Journal of Molecular Liquids 378 (2023) 121637

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Journal of Molecular Liquids

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

Corrosion inhibition of Schiff base and their metal complexes with

[Mn (II), Co (II) and Zn (II)]: Experimental and quantum chemical studies
Chérifa Boulechfar a,b, Hana Ferkous a,b,⇑, Amel Delimi a,b, Malika Berredjem c, Abdesalem Kahlouche d,
Anis Madaci e,f, Souad Djellali g, Sihem Boufas a,b, Amel Djedouani h,i, Abdelhamid Errachid e,
Azmat Ali Khan j, Abir Boublia g, Tarek Lemaoui k, Yacine Benguerba k,⇑
a
Laboratoire de Génie méncanique et Matériaux, Faculté de Technologie, University 20 Août 1955-Skikda, Skikda 21000, Algeria
b
Département de Technologie, University 20 Août 1955-Skikda, Skikda 21000, Algeria
c
Laboratory of Applied Organic Chemistry LCOA, Synthesis of Biomolecules and Molecular Modeling Group, Badji-Mokhtar-Annaba University, Box12, 23000 Annaba, Algeria
d
Research Centre in Industrial Technologies–CRTI, P.O. Box 64, Cheraga 16014 Algiers, Algeria
e
University of Lyon, Institute of Analytical Sciences, 69100 Villeurbanne, France
f
University El-Bachir El-Ibrahimi Bordj Bou Arreridj, Laboratory of Materials and Electronics Systems, 34000 Bordj Bou Arreridj, Algeria
g
Laboratoire de Physico-Chimie des Hauts Polymères(LPCHP), Faculty of Technology, University Ferhat Abbas Setif1, 19000 Setif, Algeria
h
Laboratoire de Physicochimie Analytique et Cristallochimie des Matériaux Organométalliques et Biomoléculaires, Université Constantine 1, 25000 Constantine, Algeria
i
Ecole Normale Supérieure de Constantine, Ville Universitaire Ali Mendjeli, 25000 Constantine, Algeria
j
Pharmaceutical Biotechnology Laboratory, Department of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia
k
Laboratoire de Biopharmacie Et Pharmacotechnie (LPBT), Ferhat Abbas Setif 1 University, Setif, Algeria

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

Article history: The synthesis, characterization, and examination of anti-corrosion performance of 2-furaldehyde semi-
Received 3 November 2022 carbazone Schiff base (FSC) complexes of cobalt (II), zinc (II), and manganese (II) on XC38 carbon steel
Revised 15 February 2023 immersed in 1 M HCl solution are performed using experimental investigations and quantum chemical
Accepted 12 March 2023
simulation approaches. The theoretical approach used were DFT calculations and MC simulation. The
Available online 15 March 2023
inhibition effect was also studied by electrochemical impedance spectroscopy (EIS), and potentiodynamic
polarization (PDP). Electrochemical testing results show that these chemical compounds are particularly
Keywords:
powerful inhibitors, which FSC-Mn provides a considerable inhibition of 91.48%at 500 ppm. The results
Corrosion, Inhibitor, Schiff bases
Metal complexes
also demonstrate that the inhibition effect of the four inhibitors increased with increasing inhibitor con-
XC38 carbon steel centration, revealing that these compounds adsorb significantly to the steel surface. The scanning elec-
DFT calculations tron microscopy (SEM) analyses indicated that FSC and its complexes adsorbed onto the surface of
Monte Carlo simulations XC38 carbon steel by forming a barrier between the inhibitors and the vacant d-orbital of iron.
Quantum investigations were consistent with experimental findings on the four inhibitors’ capacity to
prevent XC38 carbon steel from corroding in 1 M HCl, which were also proven effective as cathodic
and anodic type inhibitors, displacing water molecules from mild steel, and producing heterogeneous
coatings on the XC38 carbon steel surface to defend against corrosion.
Ó 2023 Published by Elsevier B.V.

1. Introduction
The structural diversity and relative ease of synthesizing Schiff
bases and their metallic complexations have made them candi-
dates for upcoming chemical and structure research. Since they
have numerous desirable chemical properties and applications,
⇑ Corresponding authors at: Laboratoire de Génie méncanique et Matériaux,
Faculté de Technologie, University 20 Août 1955-Skikda, Skikda 21000, Algeria (H.
Ferkous).
E-mail addresses: h.ferkous@univ-skikda.dz (H. Ferkous), yacinebenguerba@u-
niv-setif.dz (Y. Benguerba).
they have been the focus of much research [1,2]. Antibacterial,
antioxidant, and anti-inflammatory characteristics are only a few
of the medical applications for Schiff bases and metal complexes
[3–5]. Among the many advantages of the optimal inhibitor are
its high inhibitory efficiency, low cost, low toxicity, and ease of fab-
rication [6,7]. The use of inhibitors has the potential to lessen metal
loss caused by corrosion. Metal’s wide range of applications
includes the chemical and petrochemical industries [8,9]. Corro-
sion inhibitors are very useful for protecting metals from oxidation
in moist, humid, and acidic conditions [10], where their effective-
ness on metal surfaces is correlated to the significance of the
formed bonds. Inhibitors containing nitrogen (
N), oxygen (
O),

