Enhancing the electrochemical properties of the p-type conductive polymer on the surface of the new synthesized 2-(pyridin-3-ylmethylene) hydrazine-1-carbothioamide-modified electrode: computational and electrochemical study

Article abstract of DOI:10.1007/s13738-019-01612-7

Herein, 2-(pyridin-3-ylmethylene)hydrazine-1-carbothioamide(3PHCT)was first fabricated through a chemical method, and subsequently, polyorthoaminophenol (POAP)/3PHCT films were prepared using electropolymerization of POAP, carried out in the presence of the as-prepared 3PHCT to serve as the active electrode for electrochemical application. Geometry optimization and calculations of structural and electronic/vibrational properties of the 3PHCT system are studied (based on the quantum atom-in-molecule theory, QTAIM). In addition, the local intra-molecular electron density, and its Laplacian, and, thus, intra-molecular virial forces, of this molecule system are calculated. These results show that the oxygen and sulfur atoms play domain role in intra-molecular charge and energy transfer in this molecular system. In addition, based on the QTAIM, it is predicted that a single electrochemical molecular system can be grouped into p-type-like and n-type-like sections, and would be good candidate to reduce intra-molecular repulsion of the bipolaron during electrochemical polymerization of POAP. Galvanostatic charge–discharge experiments, cyclic voltammetry and electrochemical impedance spectroscopy, were conducted to characterize the prepared composite films and investigate the performance of the system, respectively. In this study, novel POAP/3PHCT are presented for electrochemical redox capacitors possessing the merits of high active surface area, stability in an aqueous electrolyte and ease of synthesis.

Full text of DOI:10.1007/s13738-019-01612-7

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-019-01612-7
ORIGINAL PAPER
Enhancing the electrochemical properties of the p-type conductive
polymer on the surface of the new synthesized 2-(pyridin-3-
ylmethylene) hydrazine-1-carbothioamide-modified electrode:
computational and electrochemical study
1
1
1
1
Reza Safari · Ali Ehsani · Mohamad Bigdelo · Babak Mirtamizdoust
Received: 21 May 2018 / Accepted: 23 January 2019
©
Iranian Chemical Society 2019
Abstract
Herein, 2-(pyridin-3-ylmethylene)hydrazine-1-carbothioamide(3PHCT)was first fabricated through a chemical method,
and subsequently, polyorthoaminophenol (POAP)/3PHCT films were prepared using electropolymerization of POAP,
carried out in the presence of the as-prepared 3PHCT to serve as the active electrode for electrochemical application.
Geometry optimization and calculations of structural and electronic/vibrational properties of the 3PHCT system are
studied (based on the quantum atom-in-molecule theory, QTAIM). In addition, the local intra-molecular electron den-
sity, and its Laplacian, and, thus, intra-molecular virial forces, of this molecule system are calculated. These results
show that the oxygen and sulfur atoms play domain role in intra-molecular charge and energy transfer in this molecu-
lar system. In addition, based on the QTAIM, it is predicted that a single electrochemical molecular system can be
grouped into p-type-like and n-type-like sections, and would be good candidate to reduce intra-molecular repulsion
of the bipolaron during electrochemical polymerization of POAP. Galvanostatic charge–discharge experiments, cyclic
voltammetry and electrochemical impedance spectroscopy, were conducted to characterize the prepared composite
films and investigate the performance of the system, respectively. In this study, novel POAP/3PHCT are presented for
electrochemical redox capacitors possessing the merits of high active surface area, stability in an aqueous electrolyte
and ease of synthesis.
Keywords Electrochemical characterizations · Quantum · Computational method · QTAIM · Impedance
Introduction
charge carrier transport inside the polymer and an elec-
tronic transfer at the metal–polymer interface [14]. These
processes would only be dependent on the degree of oxida-
tion of the polymer. However, it has also been suggested that
the external supporting electrolyte contacting the polymer
film could be incorporated into the polymer phase [15, 16].
This internal electrolyte phase can play an important role
in the charge-transport and charge-transfer processes of the
polymeric material. In this way, a certain fraction of the
ionic charge could be transported across the polymer film
by this excess of electrolyte and another one by the charge-
balancing inions.
