The sensing of H2O2 (Synth) through proportion of GO in this nanocomposite (9.2%). All the nanocompos-
chronoamperometry was carried out under magnetic stirring ites exhibited several losses and mass gains events at temperatures
(500 rpm) with a magnetic bar of 1 cm of length. higher than 450 °C related to the generation of polyvalent manganese
oxides, such as Mn2O3 and Mn3O4 [57]. The use of 30, 60 and 120 μL
of aniline for the ternary nanocomposites synthesized at 0.01 mol L−1
HCl led to an increase in the mass loss attributed to Pani oxidation
3. Results and discussion from 16.8 to 24 and 26.6% (from ∼ 140 to 440 °C), respectively.
The % of mass loss, the temperature range and the temperature of
3.1. Characterization of the MnO2-based nanocomposites the maximum in the mass loss rate of each event are compiled in Sup-
plementary Table S1 (Electronic Supplementary Material). The DTG
The proposed route of this work is based on obtaining MnO2 and and DSC are depicted in Fig. S1.
Pani together in one-step route using KMnO4 as oxidizing agent for The FT-IR of the nanocomposites are shown in Fig. 1C. It is clear to
aniline. The MnO2 nanoparticles and the polymer were synthesized see the band at 420 cm−1 characteristic of the νMn-O, which is propor-
simultaneously in the presence of GO, contributing to an intimate con- tional to the amount of MnO2 in each sample. Except for GO/MnO2/
tact among the three components. The use of HCl provided the doping HCl-0.01, all the nanocomposites exhibit bands at 3490 (νN-H of
of Pani, which was evidenced by the green color characteristic of the amine), 3313 (νC-H), 3267 (ν=N-H+ of protonate amine), 3122 (νO-H),
conducting form of Pani (emeraldine salt). 1587 (νC=C of quinoid rings), 1496 (νC-C of benzenoid rings), 1296
The XRD patterns of the binary and ternary nanocomposites are (νC-N in delocalized polarons), 1240 (νC-N-C of polaron structure),
presented in Fig. 1A. The nanocomposites synthesized with 1, 0.1 1145 (δN=Q=N of quinoid rings), 813/748/692 (δC-H of aromatic rings)
and 0.05 mol L−1 HCl presented only a broad signal attributed to and 501 cm−1 (δC=C of aromatic rings) attributed to Pani. These bands
the glass holder. However, the nanocomposites synthesized at are more intense for the nanocomposites synthesized at 1, 0.1 and
0.01 mol L−1 HCl exhibited two broad and low intensity peaks at 0.05 mol L−1 HCl due to the higher ratio of Pani. The GO/MnO2/
d = 2.5 and 1.4 Å characteristic of the (1 1 0) and (0 2 0) planes of HCl-0.01 also exhibits low intensity bands attributed to GO. The com-
δ-MnO2 (JCPDS No. 42–1317), respectively [55]. In addition, the bin- parison between the FT-IR spectra of this binary nanocomposite and
ary GO/MnO2/HCl-0.01 nanocomposite also exhibited a broad peak at GO, including the attribution of the GO bands, are presented in Fig. S2.
d = 7.3 Å, attributed to (0 0 1) planes characteristic of the interlayer Fig. 1D shows the Raman spectra of the nanocomposites. As
distance of the δ-MnO2 and indicates a distinct morphology of observed in FT-IR spectra, there is a direct relation between the rela-
MnO2, which is a result of the reaction between KMnO4 and GO. For tive intensity of MnO2 and Pani bands with the composition of each
the binary nanocomposites, the low consumption of KMnO4 due to nanocomposite. The nanocomposites synthesized at 0.01 mol L−1
the absence of aniline led to the formation of low mass of material, HCl exhibit intense bands at 650 (symmetric νMn-O of MnO6 octahe-

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G. Zeplin, E.G.C. Neiva Journal of Electroanalytical Chemistry 902 (2021) 115776

