Electrochimica Acta 441 (2023) 141816

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Electrochimica Acta
journal homepage: www.journals.elsevier.com/electrochimica-acta

Facile synthesis of a multifunctional ternary SnO2/MWCNTs/PANI

nanocomposite: Detailed analysis of dielectric, electrochemical, and water
splitting applications
Muhammad Zarrar Khan a, Iftikhar Hussain Gul a, *, Mutawara Mahmood Baig a, Muhammad
Aftab Akram a, b
a
Thermal Transport Laboratory, Department of Materials Engineering, School of Chemical and Materials Engineering (SCME), National University of Sciences and
Technology (NUST), H-12, Islamabad, Pakistan
b
Department of Materials Science and Engineering, Pak-Austria Fachhochschule, Institute of Applied Sciences and Technology, Khanpur Road, Mang-Haripur 22650,
Pakistan

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

Keywords: Herein, a SnO2/MWCNTs/PANI nanocomposite was synthesized using a wet chemical approach which acts as a
Dielectric properties multifunctional electrode for supercapacitor and hydrogen evolution reaction. The dielectric properties were
Supercapacitors studied using the Maxwell-Wagner model of space charge polarization. The increasing dielectric constant indi­
Water splitting
cated the suitability of synthesized NPs for telecommunication, electronics, and other high-frequency applica­
Impedance analysis
tions. The dependence of impedance and dielectric behavior on grains and grain boundaries was further
investigated via impedance spectroscopy and complex electric modulus. Based on a 6 M KOH aqueous electro­
lyte, the SnO2/MWCNTs/PANI as an electrode material for supercapacitors displays a capacity of 211 C g− 1 at 1
A g− 1 and exhibits excellent cycling stability with a capacitance retention ratio of 98% after 5000 cycles at a
current density of 2 A g− 1. For hydrogen evolution reaction in 0.5 M KOH, SnO2/MWCNTs/PANI electrode
achieves a benchmark of 10 mA cm− 2 at overpotentials of 524 mV. The results reveal that the SnO2/MWCNTs/
PANI nanocomposite act as multifunctional material that can be used for both energy storage and conversion.

1. Introduction energy storage system for uninterrupted supply as per the demand.
Among the various energy storage devices, supercapacitors have been
In the past several years, nanoscience has gained growing interest in accepted as suitable candidates for potential energy storage systems. In
developing efficient supercapacitors with increasing power density and comparison with batteries which suffer from low power density (1 kW
durability that can be used in a variety of applications such as in hybrid kg− 1) and poor cyclic stability, supercapacitors possess high power
electric vehicles as power sources, generators, backup supplies for density (~10 kW kg− 1), superior cyclic stability (>100,000), and ul­
computer memory, and other related electronics with high power pulse trafast charge and discharge rate (a few seconds) which makes them
requirements [1–4]. The rising ecological degradation and related suitable for sustainable and renewable sources of power in the
environmental crisis due to the rapid consumption of fossil fuels are the contemporary electronic industry [5–9]. Based on the principle of
major concerns in the sustainable sector of energy development. charge storage, supercapacitors are classified as electric double-layer
Furthermore, the depletion of carbon-based fossil fuels with a growing capacitors (EDLCs) and pseudo-capacitors. The former stores’ energy
population and the associated global warming resulting from environ­ across the double layer of electronic/ionic charge at the
mental contamination has also made it imperative to search for electrode-electrolyte interface i.e., non-faradaic type of charge accu­
eco-friendly, carbon-neutral, and renewable energy sources. Renewable mulation which is often achieved by carbonaceous materials whereas
non-conventional energies such as biomass fuel, solar, tidal, wind, and the latter undergoes reversible faradaic reactions at the
fusion power are the emerging long-term solution to our increasing electrode-electrolyte interface in a suitable potential range. In contrast
energy demands in the future. However, they also need an associated with EDLCs which show low capacity due to the limited availability of

* Corresponding author.
E-mail address: [email protected] (I.H. Gul).

https://doi.org/10.1016/j.electacta.2023.141816
Received 5 August 2022; Received in revised form 20 December 2022; Accepted 1 January 2023
Available online 6 January 2023
0013-4686/© 2023 Elsevier Ltd. All rights reserved.
M.Z. Khan et al. Electrochimica Acta 441 (2023) 141816