https://doi.org/10.1016/j.molliq.2023.121637
0167-7322/Ó 2023 Published by Elsevier B.V.
Chérifa Boulechfar, H. Ferkous, A. Delimi et al. Journal of Molecular Liquids 378 (2023) 121637

and sulfur ð
SÞdonor sites; unsaturated bonds, and planar conju- 2.3. Corrosive working solutions
gated aromatized compounds are recommended as effective corro-
sion inhibitors, regarding their ability to donate a single pair of Laboratory HCl and distilled water were used to make 1 M HCl
electrons or receive electrons in metals’ vacant d-orbitals [11,12]. electrolyte solutions with and without the inhibitors (ligand and
Due to the existence of the imine (> C ¼ N
) bond, the application its metal complexes). The inhibitors were used at concentrations
of Schiff bases as corrosion inhibitors in alloys and metals has been between 50 and 500 ppm.
the principal focus of several Schiff base research fields [13,14].
Consequently, several Schiff base metal complexes have been stud-
ied and evaluated for their potential as corrosion inhibitors [15,16]. 2.4. Electrochemical study
Corrosion of metals may be slowed in thin, long-lasting coatings by
the adsorption of Schiff base molecules, which may postpone In the electrochemical studies, carbon steel, platinum, and sat-
either the anodic or cathodic processes [17,18]. It is important to urated calomel were utilized as working electrode (WE), counter-
take into account experimental factors such as inhibitor concentra- electrode (CE), and reference electrode (RE), respectively. In order
tion, molecule shape, and substituent type [19]. The type of metal, to conduct electrochemical impedance spectroscopy (EIS), a
the surrounding environment, and the molecule’s size are all addi- GAMRY 600+ potentiostat-galvanostat and GAMRY software were
tional factors. Several Schiff bases and their metallic complexations utilized. The WE was soaked in the corrosive solution (1 M HCl)
have been shown to successfully prevent mild steel (Fe), aluminum for one hour before the reading was taken. The open circuit poten-
(Al), copper (Cu), and zinc (Zn) from corroding in acidic circum- tial was used to perform EIS measurements between 50 kHz and
stances [20,21]. Simulations employing density functional theory 10 MHz and 10 mV in amplitude. Potentiodynamic polarization
(DFT) and molecular dynamics (MD) have been demonstrated to curves were produced Using a scan rate of
greatly enhance the background in the fundamental processes 1 mV s
1 from
200 to þ 200 mV s
1 . The efficiency of the
driving molecule interactions with a wide variety of substances inhibition may also be determined from the Tafel plot using the
and solid surfaces [22–24]. Selecting the appropriate corrosion following formula [28–30].
inhibitor for a specific application, as an example, might improve
performance. Diverse scholars have used DFT and MD theoretical  
0
techniques to examine corrosion inhibition [25,26]. icorr
icorr
Eicorr ð%Þ ¼ 0
 100 ð1Þ
This work aims to evaluate the impact of four inhibitors based icorr
on Schiff base; 2-furaldehyde semicarbazone (FSC) complexes of
0
cobalt (II), zinc (II), and manganese (II) against the corrosion of icorr and icorr , the density of the current in the solution as deter-
XC38 carbon steel in 1 M HCl solution. Experimental studies were mined by the Tafel plot without and with the inhibitor. Using the
investigated to determine the effect of concentration on the behav- Stern-Geary relation, the polarization resistance Rp (cm2) was
ior of the corrosion inhibitors in which several concentrations were determined as follows:
tested by measuring their effects via utilizing electrochemical
impedance spectroscopy (EIS) and potentiodynamic polarization ba bc
(PDP) methods. Furthermore, the surface analysis of XC38 carbon
Rp ¼ ð2Þ
2:30icorr ðba þ bc Þ
steel was investigated by applying the scanning electron micro-
scopy (SEM) method. In addition, total energy calculations based The anodic and cathodic Tafel slopes are denoted by ba and bc.
on DFT and Monte Carlo (MC) simulations were conducted to gain The effectiveness of inhibition was determined using the following
deeper insight into the inhibitory mechanism. polarization resistance values:

 
Rp
R0p
ERp ð%Þ ¼  100 ð3Þ
Rp
2. Material and methods
R0p and Rp are the polarization resistance values before and after
2.1. Inhibitors used the inhibitor. EIS Experiments were conducted at an open-circuit
potential, with a signal amplitude of 10 mV and a frequency range
The Schiff base complexations of manganese (II), cobalt (II), and of 50 kHz to 10 mHz. Using the combined EIS data and the follow-
zinc (II) with 2-furaldehyde semicarbazone are the primary focus ing formula [31], the inhibition efficiency is expressed as:
of this research (FSC). Fig. 1 depicts the structures of these com-
pounds. The synthesis and characterization of these compounds  
were performed by Boulechfar and colleagues [27]. Rct
R0ct
EEIS ð%Þ ¼  100 ð4Þ
Rct
R0ct and Rct show how much resistance there is to charge transfer
2.2. Carbon steel samples either without or with an inhibitor.