Fig. 1. (A) X-ray diffractograms, (B) thermogravimetric curves, (C) FT-IR and (D) Raman spectra of GO/P60/MnO2/HCl-1 (a), GO/P60/MnO2/HCl-0.1 (b), GO/
P60/MnO2/HCl-0.05 (c), GO/P60/MnO2/HCl-0.01 (d), GO/P30/MnO2/HCl-0.01 (e), GO/P120/MnO2/HCl-0.01 (f), P60/MnO2/HCl-0.01 (g) and GO/MnO2/HCl-
0.01 (h). The TGA was carried out under air atmosphere at 5 °C min−1. The Raman spectra were obtained using a 514.5 nm (Ar+ laser) excitation line.

dron) and 565 cm−1 (νMn-O) that are characteristic of δ-MnO2 [58]. also collected (not shown here), however, MnO2 was not identified in
The nanocomposites synthesized at 1, 0.1 and 0.05 mol L−1 HCl pre- the samples, suggesting the presence of small MnO2 nanoparticles
sent intense bands at 1600 (νC-C of benzenoid rings), 1561 (νC=C of homogeneously spread over the nanocomposites. In contrast to the
semi-quinone units), 1505 (δN-H), 1407 (νC=NH+ of quinoid rings), samples containing Pani, the GO/MnO2/HCl-0.01 exhibited a peculiar
1341 (νC-C of quinoid rings), 1321 (νC-N*+ polarons radical cation), morphology composed of MnO2 nanoflowers sized in the range from
1242 (νC-N of polarons), 1196 (δC-H of benzenoid rings) and 0.2 to 0.8 μm and GO covered by this MnO2 lamellar structure
1175 cm−1 (δC-H of quinoid rings) attributed to emeraldine salt of Pani (Fig. 2H) [63].
[59–61]. The D, G and D’ bands at 1360, 1590 and 1615 cm−1, respec- The EDS spectra are presented in Fig. 2I and confirm the change in
tively, are characteristic of GO and could be observed only for GO/ the MnO2:Pani ratio once the lower the HCl concentration the greater
MnO2/HCl-0.01 due to the greater mass ratio of GO (Fig. S3). In addi- the intensity of Mn and O signals of MnO2. The MnO2 weight % are in
tion, the use of 632 nm excitation line intensified the characteristic accordance with the residue % from TGA analysis showing the higher
bands of Pani due to the resonance effect caused by the π-π* electron MnO2 ratio for the synthesis in 0.01 mol L−1 HCl (Table S1). The Cl
transition promoted by the laser [62]. signal can also be observed for the samples with higher proportion
The SEM images of the binary and ternary nanocomposites are of Pani and results from Cl− counter ion. Except for the ones synthe-
shown in Figs. 2 and S4. Different morphologies induced by the HCl sized with 1 and 0.1 mol L−1, all nanocomposites exhibit the K signal
concentration used in the synthesis are verified. The GO/P60/MnO2/ that becomes more intense as the HCl concentration decreases. K+ is
HCl-1 presented a continuous and rough surface of Pani. However, commonly found intercalated in δ-MnO2 when KMnO4 is used as pre-
the decrease of HCl concentration to 0.1, 0.05 and 0.01 mol L−1 pro- cursor [64]. However, the GO/MnO2/HCl-0.01 presents the more
duced agglomerated Pani spheres in the order of ∼ 220, ∼40 intense K signal probably due to the specific lamellar structure. This
and ∼ 15 nm of size, respectively. This decrease could be related to sample also exhibits a low C signal, which arises from GO.
two factors: i) the higher amount of MnO2 with lower HCl concentra- Figs. 3, S5 and S6 show the TEM images of the nanocomposites.
tions end up increasing the surface area to be covered by the polymer; The low magnification images confirm the decrease in the size of Pani
ii) the lower degree of polymerization caused by the lower HCl con- spheres according to the reduction of HCl concentration (Fig. S5).
centrations. It was also observed, for higher HCl concentrations, the Except for GO/MnO2/HCl-0.01, the TEM images revealed very small
presence of plates of Pani (Fig. S4C). The GO was only observed in MnO2 nanoparticles distributed throughout the samples with mean
the samples synthesized with 0.01 mol L−1 HCl, being covered by size of 0.98 ± 0.03, 1.05 ± 0.03, 1.10 ± 0.03 and 1.03 ± 0.02 nm
the polymer. SEM images using backscattered electrons detector were for GO/P60/MnO2/HCl-0.05, GO/P60/MnO2/HCl-0.01, GO/P120/