the electrode’s surface area, pseudo-capacitors have gained more in­ provide information about the interior structure of the material in the
terest due to their reversible fast redox reactions resulting in faster low conductivity region, which in turn distinguishes the localized or free
charge-discharge rate along with high specific capacitance. As such they band conduction behavior. Such conduction is often dominated by de­
have a power density equivalent to that of EDLCs and an energy density fects of intrinsic (vacancies) and extrinsic (dopants, fillers) nature.
that is analog to the batteries [10,11]. Considering the key technique, Among the variety of energy conversion methods, hydrogen gener­
searching for alternative materials to redevelop the electrodes to attain ation via water splitting is a potentially viable way for H2 production on
higher electrochemical activity, porous structure for fast ionic move­ a sustainable large scale with efficient yet low-cost processing. Practices
ment, and large active surface area takes precedence [12,13]. for producing H2 gas have revolved around natural gas steam reforming
Metal oxides (RuO2, MnO2, MoO, NiO, Co2O3, SnO2) have been which yielded an excess of CO2 gas pollution and photo-electrochemical
widely reported as alternate electrode materials for pseudo-capacitors. water splitting which lacks the ability to generate enough electron-hole
Among these oxides, SnO2 (n-type semiconductor, Eg = 3.6 V) has pairs so as to reach optimum efficiency. Production of hydrogen fuel via
been extensively studied due to its relatively high electrical conductivity electrocatalytic water splitting is a plausible approach to clean energy
(21.1 Ω cm), good electron mobility (100–200 cm2/V s), low potential sources in order to meet future energy demands. Generally, it involves
for ionic intercalation and higher theoretical capacity. Furthermore, due hydrogen evolution reaction (HER) which depends on the fast kinetics of
to its high abundance and inert behavior, it is cost-effective and envi­ a suitable catalyst with a high surface area, stability in an alkaline me­
ronmentally friendly. However, a trivial challenge to its widespread dium, and good electronic conductivity along with an excess of active
implementation as an anode material is its large volume expansion (≈ sites [23–25]. Currently, Pt electrodes possess the highest HER activity
240–300%), induced during the charge-discharge cycle [14,15], as their onset potential is nearly zero vs RHE with low Tafel slopes.
resulting in inevitable pulverization and diminishing specific capacity However, their high cost and scarcity have urged the researchers to
with time due to the loss of electrical contact between the individual continue searching for other viable options. SnO2 can be used as smart
particles [16]. A method to tackle this problem is to incorporate electrode material for energy production/conversion. The combination
nanometer-scale particles and disperse them within a buffering matrix of of electrical features such as optical transparency with 3.6 eV of band
carbon-based fillers which not only cushion the volume expansion but gap along with good chemical sensitivity renders SnO2 suitable material
also improves the electronic conduction. 1D multiwall carbon nanotubes for water-splitting applications. However, its low surface area and
(MWCNTs) can be employed to overcome the above-mentioned problem electrical conductivity present a major bottleneck for its application as
as they mitigate the expansion effect, have flexibility, greater aspect an electrocatalyst. The addition of porous MWCNTs might improve the
ratio, highly accessible surface area, and low density [17]. On the other performance due to enhanced active sites whereas a large number of
hand, regardless of their excellent electrical, mechanical, and buffering nitrogen atoms in PANI chains can also act as active sites for hydrogen
performance, the use of MWCNTs is still limited because of their low evolution. In this context, a ternary nanocomposite of
specific capacitance (<100 F g− 1). They suffer from polarization when SnO2/f-MWCNTs/PANI can be simultaneously used for dielectrics,
the MWCNTs electrode comes in contact with the electrolyte. Owing to supercapacitors, and water-splitting applications. In short, transition
the poor wettability of MWCNTs electrode, there is a limited usable metal oxides often suffer from low electronic conductivity which
surface area available for the electrolyte ions ‘charge accumulation over severely limits their rate of charge/discharge. This can be overcome by
the double layer which partially contributes to the lower capacitance mixing them with electronically conductive materials such as carbon
[18]. SnO2/f-MWCNTs composite itself has unresolved issues such as black, conductive polymers or carbon nanotubes (CNTs). The added
maintaining tight connection between MWCNTs and SnO2 NPs is diffi­ advantage of increased permittivity or enhanced dielectric behavior
cult for prolonged expansion and shrinkage process, which results in further validates the usage of such composites for capacitors, microwave
capacitive decay and poor cyclic performance [19]. The polarization of tunable devices, dielectric resonator oscillators etc. In our reported
MWCNTs can be reduced and their capacitance can be increased further research, a comprehensive systematic study has been established to
by introducing conductive polymers which have high capacitive energy encompass the effects of adding MWCNTs and PANI matrix onto the
density as their whole mass and volume is utilized for charge storage in electrochemical and dielectric performance of SnO2 NPs. To our
contrast to most carbon-based fillers which only use their surface area knowledge, only a handful of research articles are available covering all
[20]. PANI is the most preferable among other conductive polymers three aspects of a multidimensional composite material.
because it is easy to synthesize and has good charge storage capacity
along with high electrochemical stability which leads to its excellent 2. Experimentation
pseudo-capacitive performance (specific capacitance of 950 F g− 1),
surpassing the other such polymers. However, the disadvantages of slow 2.1. Synthesis of SnO2 nanoparticles
ions transport kinetics and poor strength due to the cracking, swelling
and shrinkage during the doping/dedoping process still prevail. PANI A simple co-precipitation route was utilized for the synthesis of SnO2
also degrades at relatively higher potentials via over oxidation, leading NPs. 7.85 g of SnCl2 was dissolved in 200 mL of deionized water to make
to a narrow working potential window. To overcome these problems, it a 0.2 M solution. 5 ml ammonia solution (1 M) was added dropwise to
is necessary to design a ternary composite of carbon based material, previously prepared SnCl2 solution until pH 10 is obtained, followed by
metallic oxide and PANI to induce synergistic effects such as fast charge vigorous stirring at ambient temperature for 90 min. With the addition
carrier mobility and enhanced electrical conduction via (i).stacking of of ammonia solution, white precipitates of stannic hydroxide Sn(OH)2
π-π conjugated quoinoid and benzenoid rings with π bonded surface of are formed which were later washed several times with deionized water
MWCNTs, (ii).interaction of carboxylic acid groups of functionalized to remove residual species (NH4+, Cl− ). In order to remove water con­
MWCNTs with amino groups of aniline, (iii).electrostatic interaction tents, the precipitates were kept in an oven at 100 ◦ C overnight during
between oppositely charged PANI and MWCNTs and (iv) strengthening which the color of the precipitates changed from white to black. This
of polymer backbone chain by stabilizing the redox sites via NPs of metal change in color can be attributed to the freshly precipitated oxide of SnO
oxides [21]. after the evaporation of water contents according to the following
Dielectric relaxation and impedance spectroscopy are other impor­ equation [26].
tant aspect of the electrical behavior of capacitors and other micro­
2Sn(OH2 )→2SnO + 2H2 O
electronic devices, considering it directly relates to the behavior of
leakage current in an actual device operating under the influence of an In order to further reduce SnO to SnO2, calcination of the obtained
electric field [22]. The dielectric and impedance measurements (ac powder was performed at 600 ◦ C for 3 h, resulting in the formation of a
conductivity, Nyquist plots, dielectric constant, and dielectric loss) well-distinct rutile phase of tin(IV) oxide (stannous oxide).

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M.Z. Khan et al. Electrochimica Acta 441 (2023) 141816

2.2. Synthesis of functionalized MWCNTs (f-MWCNTs) matrix. In this regard, 0.6 g of SnO2/f-MWCNTs and 1 mL of aniline were
added to 100 mL of 0.1 M HCl solution, followed by magnetic stirring in
Conventional oxidative treatment of pristine MWCNTs was per­ an ice bath to achieve better dispersion. An aqueous solution of 2 g APS
formed using HNO3 for their covalent functionalization. In a typical [Ammonium peroxydisulfate, (NH4)2S2O8] in 10 mL of 0.1 M HCl so­
procedure, 3 g of as received MWCNTs (Sigma-Aldrich) were refluxed in lution was dropwise added into the previous suspension along with
HNO3 (60 wt.%, 100 mL) at 120 ◦ C for 5 h using a 1000 mL round constant stirring to initiate the oxidative polymerization while the as­
bottom flask fitted with reflux condenser assembly. After cooling down sembly is simultaneously cooled at 4 ◦ C using an ice bath. Magnetic
to room temperature, the functionalized MWCNTs were collected stirring is maintained for another 2 h during which the color of the
through vacuum filtration after washing several times with deionized till precipitates turns from dark brown to dark green, indicating the for­
neutralization of pH, followed by drying in an oven at 70 ◦ C to obtain a mation of Emeraldine form. The precipitates were subsequently washed
black powder of f-MWCNTs. Such treatment leads to the introduction of with ethanol and distilled water, filtered, and dried at 100 ◦ C for 180
functional groups (e.g., carboxyl, hydroxyl, and carbonyl) and the min. A schematic illustration of the overall synthesis procedure is shown
opening of the tube caps along with the formation of holes in the side­ in Fig. 1.
walls, followed by oxidative etching throughout the tube walls with
concomitant release of CO2. Under less vigorous conditions, shortening 2.5. Preparation of electrodes
of the CNTs can be avoided, thus retaining their pristine mechanical and
electrical properties. Furthermore, the functional groups not only aid in Afterward, the nickel foam (1 × 1 cm2) substrates (NF) were washed
the uniform dispersion of MWCNTs but also act as nucleation sites for with 3 M HCl to eliminate the nickel oxide layer. The pretreated NF was
the deposition of SnO2 of the PANI layer during the facile in-situ rinsed with DI water and ethanol via sonication for 15 min. After drying
polymerization. at 80 ◦ C, the mass of Ni foam was determined. After that, the powered
electrocatalysts were dropped cast on pretreated NF by preparing syn­
2.3. Synthesis of SnO2/F-MWCNTs nanocomposite thesized powders ink via 2 h of sonication. The ink was prepared by
taking 15 mg of powder in a solution containing 600 µL, 550 µL, 50 µL DI
For the synthesis of the nanocomposite, 10 mg of f-MWCNTs were water, isopropanol, and Nafion, respectively. After drop-casting, NF was
dispersed uniformly in 200 mL of o-xylene (acting as a carrier fluid, dried over the night at 80 ◦ C. After drying the mass of the Ni foam was
owing to its good polarity. and lower density) using an ultra-sonication again measured. The total mass loading of the material was measured
bath at 45 kHz frequency. 1.9 g of pre-sonicated SnO2 NPs in o-xylene with the weight difference method using electronic weight balance
was dropwise added to the dispersion of f-MWCNTs, followed by before and after the powder deposition. The mass loading on each NF
evaporation of the carrier fluid after continuous sonication for 10 h. The was ~5 mg cm− 2.
resulting composite, thus obtained, contains 5% by weight of f-
MWCNTs. 2.6. Characterization and electrochemical testing