For the corrosion tests, all of the samples and the working elec-
trode were constructed of XC38 carbon steel, which was also uti-
lized for gravimetric and electrochemical measurements.
The samples were first immersed in a corrosive electrolyte solu-
tion, then mechanically abraded (with sandpaper ranging in mesh/
degree from 400 to 2000), Initially washed in distilled water, then
treated with acetone, and lastly heated air-dried. The dimensions
of the samples were 15 mm in diameter by 5 mm in height. They
were implanted in a non-living material with a 1.77 cm2 visible
surface area to take electrochemical readings.
2
2.5. Characterization of the surface
Samples were immersed in 1 M HCl at 298 K for 24 h with or
without inhibitors for different characterizations (500 ppm). The
products were removed, washed with distilled water, and air-
dried. The SEM analysis was used to examine the corrosion-
induced morphological changes on the surface of carbon steel.
SEM images were captured using an FEI Quanta 250 equipment
at 20 kV acceleration voltage.
Chérifa Boulechfar, H. Ferkous, A. Delimi et al.
FSC
FSC-Co
Fig. 1. Ligand and its complexes’ molecular structure.
3. Theoretical study
3.1. Quantum calculations
Theoretical simulations are extremely useful tools for evaluat-
ing the inhibition properties of novel inhibitors [31,32]. Therefore,
DFT-based total energy calculations were performed utilizing the
TURBOMOLE (TmoleX version 4.5.1) suite of programs, in which
the 3D molecular structures of the complex metals were created
and optimized utilizing the generalized gradient approximation
(GGA) at BP86 functional and TZVP foundation [33–36]. To reach
convergence, the energy difference between the two solutions
had to be less than 106 Ha, and the gradient difference had to be
less than 103 Ha/Bohr [37,38]. Based on the ionization energy in
its ground state (I) and the electron affinity (A) of its inhibitor, a
set of equations for hardness (g) and electronegativity (v) (l:
chemical potential) have derived [28,29,31,39,40]:
IþA
v ¼
l ¼
2
I
A
g¼
2 the molecules involved were modeled. Containers of varying sizes,
I ¼
EHOMO
A ¼
ELUMO
As a result of the fact that the value of the l is proportional to
the value of the chemical proton affinity (PA).
The reciprocal of hardness, softness (r) is widely acknowledged
as a characteristic strongly connected to polarizability:
r ¼ 1=g
From their electronegativity and hardness values, ions, atoms,
and molecules may be assigned an electrophilicity index (x)
[28,29,31,39,40]:
v2
x¼
2g
Journal of Molecular Liquids 378 (2023) 121637
FSC-Zn
FSC-Mn
In corrosion investigations, the number of electrons transported
(DN) from the inhibitor molecule to the carbon steel sample sur-
face was determined [29,41].
DN ¼ ½vFe
vinh =½2ðgFe þ ginh Þ ð11Þ
where vFe , vinh , ginh , and gFe are the work function, electronegativity
of inhibitor, inhibitor hardness, and (Fe) metal hardness, respec-
tively. The value of gFe is assumed to be 0 (I = A for metals in their
bulk form). For the Fe (1 1 0) surface, the work function is 4.82 eV
[42,43].
3.2. Monte Carlo (MC) simulations
In order to synthesize the experimental results and provide a
rationale for the physical adsorption behavior of our metallic com-
plexes on an iron (1 1 0) surface, MC simulations were carried out.
Metropolis Monte Carlo (MCS) simulations were used to model the
inhibitory impact using the adsorption locator module [39,40] in
ð5Þ
Materials StudioÒ 2017. Finding the inhibitor/steel configuration
with the lowest total energy is possible using the MCS approach.
In order to understand how the corrosion-inhibiting process works,
ð6Þ
such as the steel slab supercell (5x5), 1 molecule of inhibitor, 50
ð7Þ molecules of water, and 10 molecules of HCl were developed for
this specific purpose. The interaction forces were calculated using
ð8Þ the force field of Dreading [39,40] throughout the simulation.
4. Results and discussion
4.1. Polarization analysis
ð9Þ
Corrosion tests were performed on XC38 carbon steel sub-
merged in 1 M hydrochloric acid utilizing polarization measure-
ments on the FSC ligand and its metal complexes. Corrosion data
including corrosion potential (Ecorr), corrosion current density
(icorr), and percentage of inhibition efficiency (Eicorr(%)) were
ð10Þ recorded, and the Tafel polarization plots were shown in Fig. 2.
By measuring polarization, researchers could see that the current
3
Chérifa Boulechfar, H. Ferkous, A. Delimi et al. Journal of Molecular Liquids 378 (2023) 121637

a) b)

c) d)