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G. Zeplin, E.G.C. Neiva Journal of Electroanalytical Chemistry 902 (2021) 115776

Fig. 2. SEM images of (A) GO/P60/MnO2/HCl-1, (B) GO/P60/MnO2/HCl-0.1, (C) GO/P60/MnO2/HCl-0.05, (D) GO/P60/MnO2/HCl-0.01, (E) GO/P30/MnO2/
HCl-0.01, (F) GO/P120/MnO2/HCl-0.01, (G) P60/MnO2/HCl-0.01 and (H) GO/MnO2/HCl-0.01. (I) EDS spectra of the samples GO/P60/MnO2/HCl-1 (a), GO/
P60/MnO2/HCl-0.1 (b), GO/P60/MnO2/HCl-0.05 (c), GO/P60/MnO2/HCl-0.01 (d), GO/P30/MnO2/HCl-0.01 (e), GO/P120/MnO2/HCl-0.01 (f), P60/MnO2/HCl-
0.01 (g) and GO/MnO2/HCl-0.01 (h). The spectra from 2 to 7 keV were magnified 10 times.

MnO2/HCl-0.01 and P60/MnO2/HCl-0.01, respectively. These MnO2 3.2. Supercapacitor analyses

nanoparticles are responsible for the bright observed in the dark field
images once their crystalline structures diffract the electron beam After a careful structural, morphological and compositional charac-
(Fig. 3D and S6). The super-small size of MnO2 particles could be terization, the electrochemical behavior of the nanocomposites was
responsible for the absence of d(0 0 1) = 7.3 Å at the XRD patterns, once analyzed in Na2SO4 aqueous solution through voltammetry and
just a few δ-MnO2 layers are staked and do not produce X ray construc- charge–discharge measurements, aiming to evaluate their capacitive
tive interference. The TEM images of GO/MnO2/HCl-0.01 show that properties.
the MnO2 nanoflowers are, in fact, composed of many thin layers (inset The 100th cyclic voltammograms of the modified CPE in 0.1 mol
on Fig. 3G). However, these layers are also observed covering the car- L−1 Na2SO4 aqueous solution are presented in Fig. 4A. The voltammo-
bonaceous material, being differentiated from GO by their wrinkled grams exhibit capacitive responses that increases according to the
surfaces (Fig. 3G, H). GO was observed homogenously distributed over increase of MnO2 proportion in the nanocomposites. However, they
all the analyzed nanocomposites. deviate from ideal rectangular shape probably due to resistive effects

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G. Zeplin, E.G.C. Neiva Journal of Electroanalytical Chemistry 902 (2021) 115776

Fig. 3. TEM images of (A) GO/P60/MnO2/HCl-0.05, (B-D) GO/P60/MnO2/HCl-0.01, (E) GO/P120/MnO2/HCl-0.01, (F) P60/MnO2/HCl-0.01 and (G,H) GO/
MnO2/HCl-0.01. (D) presents a dark field image that corresponds to the same region of (C).