2.4. Synthesis of SnO2/f-MWCNTs/PANI Structural analysis was studied by X-ray diffractometer (XRD) in 2θ
ranging from 5◦ to 80◦ The structure and morphologies of electrode
In-situ polymerization was used to obtain HCl doped polyaniline materials were further inspected using FTIR, RAMAN, and SEM analysis.

Fig. 1. Schematic Illustration of the synthesis route.

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M.Z. Khan et al. Electrochimica Acta 441 (2023) 141816

The samples were pressed into circular-shaped pellets at 4 tons for 5 min chain’s parallel and perpendicular directions. However, the absence of
which were further used to measure dielectric and impedance properties these two characteristic peaks in the XRD pattern of SnO2/f-MWCNTs/
using the relations which have been previously reported in the literature PANI indicated the amorphous nature of PANI in the composite. The
[27]. The electrochemical measurements were performed using VSP SnO2 NPs hinder the crystallization of PANI via wrapping of polymer
multichannel potentiostat. Synthesized electrodes on NF were used as chains around their surface, as reported by Wong [28] and Haili [29].
working electrodes, a Pt. mesh as a counter, and Ag/AgCl as a reference The SEM images for our synthesized samples are shown in Fig. 3,
electrode. Cyclic voltammograms were performed at various scan rates revealing agglomerated particles with flake type structure for our
(5 to 50 mV s− 1). Galvanostatic charge-discharge (GCD) was performed ternary composite.
at various current densities (1 to 5 A g− 1). Impedance spectroscopy was
done at 12 mV from 0.1 Hz to 1 MHz. The HER activity was examined by 3.2. FTIR
linear sweep voltammetry at 5 mV s− 1 from − 1 to 0 V, in 0.5 M KOH
solution. The potentials were iR corrected by the Nernst equation To understand the bonding nature of the synthesized nanomaterials,
VRHE = V Ag + (0.059 × pH) + V oAg the FT-IR spectrum was recorded at room temperature using KBr pellets.
AgCl AgCl
Fig. (2b) shows the spectral lines of pure SnO2 NPs and their composites
Where, VRHE is the potential vs. RHE, VAg/AgCl is the measured po­ with f-MWCNTs and PANI plotted over the wavenumber range of
tential vs. Ag/AgCl and VAg/AgCl
o
= 0.198 at 25∘ C. 475–4000 cm− 1. The appearance of a strong absorption band centered
around 623 cm− 1 represents the antisymmetric stretching mode of the
3. Results and discussions oxide bridge functional group (νO-SnO) on the surface, confirming the
formation of tin oxide nanoparticles [30]. A relatively large peak around
3.1. XRD and morphology 3412cm− 1 can also be observed for pure SnO2, which corresponds to the
terminal bending νOH (Sn-OH, T) of the OH functional groups of water
To confirm the formation of crystallographic features with distinct molecules re-adsorbed from the surrounding atmosphere, whereas the
structural phase, powdered X-ray diffraction was performed at room two minor peaks around 1403cm− 1 and 1632cm− 1 can be ascribed to the
temperature, with a scanning range of 20◦ − 80◦ . Fig. (2a) depicts the X- asymmetrical vibrational harmonics of 2νas (Sn-O-Sn) bridges via the
ray diffractograms for (a) pure SnO2 NPs, (b) SnO2/f-MWCNTs, and (c) condensation of hydroxyl groups [31].In addition to the broad absorp­
SnO2/MWCNTs/PANI nanocomposite. For bare SnO2 NPs, the diffrac­ tion peak of SnO2, the IR spectral line of SnO2/f-MWCNTs shows some
tion peaks observed at 2θ = 26.5◦ , 33.8◦ ,37.9◦ ,51.8◦ ,54.8◦ ,61.9◦ ,64.6◦ additional peaks, corresponding to the attachment of functional groups
and 66.1◦ can be assigned to the planar indices (110), (101), (200), on the surface of carbon nanotubes. The bands around 3425 cm− 1 and
(211), (220), (310), (112), and (301) respectively. All the observed 1459 cm− 1 can be assigned to the stretching of -OH from the carboxylic
reflection peaks are in good agreement with the tetragonal rutile phase group (C-OH and HO-C=O) [32]. The peak around 2950 cm− 1 can be
pattern (JCPDS.No.01–088–0287), belonging to the space group of P42/ associated with the characteristic C-H stretching vibrations whereas the
mnm along with lattice parameters of a = b = 4.737 Å and c = 3.1864, C=O stretching from the carboxylic acid group corresponds to the peak
calculated from the unit cell software. The preferential growth of the around 1636 cm− 1. The characteristic C-O stretching from the hydroxyl
sample along the (110), (101), and (211) planes is evident from their group is represented by the peak around 1059 cm1− [33].
corresponding high intensities, indicating their utmost atomic densities. The IR spectral line of the ternary composite sample is shown in
The average crystallite size was calculated to be 38.19 nm (via the Fig. (2b). Successful oxidative polymerization of aniline monomers is
Scherrer equation while using the (110) plane which shows the highest always associated with the appearance of two peaks, around 3413 cm− 1,
preferential growth, occupying the apical Sn and O atoms) which is in and 1103 cm− 1 respectively [8]. The former corresponds to the N-H
agreement with the previously reported literature. No additional peaks stretching of the aromatic amines, indicating the synthesis of emeraldine
appeared in the diffraction pattern, indicating the purity of the sample. salt. The latter represents the NH+ vibrations of the B-NH+=Q structure
Furthermore, the high signal-to-noise ratio is a direct indication of the (where B and Q represent benzenoid and quinonoid rings respectively),
high crystallinity of synthesized SnO2 NPs. For SnO2/f-MWCNTs originating from the process of acid doping and thus, representing the
(Fig. (2a)), the pattern remains consistent with the graphitic reflection extent of electron delocalization. The characteristic high intensity of this
peak of hexagonal carbon in MWCNTs being superimposed by the (110) peak is the direct indication of PANI conductivity, which is further
planar reflection of SnO2, which can be ascribed to the efficient and enhanced due to the π-π interactions between MWCNTs and PANI [34].
wrapping of carbon nanotubes by SnO2 NPs. There are two broad yet The vibrational band adjacent to the NH+ stretching, around 1240 cm− 1,
low-intensity diffraction peaks for pure PANI (Fig. (2a)), around 20.7◦ originates from the stretching vibrations of C-N bonds next to the
and 25◦ which correspond to the observed periodicity along with the quinonoid ring (C-N=Q=N-C). The C=C stretching from the benzenoid
and quinonoid rings manifests around 1488 cm− 1 and 1493 cm− 1,

Fig. 2. a) XRD, b) FTIR, c) Raman anlysis of SnO2, SnO2/f-MWCNTs and SnO2/f-MWCNTs/PANI.