Fig. 2. Polarization curves for XC38 carbon steel in 1 M HCl with and without FSC ligand and metal complexes, a) FSC, b) FSC-Zn, c) FSC-Co, and d) FSC-Mn.

density was drastically decreased after adding an inhibitor. The
inhibition efficiency of all chemicals rises with increasing the inhi-
bitor concentrations since more inhibitor molecules are adsorbing
onto the carbon surface of steel [28,39]. Increasing inhibitor con-
centrations in 1 M HCl decreases simultaneous anodic and cathodic
current densities (Table 1). The existence of these inhibitors slows
down both the anodic and cathodic processes. Ecorr values that vary
by just around 17 mV relative to blank indicate that the inhibitor
has a mixed-type action, as described by the literature [40,42–
44]. It was stated that the effectiveness of inhibition increased
from [FSC-Mn] to [FSC-Co] to [FSC-Zn] to [FSC]. This is because
the Mn complex exhibits lower corrosion current density of corro-
sion compared to both the ligand as well as other metal complex-
ations. Therefore, high adsorption of the Mn metal complex onto

Table 1
FSC ligand and its complexes polarization properties.

Parameters Concentration Ecorr icorr ba bc Rp corrosion rate (mmyear
1) Correlation Eicorr

(ppm) (mV) (lA cm
2) (mVdec-1) (mVdec-1) (O cm2) (%)
Blank HCl 466.322 321.289 121.20 116.70 77.90 2.119 0.9998 –
FSC 50 477.188 135.018 113.30 92.60 139.00 0.890 0.9994 57.97
100 471.769 128.155 106,10 97.80 145.00 0.845 0.9999 60.11
200 449.582 116.503 83,50 91.10 148.00 0.768 0.9999 63.73
400 480.246 87.663 93.00 95.50 217.00 0.578 0.9980 72.71
500 460.039 74.406 97.10 101.30 279.00 0.491 0.9994 76.84
FSC-Zn 50 478.185 209.649 119.90 94.30 106.00 1.382 – 34.74
100 463.039 130.065 91.10 99.40 148.00 0.857 0.9991 59.51
200 471.891 117.201 99.00 97.30 172.00 0.773 0.9992 63.52
400 472.171 59.496 84.10 85.40 262.00 0.3924 0.9994 81.48
500 468.141 58.367 83.10 93.90 294.00 0.384 0.9992 81.83
FSC-Co 50 459.573 173.172 103.30 88.10 127.00 1.010 0.9991 46.10
100 461.975 146.197 104.70 91.40 138.00 0.964 0.9997 54.49
200 469.860 73.056 99.80 99.80 279.00 0.481 – 77.26
400 455.691 67.008 70.80 99.00 249.00 0.442 0.9983 79.14
500 467.865 53.143 82.40 100.60 368.00 0.350 0.9969 83.45
FSC-Mn 50 468.754 148.281 86.60 91.30 136.00 0.788 0.9997 53.84
100 468.794 97.807 105.50 98.30 217.00 0.645 0.9998 69.55
200 481.989 80.168 90.60 103.70 252.00 0.528 0.9980 75.04
400 467.096 71.795 98.30 105.10 284.00 0.473 0.9989 77.65
500 466.828 49.808 98.30 105.10 427.00 0.328 0.9984 84.49