specially to GO/MnO2/HCl-0.01 indicating that Pani contributes to the affect the electrochemical stability of the nanocomposites since the
better electronic conductivity of the Pani-containing nanocomposites. continuous cycling leads to a permeation of the solution into the car-
It is well known that MnO2 possesses a pseudocapacitive response bon paste accessing more electroactive sites.
related to Mn4+/Mn3+ and to the intercalation/deintercalation of The potentiality of the binary and ternary nanocomposites as super-
the cation from the support electrolyte, as represented below by equa- capacitors was evaluated and the charge–discharge curves, obtained
tion (2) [1,65]: after the voltammetric pre-treatment, are showed in Fig. 4C. Except
for GO/MnO2/HCl-0.01, all the modified CPE exhibited a typical trian-
MnO2ðsÞ + Naþ ðaqÞ + !MnOONaðsÞ ð2Þ gular-shaped curve characteristic of a capacitive behavior. The opera-
tion potential window was fixed from −0.1 to 0.8 V since the MnO2
The binary GO/MnO2/HCl-0.01 nanocomposite exhibited the high- can suffer decomposition to Mn2+ and Mn7+ upon over negative
est pseudocapacitive response, possibly as a result of its peculiar mor- and positive polarization, respectively, and solubilize in aqueous solu-
phology that provides a direct contact of the material with the support tion [1]. As verified in the voltammograms, the MnO2-richer nanocom-
electrolyte solution. Its structure also led to a different anodic current posites exhibited the highest charge–discharge time indicating that
evolution as a function of the cycling (Fig. 4B) once it gets a more MnO2 is the responsible for the charge storage. In addition, it is clear
stable signal after ∼ 50 voltammetric cycles. The CPE matrix can also to observe that GO/MnO2/HCl-0.01 shows a significant ohmic drop

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G. Zeplin, E.G.C. Neiva Journal of Electroanalytical Chemistry 902 (2021) 115776

Fig. 4. (A) 100th cyclic voltammograms, (B) anodic current at 0.6 V as a function of cycling, (C) charge–discharge curves using 10 μA and (D) 40, 60, 80 and 100
μA of GO/P60/MnO2/HCl-1 (a), GO/P60/MnO2/HCl-0.1 (b), GO/P60/MnO2/HCl-0.05 (c), GO/P60/MnO2/HCl-0.01 (d), GO/P30/MnO2/HCl-0.01 (e), GO/
P120/MnO2/HCl-0.01 (f), P60/MnO2/HCl-0.01 (g), GO/MnO2/HCl-0.01 (h) and GO/P60/HCl-0.01 (i) CPE. The cyclic voltammograms were collected in aqueous
solution of 0.1 mol L−1 Na2SO4 at 50 mV s−1.

(iR drop) in the beginning of the discharge that confirms its lower residue % from the TGA. It is clearly seen the most pronounced redox
conductivity. pair attributed to MnO2 compared to the CPE, indicating the influence
The charge–discharge current was evaluated for the nanocompos- of the electrode matrix. The differences in the profiles for the Pani-con-
ites with the highest electrochemical responses and the curves are pre- taining nanocomposites and GO/MnO2/HCl-0.01 are a consequence of
sented in Fig. 4D. As expected, the increase in the current leads to a each composition and MnO2 morphology. Although the charge–dis-
decrease in the charge–discharge time once the processes occur faster. charge curves still present a triangular shape (Fig. 5B), the inclined
However, the GO/MnO2/HCl-0.01 sample was drastically damaged by plateaus caused by the redox process are more evident in the discharge
the charge–discharge current suggesting a difficult intercalation/dein- curves for ITO modification due to the surface nature of each elec-
tercalation of Na+. The superior retention time of GO/P120/MnO2/ trode. Indeed, the electroactive sites of the nanocomposites are easier
HCl-0.01 and P60/MnO2/HCl-0.01 as a function of the charge–dis- to access over the ITO substrate. As the mass of the deposited materials
charge current can be a result of the tiny MnO2 particle size and indi- were not the same, it is necessary to calculate the capacitance for elec-
cates that the presence of Pani did not damage Na+ intercalation/ trochemical responses to be comparable, which was calculated by
deintercalation into the MnO2 structure. As expected, the ohmic drop equation (3):
increases as higher is the charge–discharge current, which had the
greatest impact on the GO/MnO2/HCl-0.01 response probably due to
C ¼ I  t=ðm  ΔVÞ ð3Þ
the absence of Pani.
−1
The specific capacitances of the nanocomposites were obtained by C (F g ) is the specific capacitance, I (A) is the charge–discharge
the modification of ITO electrodes with aqueous dispersion of the current, t (s) is the discharge time, m (g) is the mass of active material
materials. This new system was needed due to the difficulty in measur- (only MnO2) and ΔV (V) the potential window. Due to the negligible
ing the mass of nanocomposite that effectively participates of the elec- ohmic drop caused by the ITO electrode matrix, the entire potential
trochemical process. As can be seen in the SEM images of the modified window was considered. As can be seen in Fig. 5C, the nanocomposites
ITO (Fig. S7), the drop-casting produced thin islands covering the elec- containing Pani presented higher specific capacitances reaching up
trode surface. The nanocomposites containing Pani exhibit the same to ∼ 150 F g−1, as well as higher specific capacitance retention
agglomerated and small globular morphology verified before and (∼21%) than GO/MnO2/HCl-0.01 (∼5%). The specific capacitance of
GO/MnO2/HCl-0.01 presented the MnO2 nanoflowers and MnO2 lay- the MnO2-based binary and ternary nanocomposites compared to
ers covering GO. other reports based on MnO2 presented reasonable performances and
In the Fig. 5A are shown the voltammograms normalizing the cur- specific capacitance retention under a wide range of charge–discharge
rent intensities by the MnO2 mass over the electrodes that were calcu- current density (Fig. 5C). Both voltammetry and charge–discharge
lated using the mass of nanocomposites over the substrates and the analyses were carried out using a more concentrated Na2SO4 aqueous