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M.Z. Khan et al. Electrochimica Acta 441 (2023) 141816

Fig. 3. SEM ananysis of (a-c) SnO2, (d-f) SnO2/f-MWCNTs and (g-i) SnO2/f-MWCNTs/PANI.

respectively. The peak around 1569 cm− 1 corresponds to the quino­ Three of these e.g. A(1g), B(2g) and E(g) are Raman active. The
noid’s -N=C stretching vibration mode and the aromatic C-H stretching appearance of the dominant peak around 613 cm− 1 corresponds to the
vibration appears around 2930 cm− 1. All these characteristic bands A(1g) active vibrational mode tetragonal symmetry, arising due to the
matched well with the patterns reported in the literature [35–37]. Apart contraction and expansion of Sn-O bonds whereas the asymmetrical
from the broad SnO2 band, no peaks associated with f-MWCNTs were stretching results in a peak around 734 cm− 1, giving rise to the B(2g)
found, indicating their successful encapsulation by PANI. vibrational mode. The Raman inactive E(U) and A(2g) vibrational modes
were also observed around 276 cm− 1 and 557 cm− 1 respectively, which
3.3. Raman spectroscopy can be ascribed to the existence of oxygen vacancies, revealing the
crystallite size to be in the nanometer range as indicated by XRD data in
Room temperature Raman spectroscopy was performed to further the previous section. Two prominent peaks can be observed in the
determine the structural differences between the pure SnO2 NPs and Raman spectral line of SnO2/f-MWCNTs, around 1354 cm− 1 (D-band)
their composites. Insert of Fig. (3c) shows the obtained Raman spectra of and 1585 cm− 1 (G-band) respectively. The former constitutes the
SnO2 NPs which belong to the point group D4h. There are two SnO2 induced disordered feature arising from the vibration of amorphous
molecules in a unit cell, with their lattice vibrational modes at the Γ carbon structure with dangling bonds whereas the latter is associated
point of the Brillouin zone [38], represented by: with the tangential shear stretching mode of the graphitic C=C bond
plane. Because of the higher volume of lightweight f-MWCNTs, the
Γ = A(1g) + A(2g) +2A(2u) + B(1g) + B(2g) +2B(1U) + E(g) +3E(U)
major peak of SnO2 has been suppressed, as reported in the previous

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M.Z. Khan et al. Electrochimica Acta 441 (2023) 141816

literature [39–41]. An aniline molecule consists of 26 atoms, belonging 3.4. Electrical studies
to the Cs point group of symmetry with 36 vibrational modes [42],
represented by: 3.4.1. Dielectric behavior
′ ′′
The varying frequency-dependent dielectric behavior for our syn­
ΓvIb = 20A + 16A thesized samples is shown in Fig. (4) revealing a high magnitude of ε′ for
These modes contain 15 vibrational modes of C-H, 6 N-H vibrational SnO2 NPs, at the lower frequency regime. However, with the increase in
modes, 12 ring vibrational modes, and 3 vibrational modes of C-N. Most the frequency of the applied electric field, ε′ shows a sharp decrease in
of these modes are Raman active and hence, provide a deep analysis via values until it becomes frequency independent. The same pattern can
Raman spectra. The obtained spectra for the ternary composite con­ also be observed for the synthesized nanocomposites. This typical
taining PANI are shown in Fig. (3c). The characteristic markers of C=C dielectric dispersion behavior can be justified based on Maxwell
stretching in the quinonoid and benzenoid rings give rise to distinct Wagner’s model of polarization which is also in agreement with Koop’s
peaks around 1488 cm− 1 and 1592 cm− 1, respectively [43]. The peak theory. The high values of ε′ in the lower frequency region can be
around 1322 cm− 1 corresponds to the C-N.þ stretching vibrations from explained using the polarization mechanisms for dielectric nano­
the semi-quinone radicals (secondary aromatic amine), thus confirming materials. Two polarization processes are usually associated with
the doping and conductive nature of the emeraldine form [44]. The C-N enhanced dielectric behavior, namely rotation directional polarization
stretching vibrations from the diverse benzenoid ring or complex (RDP) and space charge polarization (SCP) [46,47]. The former is often
polaronic shapes give rise to small peaks around 1213 cm− 1. The peak found in n-type semiconductor oxides (SnO2) where a large amount of
around 1162 cm− 1 can be ascribed to the C-H in-plane bending vibration oxygen vacancies exits in the interface of SnO2 NPs, acting as shallow
of the quinonoid ring. The C-H out-of-plane bending deformation on the donors. Negative oxygen ions (O2− ) along with positive oxygen va­
1,4 substituted benzenoid or quinonoid rings give rise to smaller peaks cancies (V2+
O ) result in large dipole moments which rotate under the
around 819 cm− 1 whereas the bipolaronic C-C quinine ring deformation influence of an applied external field, leading to the RDP phenomenon
manifests itself around 712 cm− 1 [45]. The small peaks around 511 with huge dipole moments in the interfaces of SnO2 NPs. The latter
cm− 1 can be linked to the out-of-plane ring deformation. The superim­ (SCP) can also exist due to the large quantity of trapping states at the
position of f-MWCNTs and SnO2 peaks by PANI confirms the presence of grain boundaries (gbs) or interfaces of SnO2 NPs. From bulk solids to
PANI matrix with rich polaronic structure along with strong interactions nanostructured materials, the interfaces/cm3 increase by a factor of 1019
between SnO2/f-MWCNTs and PANI backbone, which supports the with more grain boundary density [48]. These interfaces/gbs possess a
electronic delocalization. large number of trap sites in the form of defects such as dangling bonds,
micro-pores, and vacancy clusters. These trap sites induce positive and
negative space charges with varying time constant distributions. These
space charges move towards their corresponding poles of the applied

Fig. 4. Dilectric propeties of SnO2, SnO2/f-MWCNTs and SnO2/f-MWCNTs/PANI.