4
Chérifa Boulechfar, H. Ferkous, A. Delimi et al.
the metal surface, with an optimal inhibitory efficacy of around
84.497% at 500 ppm.
4.2. Electrochemical impedance spectroscopy
Figs. 3 and 4 exhibit Nyquist and Bode graphs of XC38 carbon
steel in 1 M HCl without and with different amounts of FSC ligand
and its metal complexes, respectively. Based on these graphs, it’s
evident that raising the inhibitor concentration in 1 M HCl causes
the XC38 carbon steel’s impedance to rise. Due to the solid elec-
trode’s location below the x-axis, the semicircles in Nyquist dia-
grams have a somewhat depressing quality. Double-layer
capacitance at solid electrodes is often shown to behave non-
ideally in experiments, including impedance spectroscopy. Anion
adsorption and roughness or other inhomogeneities in the solid
electrode have been implicated in the dispersion. A constant phase
element (CPE) may be used to model the distribution of anomalous
capacitance, and its impedance (ZCPE) can be written as follows
[45,46]:
1
Z CPE ¼ n ð12Þ
Q ðjwÞ
where Q represents the double-layer capacitance, j represents an
imaginary unit (j2 =
1), n represents a phase shift satisfying a
range of 0 to 1, and w represents the angular frequency in hertz.
The relationship between the CPE constant and Cdl is shown by
the following equation [32]:
C dl ¼ Q dl ðxmax Þn
1 (13)where xmax is the angular frequency at
which the imaginary part of the impedance is the largest. Using
CPE to remedy nonideal circumstances on solid surfaces was
described above; this adjustment has to mask the other compo-
nents in the equivalent circuit. Alternatively, the CPE may be seen
as a perfect capacitor.
a)
c)
Fig. 3. Nyquist diagrams of XC38 carbon steel in 1 M HCl with and without FSC ligand and metal complexes, a) FSC, b) FSC-Zn, c) FSC-Co, and d) FSC-Mn.
5
Journal of Molecular Liquids 378 (2023) 121637
Corrosion inhibition of XC38 carbon steel by FSC and its com-
plexes at different concentrations seems to be mediated by the
same mechanism, as shown by the fact that no changes in the
impedance behavior profile were seen when the concentration of
FSC or its complexes was changed. A single high-frequency capac-
itive loop and a time constant, represented by the solution resis-
tance (Rs) and charge transfer resistance (Rct), are shown in the
Nyquist and Bode plots (Fig. 4). The almost universal presence of
a single capacitive loop in Nyquist diagrams [46] suggests that
charge transfer processes play a primary role in regulating metal
dissolution.
Using EC-Lab, we can fit the EIS data to an equivalent circuit
(Fig. 5), and from that, we can get the impedance values listed in
Table 2. The Nyquist diagram of the inhibitor-free solution was
described using the equivalent circuit with a single semicircle
(Fig. 5a). Nyquist plots of solutions inhibited by FSC and its metal
complexes were best represented by the equivalent circuit shown
in Fig. 5b. Charge transfer resistance (Rct) and double layer constant
phase element CPEdl (Qdl, ndl) were correlated (Fig. 5a). To more
precisely describe the metal/solution interface, two additional ele-
ments, Rf (reflecting the film resistance of adsorbed inhibitor mole-
cules) and CPEf (Qf, nf) (shown in Fig. 5b), were added to the
electrically equivalent circuit. In practice, the capacitance of a dou-
ble layer and a film behaves more like a constant phase element
(CPE) than a simple capacitor.
The dose-dependent increase in Rct seen in Table 2 indicates a
rise in inhibition efficiency across the board. Adsorption of the
tested compounds is likely responsible for restoring the metal’s
surface since the thickness of the adsorbed layer increases when
inhibitor dosages are increased [47,48].
Due to the substantial adsorption of inhibitors on XC38 carbon
steel surfaces, the findings reveal that the FSC ligand and its metal
complexes have a high corrosion inhibition effectiveness. Com-
b)
d)
Chérifa Boulechfar, H. Ferkous, A. Delimi et al.
a)
c)
Fig. 4. The Bode diagrams for the dissolution of XC38 carbon steel in 1 M HCl with and without FSC ligand and metal complexes, a) FSC, b) FSC-Zn, c) FSC-Co, and d) FSC-Mn.
a) b)
Fig. 5. Equivalent Electrical circuit to fitting EIS data, (a) Solution without inhibitor
(Blank) and (b) Solution containing inhibitors.
pared to FSC of Co, and Zn metal complexes, the FSC-Mn complex
exhibits the highest inhibition efficacy because of its strong
adsorption. Inhibition efficiency peaks at about 91.48 % when the
FSC-Mn metal complex is present at a concentration of 500 ppm
on the metal’s surface.
For corrosion of XC38 carbon steel in 1 M HCL, the order of inhi-
bition efficiency reported by this approach is ([FSC-Mn] > [FSC-C
o] > [FSC-Zn] > [FSC]). Corrosion research using XC38 carbon steel
by the chosen inhibitors film EIS measurements showed excellent
agreement with the conclusion of Tafel polarization.
4.3. Scanning electron microscopy
Fig. 6 displays carbon steel’s 24-hour immersion surface mor-
phology in 1 M HCl solution with and without the appropriate inhi-
bitor concentration (500 ppm). Significant corrosion damage may
be seen when metal is submerged in an acidic solution without
6
Journal of Molecular Liquids 378 (2023) 121637
b)
d)
an inhibitor (Fig. 6b) [45,49]. In pictures, carbon steel immersed
in an acid media containing inhibitors shows reduced corrosion
on its surface (Fig. 6c-f), suggesting that the inhibitor molecules
have formed layers to shield the steel from further deterioration.
For this reason, FSC and their complex molecules are adsorbed onto
the XC38 carbon steel surface, where they act as a barrier between
the inhibitors and the vacant d-orbital of iron [50–52].
4.4. Theoretical study
4.4.1. Quantum calculations
In Fig. 7, the optimal structures of the examined systems are
shown together with the atom-atom distances (in Å) for several
important places. In Table 3, we see the calculated orbital energies
for the FSC ligand, the metal complexes, and the Fe20 cluster,
together with various chemical descriptors including l, g, and v.
The energy gap value affects inhibitor molecule adsorption on
metal surfaces, making it important. Reactivity and inhibition effi-
ciency improves with decreasing Gap values [53,54]. Since the
energy is required to take an electron out of the last occupied orbi-
tal (HOMO), the inhibitory activity improves [55]. A ‘‘soft” mole-
cule in chemistry has a small Gap value, suggesting strong
chemical activity and poor kinetic stability [56]. Organic com-
pounds are efficient corrosion inhibitors by offering electrons to
the empty orbit of metal and accepting free electrons from a metal
[57–59]. Table 3 demonstrates that FSC has the lowest Gap (at
3.239 eV) and is the least reactive inhibitor of all the metal com-
plexes investigated. The FSC-Mn had the highest Gap of the
metal-FSC inhibitors at 1.875 eV. These results show that FSC is
the most stable molecule in the system. Due to its low hardness
and small Gap, the Fe20 cluster proved to be the most reactive. Cor-
Chérifa Boulechfar, H. Ferkous, A. Delimi et al. Journal of Molecular Liquids 378 (2023) 121637

Table 2
Impedance characteristics and corrosion inhibition efficacy of XC38 carbon steel in 1.0 M HCl at different inhibitor concentrations of ligands and metal complexes.