Poly-o-aminophenol (POAP) is an electroactive polymer,
which has been synthesized on different electrode materi-
als [1–4] and characterized using different electrochemical
techniques [5–7]. Several practical applications of POAP in
the field of biosensors [8–10] and electrocatalysis [11–13]
have been reported in the recent literature.
It is well known that, without redox species in solution,
the charge-transport process of an electrode modified by
an electroactive polymer film is affected by ionic transfer
at the polymer–electrolyte interface, ionic and electronic
That various results referring to the conductivity of the
POAP film have been reported in the literature [17–28]
demonstrates not only the experimental procedure utilized
for the production of the polymer film but also the dopant
anions and purity of the starting monomer can strongly
*
Reza Safari
safari_physicalchemistry@yahoo.com; r.safari@qom.ac.ir
1
Department of Chemistry, Faculty of science, University
of Qom, Qom, Iran
Vol.:(0
1
123456789)
3

Journal of the Iranian Chemical Society
affect the electrochemical response of POAP. The elec-
trical and dielectric properties of conductive polymers
can be modified through the addition of different organic
compounds and nanoscale inorganic fillers, the most
interesting ones owing to possessing superior properties
arising from their nanosize structure and large surface
area.
Experimental approach
Reagent and materials
All the chemical materials used in this work, obtained from
Merck Chemical Co., were of analytical grade and used
without further purification. Double-distilled water was used
throughout the experiments.
In this study, at the first time, the new organic ligand
(
Scheme 1) was synthesized and placed on the surface of
the working electrode. The synthesized ligand is electro-
active, and, during polymerization process, can be oxi-
dized and reduced, as well as reducing the repulsion of
redox centers in the formed bipolaron. In this regards,
the electronic properties of the ligand were first studied
with DFT calculation, and then, the effect of presence
of the ligand during electropolymerization process of
conductive polymer (polyortho aminophenol) is investi-
gated in detail. Cyclic voltammetry, galvanostatic charge
discharge, and impedance spectroscopy techniques were
utilized to investigate the capacitive behavior of the pre-
pared composite.
Characterization
All the electrochemical experiments were conducted through
an Autolab General Purpose System PGSTAT 30 (Eco-
chime, Netherlands). A traditional three-electrode cell,
including an Ag/AgCl reference electrode (Argental, 3 M
KCl), a platinum wire as the counter electrode, and a carbon
paste electrode as the working electrode, was utilized for
electropolymerization of the POAP.
Synthesis of 3PHCT
To synthesize 2-(pyridin-3-ylmethylene)hydrazine-
1
-carbothioamide (3phct), A solution of nicotinaldehyde
(
5 mmol) in EtOH (20 mL) was added dropwise to a solution
of hydrazinecarbothioamide (5 mmol) in EtOH (20 mL). The
mixture was refluxed for 12 h. The white precipitates were
removed by filtration and recrystallized from the EtOH solu-
tion (Scheme 2). m.p. = 200 °C, yield: 83%. Analysis: found
C: 46.50, H: 4.50, N: 31.00%, calculated for C H N S: C:
7
8
4
4
6.68, H: 4.47, N: 31.09%.
−
1
IR (cm ) selected bonds: 620, 728, 728 1091 (ν
),
N–N
1
426 (ν
C–H
-aromatic), 1613 (ν
), 1705 (νC = O), 2979
C = C
C = N
(
ν
-aliphatic), 3068 (ν -aromatic), 3162 (ν ), and
C–H
NH2
Scheme 1 Molecular structure of 3PHCT
3412 (ν ).
NH2
Scheme 2 Synthesis reaction for 3PHCT
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Journal of the Iranian Chemical Society
Synthesis of POAP and POAP/3PHCT
Results and discussion
POAP/3PHCT composites were fabricated through
stirring a solution-containing 0.01 M monomer, 0.1 M
Computational results
−
3
LiCO , 0.5 M HClO , and 5.0 × 10 M sodium dode-
Geometry optimization and calculations of structural and
electronic/vibrational properties of the molecular system are
studied in this work (Fig. 1), which have been carried out at
B3LYP/6-311G* level of theory. Samples of the results are
demonstrated in Figs. 1 and 2 and Table 1 (not reported all
here for brevity).