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M.Z. Khan et al. Electrochimica Acta 441 (2023) 141816

electric field. However, their blockage because of the defects leads to the polarization shows retardation of phase with respect to changing cur­
formation of dipole moments, causing the SCP phenomenon in the rent, by 90-δ instead of being 90◦ advanced, where δ is the phase dif­
sample. The high values of ε′ at the low-frequency region are a net result ference between the applied field and induced current. Taking the
of these two polarization processes. According to the Maxwell Wagner tangent of this phase difference within a complex plane gives us the
Model, dielectric nanomaterials are made up of conducting grains, equation tanδ = 2πfC1P RP . This phase shift arises from electron hopping
separated by insulator grain boundaries. At the lower frequency region, and dipole polarization relaxation. The delay between these two ac­
the induced dipoles or space charge carriers accumulate across the grain counts for the inherent loss of energy, exhibiting the same pattern with
boundaries (acting as potential barriers) by migrating through conduc­ frequency as ε′ and ε′′ . However, the low values of tanδ indicate that the
tive grains while following the polarity change of the applied ac field, synthesized samples can be used for capacitor applications.
thus giving rise to high values of ε′ . At a high-frequency regime, the The general relation for AC conductivity (σac) and its frequency
polarity of the applied ac field changes more abruptly and the oscillation dependence is given by the following relation.
of induced dipoles or charge carriers lags, which reduces the polariza­
tion and leads to the decline of ε′ values. σ tot (ω) = σdc (T) + σac (ω, T) = σdc (T)+Bωn
Fig. (4a) depicts the dependence of ε′ on the compositions of syn­
thesized samples, which can be directly related to the varying magni­ where σdc(T) represents the frequency-independent DC conductivity
tude of polarization. A massive increase of ε′ values can be observed for contributed by the conduction band and σac(ω, T) is the frequency-
SnO2/f-MWCNTs nanocomposite due to the formation of the conductive dependent AC conductivity contributed by electron hopping between
network within the SnO2 matrix. Conductive MWCNTs act as parallel charge carriers. The former conductivity is more significant at low fre­
plate capacitors within the matrix, between which the enhanced po­ quency and high temperature whereas the latter is more predominant at
larization effect originates via dipole formation, thus enhancing the low temperature and high frequency. B is the pre-exponential constant
capacity of storing charge via increased stored charge contents [49]. having the same units as conductivity, ω = 2πf is the angular frequency
With the addition of conductive nanotubes, the inhomogeneity of and n is the temperature-dependent frequency component. For n<0, the
dielectric structure increases as there are more heterogeneous interfaces samples show frequency-independent behavior whereas for n<1,
which leads to enhanced interfacial polarization via the accumulation of frequency-dependent behavior is dominant [53]. The calculated values
dipoles or charge carriers at these heterogeneous interfaces. Encapsu­ of n obtained from the slope of the graph between log (σac) and log (ω)
lation of SnO2/f-MWCNTs nanocomposite in p-doped PANI results in a satisfy the condition of n<1 i.e. they were found to be in the range of 0.2
further increase of ε′ values. SnO2/f-MWCNTs have a dielectric value of to 0.50, predicting the frequency-dependent behavior for AC conduc­
381 at 100 Hz which reduces to 12 at 5 MHz. However, after in-situ tivity. Fig. (4d) represents the typical AC conductivity behavior for pure
polymerization of HCl-doped PANI, the resulting ternary composite SnO2 NPs, showing a slow increase in σac at the lower frequency region.
(SnO2/f-MWCNTs/PANI) exhibits a dielectric value of 760 at 100 Hz However, such an increment becomes extremely sharp at higher fre­
which then reduces to 19 at 5 MHz. Such an increase of ε′ values pertains quencies. According to the charge carrier hopping model, limited hop­
to the interfacial interaction between PANI-CNTs and PANI-SnO2. The ping of electrons between charge carriers (Sn4+/Sn2+, generated
heterogeneous interfaces between exposed f-MWCNTs surface and PANI through sintering operation) results in lower σac values at lower fre­
layer serve as accumulation sites of polarons or charge carriers, inducing quencies [54]. However, enhanced hopping of electrons occurs via a rise
dipolar orientation polarization which contributes to the overall polarity in AC field frequency, giving rise to high conductive values
of the ternary composite [50]. Another mechanism, proposed by Mur­ (Sn4+⇔Sn2++2e− ). The addition of f-MWCNTs further provides the
ugan [51] is the formation of a heterogeneous p-n junction between the highly conductive network within the SnO2 matrix, resulting in high
p-type PANI and n-type SnO2 components. In our hybrid composite, values of σac via enhanced electrons hopping process. At any given
electron transfer takes place from n-type SnO2 to p-type PANI. These frequency, the σac value of the ternary composite is much higher than
electrons occupy vacant energy levels in PANI till the equalization of either of the SnO2 NPs and SnO2/f-MWCNTs composite. It is interesting
fermi levels across the entire composite material. This produces positive to known that even though all the synthesized samples exhibit a σac
and negative poles in n-SnO2 and p-PANI respectively. Such a charge plateau of constant ac conductivity (which increases steeply after 105Hz
transfer results in a proportional increase of ε′ values under the influence frequency), the increase for the σac values of the ternary composite is
of the external field. much more exponential. This can be attributed to the increased polarons
The dielectric loss (ε′′ ) is a direct measure of the dissipated energy contribution, supported by the increasing charge motion in the amor­
loss within the dielectric material under the influence of an applied phous region [55]. As such, the isolated polarons are moving along
electric field. The frequency-dependent variation of ε′′ , resembling with smaller distances in the polymer chain with increasing frequency which
dielectric constant, is shown in Fig. (4b) For all the synthesized com­ can be attributed to the contribution of charge motion in the amorphous
positions, a general trend of high ε′′ values in the low-frequency region regions [56].
can be observed, indicating high energy losses as more energy is
required for charge carriers hoping between the energy levels. However, 3.4.2. Impedance spectroscopy
such a hopping of electrons between energy levels is promoted at a Fig. (5a) illustrates the dependence of the real part (Z/) of the
higher frequency, vis a vis smaller energy loss is evident in the higher impedance on frequency variation. All three samples show a plateau in
frequency region. According to Koop’s theory, the low-frequency region the lower frequency region, followed by the onset frequency where the
is predominated by grain boundaries where high energy is required for magnitudes significantly decrease, eventually merging in the higher
the hopping of electrons which contributes to high dielectric loss frequency region, attaining constant values. The observed trend is in
whereas the high-frequency region corresponds to the conductive grains accordance with the increasing dielectric trend in the lower frequency
where the charge deficient dipoles have decreased relaxation with region and increasing AC conductivity values in the higher frequency
increasing frequency which leads to the decrease of ε′′ values in the region, as discussed in the previous section. The lower frequency plateau
higher frequency region [52]. The addition of MWCNTs and PANI region in each case corresponds to the dipolar space charge relaxation
resulted in neighboring phases with compositional differences, causing whereas, at high frequencies, the space charge has lesser time to relax,
the formation of heterogeneous interfaces which act as centers for leading to faster recombination i.e., lowering barrier properties leading
interfacial polarization relaxation via the accumulation of charges, thus to electrons with more energy to overcome the barrier height which
increasing the overall energy expenditures. results in the release of space charge[57]. In the composites, the pres­
The dielectric loss factor (tanδ) as a function of frequency is shown in ence of conductive networks e.g., f-WMCTS and PANI between high and
Fig. (4c) Upon the application of the external field, the time taken for low conducting regions of SnO2 ultimately results in smaller conducting