Parameters Concentration (ppm) Rs Rct ndl Qdl  10
5 Rf nf Qf  10
5 EEIS (%)
(X.Cm2) (X.Cm2) (lF sndl-1 cm
2) (X.Cm2) (lFs nf-1 cm
2)
Blank HCl 0.673 26.680 0.84 164.00 – – – –
FSC 50 1.678 61.800 0.77 128.00 3.381 0.95 20.80 56.83
100 0.954 69.480 0.72 232.00 3.499 1.00 42.40 61.60
200 0.873 81.030 0.75 288.00 2.264 1.00 8.630 67.07
400 1.413 109.40 0.73 127.00 6.182 1.00 16.70 75.61
500 0.818 154.70 0.73 171.00 0.027 0.73 11.02 82.75
FSC-Zn 50 1.051 78.200 0.77 155.00 2.951 1.00 31.80 65.88
100 1.479 94.590 0.80 103.00 6.627 0.79 0.250 71.79
200 1.217 113.30 0.77 141.00 4.101 1.00 27.40 76.45
400 1.019 161.90 0.74 129.00 3.618 1.00 22.60 83.52
500 0.938 210.70 0.52 96.800 0.811 0.82 109.0 87.34
FSC-Co 50 1.146 74.110 0.86 53.400 1.694 0.83 70.10 64.00
100 1.011 81.590 0.76 183.00 2.737 0.90 4.790 67.30
200 1.580 121.80 0.84 59.400 1.616 0.81 77.80 78.10
400 0.957 144.60 0.84 60.500 1.059 1.00 8.880 81.55
500 1.070 235.60 0.78 92.300 8.735 0.95 6.210 88.68
FSC-Mn 50 1.284 150.70 0.79 55.300 9.715 1.00 6.740 82.30
100 1.829 170.00 0.80 74.500 4.358 1.00 24.10 84.31
200 1.113 194.00 0.77 107.00 4.834 1.00 15.40 86.25
400 1.408 229.20 0.89 25.700 3.214 0.89 27.70 88.36
500 1.375 313.10 0.85 29.700 4.094 0.86 34.20 91.48

a) b) c)

d) e) f)

Fig. 6. SEM images of the carbon steel surface a) before immersion in HCl, b), c), d), e), and f) after immersion in HCl, HCl + FSC, HCl + FSC-Zn, HCl + FSC-Co, and HCl + FSC-Mn,
respectively, with 500 ppm of FSC ligand and its metal complexes.

rosion of XC38 carbon steel is inhibited most effectively by [FSC- Based on thermodynamic parameters, Parr et al. [60] estab-
Mn], followed by [FSC-Co], [FSC-Zn], and finally [FSC]. This ranking lished the electrophilicity index ðxÞ to quantify the positive energy
is based on the minimum energy gap theory. shift that occurs when a chemical system approaches saturation by

7
Chérifa Boulechfar, H. Ferkous, A. Delimi et al. Journal of Molecular Liquids 378 (2023) 121637

Fe20-Cluster FSC FSC-Mn

FSC-Zn FSC-Co

FSC-Zn@Fe20 FSC-Mn@Fe20 FSC-Co@Fe20 FSC@Fe20

Fe-O

Fe-N (NA)

Fig. 7. Optimized structures (bond length is in Å).

Table 3
Global reactivity descriptors.

Isomer EHOMO (eV) ELUMO (eV) GapðeVÞ v g x DN

Fe20
4.423
4.409 0.014 4.416 0.007 1392.933 0.000
FSC
5.094
2.258 2.836 3.676 1.418 4.765 0.285
FSC-Zn
5.753
3.157 2.596 4.455 1.298 7.645
0.812
FSC-Co
4.936
3.305 1.631 4.121 0.816 10.410 7.776
FSC-Mn
4.292
3.937 0.355 4.115 0.178 47.688 0.183

adding electrons. The transfer of electrons from the donor (HOMO) Table 4
level to the acceptor (LUMO) level results in energy dissipation. Adsorption conformations’ characteristics.