7
G. Zeplin, E.G.C. Neiva Journal of Electroanalytical Chemistry 902 (2021) 115776

Fig. 5. (A) 100th cyclic voltammograms, (B) charge–discharge curves using 2, 10 and 20 μA, (C) specific capacitance as function of the specific current, (D)
capacitance as function of the number of depositions of GO/P120/MnO2/HCl-0.01 at 1.8 (a) and 7.1 A g−1 (depositions)−1 (b), and (E) capacitance retention as
function of cycling at 1.78 A g−1. The curves in (A-C) and (E) correspond to GO/MnO2/HCl-0.01 (a), P60/MnO2/HCl-0.01 (b) and GO/P120/MnO2/HCl-0.01 (c).
The current in the cyclic voltammograms (A) were normalized by the MnO2 mass over each electrode. The voltammetric and charge–discharge analysis were
carried out in aqueous solution of 1 mol L−1 Na2SO4 and the voltammograms were collected at 50 mV s−1. (C) depicts the capacitance data from reports of the
literature using MnO2 nanowires (d) and MnO2-Pani (d’) [80], MnO2 in KOH (e) and K2SO4 solutions (e’) [1], MnO2 (f) and rGO/KMn8O16 (f’) [12], MnO2 (g) and
MnO2/CNT (g’) [65], MnO2/Graphene (h) [81] in a three-electrode cell configuration.