7
M.Z. Khan et al. Electrochimica Acta 441 (2023) 141816

Fig. 5. Impedance analysis of SnO2, SnO2/f-MWCNTs and SnO2/f-MWCNTs/PANI.

grains, thus justifying the shift of onset frequency towards a higher appears when the hopping frequency of charge carriers or localized
frequency region [58]. The addition of both f-MWCNTs and PANI in the electrons matches with the applied electric field frequency, whereas the
system decreases the overall resistance, which manifests in the form of narrowing of the peaks can be related to the decrease of relaxation times
diminishing Z/ values in the lower frequency region. The imaginary part [59], caused by the increased mobility of charge carrier species/elec­
(Z//) of the impedance shows Fig. (5b) the typical nature of variation trons upon the addition of f-MWCNTs and PANI, ultimately leading to
with frequency, indicating that Z// initially shows a peaking behavior lower Z// values [52]. The shifting of the peak towards higher frequency
with increasing frequency, attaining a maxima (Z// max) at a particular can be justified by the relaxation process which is becoming faster as the
frequency and then decreases with further increment in frequency. enhanced polar interaction with conductive fillers results in more
Furthermore, with the addition of f-MWCNTs and PANI, the position of boundedness between f-MWCNTs and PANI. This leads to faster relax­
this maxima shifts towards higher frequency along with the peak nar­ ation of charge carriers within the system and gives rise to decreased
rowing and diminished magnitudes of Z//. Such a peaking behavior relaxation time. The Nyquist plots (Z/ vs Z//) are an effective tool to

Fig. 6. Cyclic voltammograms of (a) SnO2, (b) SnO2/f-MWCNTs and (c) SnO2/f-MWCNTs/PANI, (d) comparison of CV curves at 50 mV/s.

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M.Z. Khan et al. Electrochimica Acta 441 (2023) 141816

separate the contribution of spectral components (grain, grain bound­ SnO2/f-MWCNTs. Such a behavior can be attributed to the following: (i)
ary, and electrode) towards the resistance of the material. The complex Increase of effective surface area due to better electrical contact between
Nyquist plots for our synthesized samples are shown in Fig.(5c), SnO2− MWCNTs-PANI phases, resulting in enhanced charge carrier
exhibiting the formation of only a single semicircular arc, which cor­ concentrations [35]; (ii) Increased faradaic reactions due to the devel­
responds to the grain boundary contribution towards the impedance. opment of π-π interactions as the exposed π bond surface of MWCNTs
With the addition of f-MWCNTs and PANI, the radius of the arcs de­ may interact with the conjugated PANI structure through π stacking,
creases which corresponds to the decreased impedance as a result of resulting in the preferential protonation of amine nitrogen atoms via the
increased conductivity. The absence of the electrode and grain contri­ enhanced degree of e− delocalization [68]; and (iii) Switching of PANI
bution indicates that all the constituent phases are existing in a compact between n/p doped states during which the ions of electrolyte are either
manner such as a core-shell type of particles [60] or due to the highly inserted or extracted from the chain’s backbone[18]. PANI becomes
dense nature of the pellets [61]. poly-cationic during the charging process (oxidative p-doping), further
attracting anions (OH− ) from the electrolyte which intercalate into the
3.4.3. Electrochemical studies backbone chains to achieve electro-neutrality. Thus the polymer is
To investigate the electrochemical performance of SnO2 nano­ oxidized via p-doping with anions (Pm +x(OH− )-xe− ⇔ Px+m(OH− )x).
particles and their composites with f-MWCNTs and PANI, cyclic vol­ During discharging, PANI is reduced via n-doping (Pm+Y(K+)+Ye− ⇔
tammetry (CV) and galvanostatic charge-discharge (GDC) analysis were Py-m(K+)y). Here m is the degree of polymerization and P represents
deployed using a three-electrode assembly, with 6 M KOH solution as an PANI. Thus, the entire surface area of PANI participates in high electron
electrolyte. The measurements were carried out at the scan rate of 5 to transfer via enhanced electrolyte access, which in return results in high
50 mV s1− , with Pt as an auxiliary electrode and Ag/AgCl as a reference current densities.
electrode. Fig. 6(a-c) represents the cyclic voltammograms, measured at To further analyze the electrochemical performance of our synthe­
room temperature within the potential window of 0 to 0.6 V (vs Ag/ sized samples, anodic and cathodic peak currents ip (mA cm− 2) was
AgCl). It can be perceived from Fig. 6(a) that the CV curves for SnO2 NPs plotted as a function of scan rate, showing an increase in current density
appear to be non-rectangular with clear redox peaks, affirming the due to the reduction of diffusion layer with increasing scan rates
battery-type behavior of the active transition metal oxide as reported (Fig. (7a-c). According to the Randles-Sevcik equation, the peak current
previously in the literature [62–65]. The charge storage process for (ip) of a reversible electrochemical reaction, involving electron transfer
metal oxides such as SnO2 usually involves two mechanisms. The first via diffusion of redox species, can be related to the square root of the
occurs by the intercalation/deintercalation of protons (H+) or alkali scan rate (ν1/2) as:
metal cations over the bulk NPs for the reduction and oxidation of Sn
D1/2 CV 1/2
ions. This process can be attributed to the following equation. ip = 0.4663n3/2 F3/2 A
(RT)1/2
SnO2 + A+ + e− →SnOO− A+ (A+ = K + )
Whereas n is the number of electrons transferred, F is the Faraday
The second mechanism is at the surface or near-surface region of Constant, A is the active area of the material, D is the diffusion coeffi­
electrodes where adsorption/desorption of electrons and ions of the cient, R is the Rydberg coefficient and C represents the electrolyte
electrode/electrolyte interface of alkali metal cations takes place, onto concentration. An adsorption-controlled electrochemical process on the
the surface of SnO2. electrode would show a linear relationship between the peak currents
(SnO2 )surface + A+ + e− →(SnOO− A+ )surface and the square root of scan rates [69]. However, the inserts of Fig. (7a-c)
indicate an almost non-linear relation, suggesting a diffusion-controlled
With the increasing scan rates, the voltammograms still retain their charge transfer process on the electrode.
shape with the negligible shifting of peaks, thus suggesting a high degree Usually, the relationship between current (i) and scan rates (v) obeys
of reversibility for the electrochemical reactions taking place with a the power law i = avb where a and b are appropriate values. The elec­
good performance of the active material. However, the fast scans also trochemical process is a diffusion-controlled process for a b-value of 0.5,
yield high current density which can be attributed to fast ion exchange whereas, for a b-value of 1, it corresponds to a non-diffusion-controlled
during the charge-discharge cycle via the reduction of the diffusion process. Therefore, the non-diffusion-controlled behavior (capacitive
layer. The translational nature of OH− ions adsorption onto the surface effect) and the diffusion-controlled behavior could be appropriately
of SnO2 NPs might be the critical step for the reversibility of the elec­ recognized depending on the value of b [70–72]. To verify the charge
trode material. storage mechanism, the plot of log(i) versus log(v) from 5 to 50 mV s− 1
for the anodic peaks is shown in Fig. 7(d-f). The value of “b” obtained for
SnO2 + OH − →SnO2 (OH)e−
the anodic current of all electrodes is close to 1, confirming that the
As shown in Fig. (6b), the voltammograms for SnO2/f-MWCNTs charge storage mechanism is a non-diffusion-controlled process, thus
exhibit increased integrated areas under the curves with current den­ delivering superior rate capability.
sities that are 5 times more than those observed for pure SnO2 NPs at the To further investigate the charging-discharging performance of
same scan rates. These observations can be related to the synergistic synthesized electrode materials, GCD measurements were performed as
effects among SnO2 NPs and MWCNTs, resulting in enhanced capacitive a function of time within the potential window of 0 V to 0.6 V, while
behavior as compared with the SnO2 sample [66,67]. Apart from the using the same 6 M KOH electrolytic solution. Fig. (8a-c) shows the GCD
high conductivity, enhanced surface area with more open structure is to curves of SnO2, SnO2/f-MWCNTs, and SnO2/f-MWCNTs/PANI nano­
be expected from MWCNTs, thus facilitating the access of electrolytes in composites with varying current densities, between 1 A g− 1 to 5 A g− 1.
addition to the contribution/coverage of SnO2 NPs. However, the shape All the curves exhibit a non-symmetrical triangular shape with a char­
of the curves still remains consistent with the increasing scan rate, acteristic decay trend i.e., a rapid decay upon discharge followed by a
demonstrating the stable reversibility of the electrode. The gradual delayed response. The rapid drop, known as IR drop or ohmic drop,
shifting of redox current peaks can also be observed for the varying scan occurs due to the electrolyte’s intrinsic resistance or poor electrical
rates, which can be attributed to the electrode resistance, originating contact between the electrode materials. The slowed decay indicates the
from the formation of interfaces that hinder the electronic transitions to battery type nature via the presence of faradaic processes, thus differ­
a trivial extent. The CV curves for SnO2/f-MWCNTs/PANI (Fig. (6c)) entiating from the EDLC nature of charging and discharging curves. A
further display the superior electrochemical response with current minor decrease in the IR drop can be observed for the ternary composite,
densities that are even 1.5 times higher than those measured for indicating enhanced electrical conductivity within the electrode