For a system containing metallic atoms like Fe and a single Bond Bond length (Å) Total energy (Ha)
molecule of an inhibitor such as FSC, FSC-Mn, FSC-Zn, or FSC-Co, FSC@Fe20 Fe-O 2.3430
3420.0369
electrons will go from the less electronegative to the higher elec- Fe-N 2.2280
3420.0526
tronegative one. From Table 3, it is concluded that electron flow FSC-Zn@Fe20 Fe-O 4.1550
5143.2093
will be from FSC, FSC-Mn, and FSC-Co to iron (positive DN) and will Fe-N – –
FSC-Co@Fe20 Fe-O 2.5260
5055.5611
have the opposite flow direction for the case of FSC-Zn (negative
Fe-N 2.2020
5055.5699
DN). The chemical potentials will remain unbalanced until this FSC-Mn@Fe20 Fe-O 2.4800
5086.9353
electron flow stops. Fe-N 2.2950
5086.9710
Pearson’s electronegativity scale was used to determine the
number of electrons given up by the inhibitor molecule to the
metal atom. The estimated electron transfer (DN) from inhibitor orbital that is not occupied. Thus, the potential for building a feed-
to iron is also shown in Table 4. With these DN values, we may back link would be determined by the magnitude of ELUMO. When
infer that electron donation plays a significant role in the efficiency the ELUMO energy is small, it is simpler for electrons in the metal’s
with which inhibition occurs. d-orbital to be accepted. This is followed by FSC-Mn, which has the
EHOMO =
4.292 eV and ELUMO =
3.937 eV for FSC-Mn, respec- lowest energy at
3.937.0 eV. The obtained values for ‘‘DEBack-
donation” are proportional to ‘‘global hardness,” hence ‘‘-g/4 is the
tively, show that it has the greatest and lowest inhibition efficien- 00

cies. Furthermore, it has been shown that inhibitors may create a correct formula. As a result, because g > 0 for all four molecules,
feedback connection by accepting electrons from the metal’s d- DEBack-donation < 0 [31]. Upon receiving a charge, a molecule may

8
Chérifa Boulechfar, H. Ferkous, A. Delimi et al. Journal of Molecular Liquids 378 (2023) 121637

donate that charge to another atom, resulting in a net energy gain. to Boltzmann probability). FSC-Zn can only bind to Fe20 through
Since all inhibitory chemicals will interact with the same metal, it oxygen (Fe-O). The latter (see Table 4) was found to be very weak,
will be possible to assess how well they are stabilized against each with a length of 4.155 Å, which explains why this inhibitor was
other. Back-donation is preferred for FSC-Mn since its expected extremely weak in inhibitory activity. Additionally, the inhibitor’s
effectiveness as an inhibitor decreases with increasing hardness: inability to form Fe-N bonds with the iron surface further reduces
[FSC-Mn] > [FSC-Co] > [FSC-Zn] > [FSC]. its chances of attaching to the iron, making it the least strongly
In the FSC and FSC-Zn structures, the HOMO was positioned on attached complex to the surface to protect against corrosion.
the double-bounded atoms (conjugated C ¼ C and C ¼ N), but in
the FSC-Mn and FSC-Co structures, it was mostly located in the
4.4.2. Monte Carlo simulations
metal neighborhood. For FSC, FSC-Co, and FSC-Zn, the LUMO was
Another Monte Carlo (MC) simulation of the physical adsorp-
located on the furaldehyde carbons, while for FSC-Mn, the LUMO
tion of the various complexes on an iron (1 1 0) surface was per-
was located on the metal atom, as well as the OH and C ¼ O (car-
formed (Table 5). This time, the forces at work are physical (Van
bazone). Strong electron affinity and a low energy level at the low-
der Waals and electrostatic). In addition, the adsorption system’s
est LUMO of the compounds under study make them simple to
stability may be established by the magnitude of the adsorption
decrease (Fig. 8). As the FSC or FSC complexes interact with the
Energy (Eads). Higher absolute values for Eads indicate stronger
Fe20 cluster, Fe-O or Fe-N connections are created (See Table 4
inhibitor-Fe (1 1 0) interactions and hence more efficient corrosion
and Fig. 8).
inhibition.
For example, it was found for FSC-Mn@Fe20 that the Fe-N Bond
The results of this investigation indicate that FSC-Mn is the best
length is 2.295 Å rather than 2.480 Å for Fe-O, indicating a stronger
complex, actively interacting with the iron surface and possessing
bond. The total energies of all molecules interacting with the Fe-
adsorption energy of around
1068.656 kcal/mol. Additionally, we
cluster were comparable in both situations. This shows that the
see that the other two complexes lag significantly behind FSC-Mn
two alternatives are energetically more advantageous (according
in adsorption energies.

Molecule HOMO LUMO

Fe20 Cluster

FSC

FSC-Zn

FSC-Co

FSC-Mn

Fig. 8. Frontier molecular orbitals of the inh@Fe20 systems.

9
Chérifa Boulechfar, H. Ferkous, A. Delimi et al. Journal of Molecular Liquids 378 (2023) 121637

Table 5
Adsorption energies (kcal/mol) of the complexes on the Fe(1 1 0) plane: M = Zn, Co, Mn.