4
4
cyl sulfate (SDS) on the surface of the 3PHCT-modi-
fied working electrode. Moreover, the POAP electrode
was prepared in such a solution without the addition of
3
PHCT in the surface of the working electrode. Then, the
electropolymerization was carried out via 40 consecutive
cycles in the potentials between − 0.5 and 1.0 V at the
The quantum theory of atoms in molecules (QTAIM) is
a generalization of quantum mechanics to open systems
(as opposed to closed whole systems). QTAIM defines the
open systems in terms of the topology of the electron den-
sity, that we can calculate, and that determines chemical
behavior and reactivity [29, 30]. Based on the QTAIM, the
−
1
sweep rate of 50 mV s . Assuming a current efficiency
of 100% for the electropolymerization process, the mass
of POAP films was estimated using Faraday’s law.
total atomic electronic energy, E (Ω), is the sum of
e
Fig. 1 The molecular structure is studied in this work (a). The molecular orbital energy diagram (b) and HOMO/LUMO molecular orbitals (c/d)
of the molecular system is studied in this work, are calculated at B3LYP/6-311G*level of theory
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Journal of the Iranian Chemical Society
Fig. 2 The IR spectrum (a) and intra-molecular electrostatic potential, ESP (b) of the molecular system is studied in this work, which are calcu-
lated at B3LYP/6-311G*level of theory
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Journal of the Iranian Chemical Society
Table 1 The value of the some thermal/electronic properties of
molecular structure is studied in this work, Scheme 1, which are cal-
culated at B3LYP/6-311G*level of theory
Electrochemical results
The typical multi-sweep cyclic voltammograms, which carried
out during electropolymerization of POAP in the presence of
Thermal correc- Thermal correc- Sum of elec-
Sum of
tion to energy
in Hartree/
particle)
tion to enthalpy tronic and zero- electronic and
3
PHCT, is represented in Fig. 4. As depicted in the figure,
(
point energies
thermal free
energies
ortho aminophenol has been oxidized irreversibly around
about 600 mV with no corresponding cathodic processes in the
reverse scan. Furthermore, the peak current of POAP/3PHCT
composite is higher in comparison with pure POAP film.
The electrochemical performance of the composite films
was evaluated through conducting CV measurements in 0.5 M
0
.163104
0.164048
−888.69113
−888.729736
Table 2 The average value of the electron density, ꢀ(r), Laplacian
2
HClO to illustrate the electrochemical activity of 3PHCT and
4
of the electron density, ∇ ꢀ(r), and atomic electronic kinetic energy,
its impact on the POAP films properties. According to the
presented CV in Fig. 5, 3PHCT is electroactive in the acidic
media and has two reversible peaks. In the absence of poly-
mer, this material exhibited these peaks at very low intensity,
but, in the presence of polymer, peaks showed a significant
increase, indicating that there is an appropriate interaction and
synergism effect between the polymer and the 3PHCT. Based
on DFT results, the position of HOMO orbitals is located in
the sulfur region and the possibility of changes during the
oxidation process and reduction can be related to this area.
The CVs referring to POAP and POAP/3PHCT electrodes
is depicted in Fig. 5, in which the capacitance of composite
electrode is greater than that of POAP electrode, demonstrat-
ing the effect of 3PHCT in enhancing the capacity of the
POAP electrode. The shape of CV curves may be affected
through the synergetic effect originating from the interactions
between POAP and 3PHCT. It can enhance the capacitance of
the composite, arising from the redox transitions of 3PHCT,
and maintain its superior capacitive behavior.
K(Ω), for some/critical atomic basins (Ω), of the molecular system
shown in Scheme 1, are calculated using QTAIM theory (all in a.u.)