solution (1 mol L−1) for the modified ITO electrodes to maximize their The oxidation peak in the first voltammetric cycle was not supposed
electrochemical responses. to occur since the oxidation state of manganese is 4+ in MnO2. How-
The thickness of the nanocomposite over the ITO substrate can ever, the presence of contaminants in the MnO2 structure as cations,
affect the final specific capacitance once thicker films can hinder the protons and water molecules as well as oxygen vacancies can produce
access to the inner electroactive sites. Thus, the influence of the num- Mn3+ sites in the MnO2 matrix [1,68]. Besides the preparation method
ber of depositions was evaluated for the ternary nanocomposite directly affects the valance state of Mn [69], several reports described
(Fig. 5D and S8). It was verified that the 4 depositions did not damage that birnessite MnO2 structure is composed by a mixture of Mn3+ and
the specific capacitance using both 1.8 and 7.1 A g−1 (Fig. 5D and S8) Mn4+ as evidenced by XPS data [55,68,70]. The voltammograms also
and probably more depositions could be done. exhibit an initial reduction from −0.1 to ∼ 0.1 V that may have con-
The specific capacitance stability under continuous cycling was tributed to this oxidation peak. The continuous cycling led to a sup-
evaluated for GO/MnO2/HCl-0.01, P60/MnO2/HCl-0.01 and GO/ pression of the redox pair for all the nanocomposites, which
P120/MnO2/HCl-0.01 nanocomposites using 1.78 A g−1 (Fig. 5E). In indicates a modification in the MnO2 morphology and/or structure
fact, the Pani-containing nanocomposites exhibited better perfor- leading to a less electroactive MnO2 (Fig. S9). The low intensity of
mances than GO/MnO2/HCl-0.01 due to the differences in the MnO2 the cathodic peak compared to the anodic peak corroborates this
morphology and Pani coating. Despite the specific capacitances of hypothesis. The electrocatalytic behavior of MnO2 before and after
P60/MnO2/HCl-0.01 and GO/P120/MnO2/HCl-0.01 were similar in the voltammetric pre-treatment was verified to GO/P120/MnO2/
the charge–discharge current density range used (Fig. 5C), the pres- HCl-0.01 by chronoamperometry with H2O2 additions (Fig. 6B). The
ence of GO and the higher Pani % in the ternary nanocomposite led MnO2 reacts with H2O2 to produce O2 and Mn(OH)2 and/or Mn2O3
to a higher specific capacitance stability under 500 cycles (68.2, 52 [71,72]. Once this reaction occurs at high potential, the Mn2+ and
and 23% for GO/P120/MnO2/HCl-0.01, P60/MnO2/HCl-0.01 and Mn3+ is reoxidized to MnO2 and leads to a current increment. How-
GO/MnO2/HCl-0.01, respectively). ever, the chronoamperogram changes dramatically with the voltam-
metric pre-treatment, showing a lower electrocatalytic behavior that
3.3. H2O2 electrochemical sensing confirms the less electroactive MnO2 produced with the voltammetric
cycling.
MnO2 presents an impressive electrocatalytic behavior for a wide Once the voltammetric cycling damages the electrocatalytic behav-
range of simple and complex molecules. Therefore, the binary and ior of MnO2, the optimizing of the H2O2 detection was carried out with
ternary nanocomposites with higher proportion of MnO2 were applied non-pretreatment step. Firstly, the potential applied in the chronoam-
as sensors to H2O2. Fig. 6A shows the 1st and 30th voltammetric cycles perometry was evaluated and the chronoamperograms, along with the
of GO/MnO2/HCl-0.01, P60/MnO2/HCl-0.01 and GO/P120/MnO2/ analytical curves obtained, are presented in Figs. S10 and 6C, respec-
HCl-0.01 over ITO in PBS (pH 7). The redox pair observed in the first tively. The use of 0.6, 0.8 and 1 V led to similar sensitivities of
cycle is attributed to the interconversion between MnO2 and the two 63.6 ± 9.9, 59.3 ± 4.6 and 53.3 ± 7.7 μA (mmol L−1)−1, respec-
Mn3+ and Mn2+ species, as Mn2O3 and MnO, respectively [66,67]. tively. The use of 0.4 V did not lead to electrocatalytic behavior prob-

8
G. Zeplin, E.G.C. Neiva Journal of Electroanalytical Chemistry 902 (2021) 115776

Fig. 6. (A) 1st and 30th cyclic voltammograms of GO/MnO2/HCl-0.01 (a), P60/MnO2/HCl-0.01 (b), GO/P120/MnO2/HCl-0.01 (c) and non-modified ITO (d) at
50 mV s−1. (B) Chronoamperograms with (a) and without (b) previous voltammetric stabilization for GO/P120/MnO2/HCl-0.01 with five additions of 0.1 mmol
L−1 H2O2 applying 0.8 V. (C) Analytical curves for GO/P120/MnO2/HCl-0.01 applying 0.6 (a), 0.8 (b) and 1 V (c). The inset in A shows in more detail the
voltammograms after 30 cycles. The voltammetric and chronoamperometric analyses were obtained in aqueous solution of 0.1 mol L−1 PBS (pH 7).