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M.Z. Khan et al. Electrochimica Acta 441 (2023) 141816

Fig. 7. Variation of peak current with scan rate and variation of peak current with square root scan rate (inset) for (a) SnO2, (b) SnO2/f-MWCNTs and (c) SnO2/f-
MWCNTs/PANI. b-values for (d) SnO2, (e) SnO2/f-MWCNTs and (f) SnO2/f-MWCNTs/PANI.

material. It is also evident that with the increasing current density, the rate of Cs values of the ternary composite can be justified by the reduced
charge-discharge duration decreases. This can be well explained by the internal resistance of the electrode material as the addition of PANI leads
fact that at lower current densities, proton (H+) or alkali metal cation to enhanced electrical contact within the ternary system, which is also
(K+) can easily penetrate the interior surface of the electrode material. consistent with the decreased ohmic drop in the GCD curves. The overall
However at higher current densities, only the electrode’s outer surface is decreasing trend of the specific capacity with increasing current density
utilized as the electrochemical kinetics cannot cope with the rapid is due to the inability of the ions to access the bulk of the electrode
changes in potential due to reduced ion mobility and less utilization of material due to the rapid potential changes.
active surface area [69,73]. The specific capacitance (Cs) was deter­ Electrochemical impedance spectroscopy was employed to evaluate
mined from the GCD data by using the following relation: charging kinetics in relation to capacitive behavior. Fig. (9a) displays
the Nyquist plot of all synthesized electrodes. Normally a semicircle
i.Δt
Cs = could be observed in the Nyquist plot in the high-frequency regime,
m.Δv
which is attributed to charge transfer resistance (Rct) caused by faradic
Where i is the current applied, Δv is the applied potential window, m reactions. The semicircle span on the real impedance axis provides Rct at
represents the active mass and Δt is the discharging time. Fig. (8d) a boundary, which was observed to be 2.314 Ω 2.625 Ω, and 3.459 Ω for
demonstrates the calculated specific capacity (Cs) as a function of SnO2, SnO2/f-MWCNTs, and SnO2/f-MWCNTs/PANI electrodes,
varying current densities. It is to be inferred that the ternary nano­ respectively. The solution resistance for the SnO2, SnO2/f-MWCNTs, and
composite of SnO2/f-MWCNTs/PANI delivered the maximum Cs value of SnO2/f-MWCNTs/PANI electrodes was 18.556 Ω, 19.564 Ω, and 26.957
211 C g− 1 at 1 A g− 1 as compared to the binary SnO2/f-MWCNTs Ω, respectively. The “Warburg impedance” sloped to the Z’’ axis could
nanocomposite (128 C g− 1) and SnO2 NPs (74 C g− 1) at the same current be observed in the intermediate frequency regime. The Warburg
density. Apart from the general decreasing trend of Cs with increasing impedance for both electrodes is inclined at 45◦ , demonstrating the
current density, it is also evident from the plots that the decreasing rate electrodes’ battery-type nature. The bode plot of synthesized electrodes
of Cs, with increasing current density, in the case of ternary nano­ is displayed in Fig. (9b). The impedance features of a supercapacitor lie
composite is slower as compared to the other two samples i.e., SnO2/f- among the ideal resistors and ideal capacitors having a phase angle
MWCNTs/PANI retains 56% of its Cs value at 5 A g− 1 while SnO2/f- between 0◦ to 90◦ The phase angle for all synthesized electrodes is close
MWCNTs and SnO2 retain 50% and 47% of their Cs values at 5 A g− 1 to 90◦ , demonstrating the outstanding capacitive nature of both elec­
respectively. The significant capacitive values of the ternary composite trodes. Fig. (9c) shows the excellent cycling stability of SnO2/f-
can be attributed to the synergistic effects of all three components. The f- MWCNTs/PANI with a capacitance retention ratio of 98% after 5000
MWCNTs form an excellent charge transfer complex within the com­ cycles at a current density of 2 A g− 1.
posite as they are excellent electron donors owing to their minimum
resistivity. Their interconnected network decreases the migration and 3.4.4. Hydrogen evolution reaction (HER)
diffusion of electrolyte ions, leading to an improved specific capacity. To investigate the electrolytic HER performance of as-synthesized
The addition of PANI leads to nano-porous three-dimensional SnO2 NPs and their composites with f-MWCNTs and PANI, Linear
morphology with enhanced electroactive chemical sites, leading to high Sweep Voltammetry (LSV) was performed using a three-electrode
faradaic reactions via its characteristic high surface area whereas the configuration system with 0.5 M KOH electrolyte. The obtained LSV
SnO2 NPs play the role of backbone for PANI by preventing it from high curves were collected in the potential range of 0 to − 1 V with a sweep
volumetric changes (shrinkage and breakage) during the GCD cycles, rate of 5 mV s1− . From these plots (Fig. (10a)), improved HER activity
thus ensuring the stability of the electrode material. The slower decay can be observed with decreasing onset overpotential values at the

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M.Z. Khan et al. Electrochimica Acta 441 (2023) 141816

Fig. 8. GCD profiles of (a) SnO2, (b) SnO2/f-MWCNTs, (c) SnO2/f-MWCNTs/PANI (d) calculated capacity at different current densities.