2
∇ ꢀ(r)
Ω
ꢀ(r)
K(Ω)
−
2
2
S
15.935
8.110
1.790 × 10
3.9760 × 10
−
2
1
N (Ph ring)
N (N–H group)
N (N–N bond)
N (N –N bond)
H (N–H group)
C (C–S bond)
−1.187 × 10
−1.113 × 10
−1.373 × 10
−1.230 × 10
−7.513 × 10
−1.649 × 10
5.514 × 10
−
2
1
8.085
5.512 × 10
2
*
−2
−2
−4
1
7.710
5.4933 × 10
*
1
7.729
5.4934 × 10
−
1
−1
2
5.913 × 10
5.582 × 10
−
3
1
5.485
3.755 × 10
involving kinetic and potential energies, K(Ω) and V(Ω),
as E (Ω) = K(Ω) + V(Ω), where Ω denotes the atomic
e
basin. The expectation value of a quantity corresponding
to an operator averaged over all space is given by the sum
of the expectation values of this operator averaged over the
All Atoms
∑
Figure 6 shows the cyclic voltammograms of
POAP/3PHCT films, recorded in various potential sweep
atomic basins, as < A>Molecule
=
A(Ω).
Ω
−
1
In this work, based on the QTAIM, the local intra-
molecular electron density, and its Laplacian, and thus
intra-molecular virial forces, of the molecular is studied
in this work are calculated and samples of the results are
shown in Table 2, and demonstrated in Fig. 3.
rates in the range of 25–400 mV s , in which the slope of
the straight line between the anodic peak current and poten-
tial sweep rate in log–log scale provides the value of frac-
tal dimension for each film 23–25. The fractal dimension
amount of 2.67 was obtained for the electrosynthesized film,
confirming the porous structure of the electrosynthesized
composite film.
Analysis of these results (not reported here for brevity)
shows that the local/atomic electronic properties are gen-
erally dependent on the atomic basin properties, and this
results show that the oxygen and sulfur atoms plays domain
role in intra-molecular charge and energy transfer in this
molecular system. In addition, based on the QTAIM, it is
predicted that a single electrochemical molecular system
can be grouped into p-type-like (as intra-molecular donor
section) and n-type-like sections (as intra-molecular accep-
tor section) (Fig. 3). In addition, once local intra-molecular
charge/energy transfer can be studied (described) via quan-
tum mechanical calculations; it will be possible to study/
calculate the intra-molecular electrochemical transport
properties in electrochemical systems also.
Galvanostatic charge/discharge method was utilized to
ascertain the capacitance characteristic of POAP/3PHCT
composite electrode. The charge/discharge behavior of
POAP and POAP/3PHCT electrodes is depicted in Fig. 7 in
the potential range from −0.6 to 0.6 V, between which a tri-
angular shape can be observed, exhibiting not only excellent
columbic efficiency but also superior capacitive behavior of
POAP/3PHCT as electrode in supercapacitor application.
The specific capacitance (SC) of electrodes can be deter-
mined from the CV curves as follows: 30.
I ΔT
C =
.
(
1)
ΔV m
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Journal of the Iranian Chemical Society
Fig. 3 The local contour map (in molecular plan) of electron density
sity scheme grouped into p-type-like/ n-type-like sections (f) of the
molecular is studied in this work, which are calculated at B3LYP/6-
311G*level of theory
(
a), Laplacian of electron density (b), Lagrangian kinetic energy den-
sity. KEG (c), Hamiltonian kinetic energy density. KEK (d), intra-
molecular virial force (e), and the local intra-molecular electron den-
In this equation, I is the current, V is the potential, and
m is the mass of the reactive material. Based on the above-
mentioned equation, the SC of POAP/3PHCT electrodes was
the nanocomposite retained more than 90%, even after 1000
cycles (Fig. 7d), indicating good electrochemical cycling
stability in comparison to pure POAP.
−
1
found to be 620 F g
.