Fig. 7. (A) Chronoamperograms and (B) analytical curves for GO/MnO2/HCl-0.01 (a), P60/MnO2/HCl-0.01 (b), GO/P120/MnO2/HCl-0.01 (c), GO/P60/HCl-0.01
(d), non-modified ITO (e) and GO/P60/MnO2/HCl-0.01 (f) with five additions of 0.1 mmol L−1 H2O2 using 0.6 V in aqueous solution of 0.1 mol L−1 PBS (pH 7).

ably because it is not high enough to oxidize Mn3+/Mn2+ to Mn4+ current increments for the H2O2 additions indicating that MnO2 is
after the reaction with H2O2 (Fig. S10). Thus, 0.6 V was used to eval- the only component responsible for the electrocatalytic behavior.
uate the electrocatalytic behavior of the nanocomposites since it The GO/MnO2/HCl-0.01 showed a continuous decreasing of the cur-
would be able to promote the oxidation of Mn3+/Mn2+ species and rent increments suggesting a higher susceptibility to morphological/
avoid side reactions with interferents and solvent oxidation. structural changes in the MnO2 in the absence of Pani. This behavior
Fig. 7A and 7B present the chronoamperograms and the analytical led to the lowest sensitivity of 15.23 ± 13.03 μA (mmol L−1)−1.
curves for H2O2 detection, respectively, of non-modified ITO and bin- The nanocomposites containing MnO2 and Pani exhibited similar sen-
ary and ternary nanocomposites synthesized using 0.01 mol L−1 HCl. sitivities of 64.9 ± 4.3, 55.8 ± 3.2 and 62.5 ± 8.6 μA (mmol L−1)−1
Non-modified ITO and GO/P60/HCl-0.01 did not exhibit significant for P60/MnO2/HCl-0.01, GO/P60/MnO2/HCl-0.01 and GO/P120/

Table 2
Comparison of the optimized MnO2-based sensor with other published reports in aqueous solution of 0.1 mol L−1 PBS.

Electrode LDRa (μmol L−1) Sensitivity (μA (mmol L−1)−1 cm−2) LDb (μmol L−1) Reference

GO/MnO2 5–600 38.2 0.8 [37]

MnO2 nanorods – – 5 ± 2.5 [73]
MnO2(α- β)-carb-nanoPANI – – 8.4 [74]
AuNPs/MnO2(α)/CNT 0.4–626.8 452 0.1 [75]
MnO2(α)/rGO 0.25–2245 – 0.07 [76]
MnO2-ERGO 100–45400 59 10 [77]
MnO2-Co3O4/Graphene 5–1200 53.7 0.8 [78]
MnO2(δ)/MWCNT 100–20500 13.9 6.97 [79]
MnO2(α) hollow urchin 0.24–100 550 0.08 [75]
GO/P60/MnO2(δ)/HCl-0.01 100–500 223.2 3.03 ± 0.22 This work
a
Linear detection range.
b
Limit of detection.

9
G. Zeplin, E.G.C. Neiva Journal of Electroanalytical Chemistry 902 (2021) 115776

MnO2/HCl-0.01, respectively. Thus, the Pani proportion and the pres- authors thank Professor Dr. Aldo José Gorgatti Zarbin and the Materi-
ence of GO in the nanocomposites did not affect the electroactivity of als Chemistry Group-UFPR for the Raman (Ar+ laser), SEM/EDS, XRD,
the MnO2 nanoparticles. In addition to the polymer coating, the mor- TGA/DSC and the charge-discharge analyses.
phology of the MnO2 nanoparticles also contributed to a better electro-
catalytic behavior of the Pani-containing nanocomposites. The limit of
Appendix A. Supplementary data
detection (LD) and the limit of quantification (LQ) were calculated
using the Eqs. (4) and (5), respectively [50].
Supplementary data to this article can be found online at
LD ¼ ð3  sÞ=α ð4Þ https://doi.org/10.1016/j.jelechem.2021.115776.

LQ ¼ ð10  sÞ=α ð5Þ

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