Fig. 9. (a) Nyquist (b) Bode Plote of SnO2, SnO2/f-MWCNTs and SnO2/f-MWCNTs/PANI, (c) cyclic stability of SnO2/f-MWCNTs/PANI electrode at 2 Ag− 1.

current density of 10 mA cm− 2. The most significant improvement in favored by the presence of N atoms (from –NH2 groups, acting as active
terms of HER activity was observed for SnO2/f-MWCNTs/PANI with sites) in PANI [72,79-81]. The comparison of HER catalytic efficiency of
overpotential values of 524 mV, 546 mV, and 562 mV at a current different MWCNTs-based electrocatalysts is shown in Table 1.
density of 10, 50, and 100 mA cm− 2. At the same time, the composites Tafel slope (Fig. (10b)) is an inherent property of an active electro-
display higher current densities at the same potential, depicting catalyst and is often used to assess the reaction kinetics at the elec­
enhanced catalytic performance with respect to HER in addition to trode materials. There are two steps involved in hydrogen evolution
capacitive performance. With the incorporation of f-MWCNTs and PANI, reactions. The first step is the most common for all the catalytic reactions
the porosity of the synthesized samples increases [74–78], this in turn constituting hydrogen evolution, called the Volmer reaction in which a
increases catalytic active sites for the adsorption of hydrogen. The proton from an H2O molecule combines with electrons (e− ) to form an
generation of Hads (metallic hydrogen adsorbed) from H+ ions is also adsorbed intermediate (Hads) [82–84]

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M.Z. Khan et al. Electrochimica Acta 441 (2023) 141816

Fig. 10. (a) LSV curves (b) Tafel slopes of SnO2, SnO2/f-MWCNTs, and SnO2/f-MWCNTs/PANI (c) chronopotentiometry analysis of SnO2/f-MWCNTs/PANI for 24 h.

binary SnO2/f-MWCNTs nanocomposite were also prepared via tradi­

Table 1
tional co-precipitation and carrier fluid ultra-sonicated dispersion,
Comparison of HER catalytic efficiency of different MWCNTs-based
respectively. Structural and morphological investigations were carried
electrocatalysts.
out using XRD, FTIR, Raman, and SEM analysis, validating the successful
Catalyst Electrolyte Overpotential Tafel Slope Ref synthesis of all the samples. Improved dielectric properties were
(mV) J (mV
dec− 1)
exhibited by the ternary hybrid of SnO2/f-MWCTs/PANI (ε′ of 207 for
SnO2 NPs was observed at 100 Hz, which increases to 380 and 759 for
Ni0.5Fe0.5Se2/MWCNTs 0.5 M 200 71 [87]
binary and ternary nanocomposites, respectively) which can be ascribed
H2SO4
CoSe2/rGO/MWCNT 1 M KOH 131 52 [88] to the enhanced interfacial polarization in accordance with Maxwell-
MoSx/ 0.5 M 198 53 [89] Wagner model of space charge polarization. The overall decrease of
PDOPA@MWCNTs H2SO4 impedance with increasing conductive contents is also suggestive of
PdCu NPs/SBA-15- 0.5 M 360 45 [90] potential applications in dielectrics. Cyclic voltammetry and Galvano­
MWCNT H2SO4
Pt/f-MWCNTs 0.5 M 200 48 [91]
static charge-discharge cycles were carried out to investigate the elec­
H2SO4 trochemical performance of our synthesized samples. The specific
MoS3/MWCNTs 1 M H2SO4 130 40 [92] capacitance value of 211 C g− 1 at 1 A g− 1 was measured which is higher
SnO2/MWCNTs/PANI 0.5 M KOH 524 78 This than pure SnO2 (74 C g− 1) and SnO2/f-MWCNTs (128 C g− 1). The CV
work
plots also displayed pseudo-capacitive response with higher current
densities than either of the remaining two samples. Such an enhanced
H2 O + A + e− →A − Hads + OH − electrochemical response originates from the f-MWCNTs providing sta­
bility and conductivity along with higher surface area whereas PANI
The second step takes place via the Heyrosky reaction, given by: provides better electrical contact along with π stacked conjugated
A − Hads + H2 O + e− →H2 + OH − structure. At the same time, the ternary hybrid also exhibited improved
HER activity with an over-potential of 524 mV to achieve a current
Here A stands for the active site. The linear parts of the plotted Tafel density of 10 mA cm− 2. Hence, SnO2/f-MWCNTs/PANI can be used as a
curves were fitted into the Tafel equation: multifunctional electrode material for both supercapacitor applications
as well as a catalyst for HER. Our reported study suggests an easy and
η = a + blog|j|1
low-cost synthesis route for an improved multipurpose material that can
Here η represents the overpotential whereas a and b are two be used for both energy storage and conversion.
adjustable parameters, among which b represents the Tafel slope. The
obtained Tafel slope values further confirm these reaction kinetics with CRediT authorship contribution statement
the Heyrosky reaction as the rate-limiting step as supported by the
literature [79,82,85]. The decreasing values of the Tafel slope indicate Muhammad Zarrar Khan: Methodology, Investigation, Formal
faster charge transfer i.e. smaller overpotential to increase the same analysis, Validation, Data curation. Iftikhar Hussain Gul: Supervision,
current density [86]. Such an improvement can be attributed to the Conceptualization, Project administration, Resources. Mutawara
synergistic effects of f-MWCNTs and PANI as they have a high surface Mahmood Baig: Writing – original draft, Writing – review & editing,
area and good electrical conductivity. Furthermore, the chro­ Formal analysis. Muhammad Aftab Akram: Resources, Writing – re­
noamperometry (i-t) test was performed to ensure the electro-catalytic view & editing, Formal analysis.
stability of our synthesized SnO2/f-MWCNTs/PANI hybrid. Fig. (10c)
illustrates the i-t stability curve obtained for 48 h in 0.5 M KOH. No Declaration of Competing Interest
significant decrease in current density was observed, indicating the high
alkaline media stability. As such, the ternary composite proved to be a None
promising HER catalyst along with high alkaline media stability.
Data availability
4. Conclusion
Data will be made available on request.
Inorganic-organic nano-hybrid (SnO2/f-MWCNTs/PANI) was syn­
thesized via in situ polymerization of aniline monomers in the presence
of stannic oxide and functionalized MWCNT. The hybrid was investi­ References
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