The electrode kinetics and other properties of the as-
prepared materials were investigated using electrochemical
impedance spectroscopy (EIS) 31–35. Not only two partially
overlap semicircles in the high- and medium-frequency
regions, but also an inclined line in the low-frequency region
is generally observed in the impedance curves, as depicted in
The long-term cycle performance and stability are of
great importance for practical applications of electrochemi-
cal supercapacitors. The cycling performance of the com-
posite was examined by galvanostatic charging and discharg-
ing at a current of 1 mA for 1000 cycles. The capacitance of
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Journal of the Iranian Chemical Society
Fig. 4 The typical multi-sweep cyclic voltammograms during the
electropolymerization of POAP/3PHCT
Fig. 6 Cyclic voltammograms of POAP/3PHCT films in various
potential sweep rates
According to the our previous works [36, 37], the
behavior of space charge capacitance vs E (potential)
dependence and the observed capacitance values were typ-
ical of a thin-film semiconductor electrode and suggest the
formation of space charge or depletion region within the
polymer film. This conclusion is consistent with numerous
result of other authors who demonstrated the formation
of a space charge region (SCR) on conducting polymer
modified electrodes. At the negative potentials, the space
charge region extends over whole film. As the potential
drops across the SCR decrease, its thickness becomes
smaller than the film thickness, and a quasi-neutral region
is formed and the electrode capacitance increases. The
dependence of the electrode capacitance on the potential
in the simplest case is given by the Mott–Schottky equa-
tion [38, 39]:
Fig. 5 Cyclic voltammograms of POAP and POAP/3PHCT elec-
−
1
trodes in 0.5 M HClO at the sweep rate of 100 mV s . Inset shows
4
3
PHCT CV in acidic solution
ꢀ
ꢁ
2
KT
−
2
C
=
E − E −
fb
,
(2)
ꢀ
ꢀ0eNA2
e
Fig. 8. Z-view software was utilized to calculate the imped-
ance of the material according to an equivalent circuit, as
represented in Fig. 8 as an inset. To simulate the double-
layer capacitance, the EIS data can be fitted via a bulk solu-
where C is the space charge capacitance, ε is the dielectric
constant of the polymer, ε is the permittivity of free space,
0
’
e is the elementary charge, k is Boltzmann s constant, T is
tion resistance R , a pseudocapacitance (CPE2) from redox
the absolute temperature, N is the carrier density that set
s
process of the materials, a charge-transfer resistance R and
up the space charge, and (E−E ) is the absolute value of
ct
fb
a constant phase element (CPE1). Not only the bulk-film
the potential drop across the SCR. The flat band potential
transport of electrons but also the charge-transfer resist-
E
is the potential at which the thickness of the SCR is
fb
−
2
ance (R ) of the composite was found to be considerably
zero. From Eq. (2), it follows that C vs. E line is known
ct
poor, based on the results acquired from Nyquist plots. The
slope of the impedance plot increased and tended to become
purely capacitive (vertical line is the characteristic of a limit-
ing diffusion process CPE2) in the low frequency, indicating
the higher electrochemical capacitance of this material.
as Mott–Schottky plots. The values of the carrier density
1
9
in two cases can be also be calculated as 1.85× 10 and
1
9
−3
6.19×10 cm for the film in the absence and presence of
3PHCT, respectively, from the slop of the plots. The higher
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Journal of the Iranian Chemical Society
Fig. 7 Charge and discharge measurements of a POAP and POAP/3PHCT electrode in 0.1 M HClO solution at 0.005 mA, b different current
4
for composite, c during consecutive 10 charge–discharge, and d during consecutive 100 charge–discharge of composite film
density of carriers in the presence of 3PHCT than pure
POAP film, indicating that there is an appropriate interaction
and synergism effect between the polymer and the 3PHCT.
Furthermore, the negative slopes of Mott–Schottky plots of
them show that we can categorize them as p-type semicon-
ductors where the space charge is established by counter
anions. In this case, polarons or bipolarons act as holes in
ordinary semiconductors [40].
carried out in the presence of the as-prepared 3PHCT to
serve as the active electrode for electrochemical applica-
tion. Geometry optimization and calculations of structural
and electronic/vibrational properties of the 3PHCT sys-
tem are studied, and based on the QTAIM theory, the local
intra-molecular electron density, and its Laplacian, and thus
intra-molecular virial forces, of the molecular is calculated.
Analyses of these results show that the local/atomic elec-
tronic properties are generally dependent on the atomic
basin properties and this results show that the oxygen and
sulfur atoms plays domain role in intra-molecular charge
and energy transfer in this molecular system. The 3PHCT
represents an evident improvement effect by providing more
active sites on the composites for faradic reaction as well as
larger specific capacitance in comparison with pure POAP.
Conclusions
Herein, 3PHCT was first fabricated through a chemical
method, and subsequently, POAP/3PHCT hybrid films
were prepared using electropolymerization of POAP, which
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Journal of the Iranian Chemical Society
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