Total Energy Adsorption Energy Rigid adsorption Energy Deformation Energy FSC
M : dEad=dNi HCl : dEad=dNi
FSC-Zn 311.456
885.929
16.289
869.640
875.710
1.136
FSC-Co 84.930
695.942
13.841
682.101
684.824
0.728
FSC-Mn 67.023
1068.656
16.721
1051.935
1058.244
1.180

According to the principle of higher absolute values of the
adsorption energy, the order of inhibitory efficiency of the
studied complexes is the following: [FSC-Mn] > [FSC-Co] >
[FSC-Zn] against corrosion of XC38 carbon steel in 1 M HCl
solution.
4.5. Mechanism of inhibition
4.5.1. Protonation of inhibitors
The amine function of the Schiff base with three metal com-
plexes (Fig. 9) is protonated, mainly at the central nitrogen atom,
due to the presence of HCl acid in the media. In recent years, cor-
rosion inhibitors have increasingly used organic molecules like
Schiff’s bases and complexes.
4.5.2. Adsorption of inhibitors
The mechanism of reactivity of FSC ligand and its metal com-
plexations with the surface of XC38 carbon steel has been eluci-
dated using a straightforward strategy developed by us. Because
of their positive charge in the HCl solution, donor-acceptor interac-
tions play a significant role in the interactions of organic inhibitors
with metal surfaces [61–64]. The molecular structure of inhibitors
is critical to the efficiency of FSC and its metal complexes. Heteroa-
tom and functional group lone pairs may affect inhibitor
compound-iron atom binding. The idea proposes that oxygen and
nitrogen, negatively charged particles that may swiftly donate
electrons to vacant electronic orbitals of the metal, are the active
locations where inhibitor adsorption occurs on the metallic sur-
face. Because oxygen has a stronger negative charge than nitrogen,
it forms stronger bonds with metal surfaces and is more readily

Fig. 9. Mechanism of protonation for the studied compounds in an acidic medium (1 M HCl).

10
Chérifa Boulechfar, H. Ferkous, A. Delimi et al.
adsorbed [65,66]. Fig. 10 shows the FSC ligand and metal com-
plexes adsorbing onto the surface of XC38 carbon steel in an acidic
solution (1 M HCl). The rapid oxidation of carbon steel occurs
because of its exposure to a harsh environment, which causes
the metal’s surface to become positively charged and attract nega-
tively charged chloride ions, producing a negatively charged metal
surface (Fig. 10 a). In addition, inhibitor molecules are easily proto-
a)
b)
c)
Fig. 10. Mechanism of interactions between inhibitors and XC38 carbon steel surface in 1 M HCl solution; a) Without inhibitors, b) With [inhibitor]+, c) With [FSC-Zn]+.
11
Journal of Molecular Liquids 378 (2023) 121637
nated in the presence of an HCl solution [67,68]. The protonated
inhibitor molecules will likely attract the preabsorbed Cl ions
through attractive electrostatic interactions (physical adsorption)
[69]. This first step takes little time at all (Fig. 10 b). Oxygen and
nitrogen lone pairs and conjugated double bonds are involved in
chemisorption Two mechanisms contribute to this inhibitory
effect: (1) electron transfer from the inhibitor’s active sites to the
Chérifa Boulechfar, H. Ferkous, A. Delimi et al.
iron’s vacant d orbital, and (2) back-donation of the lone pairs in
the iron’s d orbital to the electron-poor C ¼ C bonds [70]. Experi-
mental and theoretical research has shown that chemisorption is
the primary adsorption process; nevertheless, mild physisorption
cannot be ruled out. As a result, it is reasonable to assume that
physisorption, chemisorption, and back-donation are the three
processes responsible for the adsorption of FSC Schiff base and
its metal complexes on the metal surface of XC38 carbon steel in
an aggressive acidic solution (1 M HCl) (Fig. 10 c). Whereas [FSC-
Mn] > [FSC-Co] > [FSC-Zn] > [FSC] a bigger molecule size, covering
a greater surface area, is responsible for the observed increase in
inhibitory effectiveness across all methods of testing and theoret-
ical computations. Furthermore, the theoretical and experimental
analyses show a strong connection, highlighting the exceptional
efficacy of these inhibitors in preventing corrosion in XC38 carbon
steel.
5. Conclusion
Using experimental studies and quantum calculations, the cor-
rosion inhibition of XC38 carbon steel was evaluated in 1 M HCl in
the presence of FSC Schiff bases complexes of Co, Zn, and Mn-based
inhibitors using different concentrations. With increasing inhibitor
concentration, the effectiveness of inhibition increased. The rank-
ing FSC-Mn > FSC-Co > FSC-Zn was described as the order of inhi-
bitory action, which demonstrates that FSC-Mn had the highest
inhibitory effectiveness, at roughly 91.48 %. EIS and PDP results
were found to be proportional. Additionally, these chemicals took
part as mixed-type inhibitors, as shown by the PDP findings. SEM
analysis showed that the adsorption of these chemicals caused
the inhibition onto the surface of XC38 carbon steel in an acidic
solution (1 M HCl). The experimental findings and quantum calcu-
lations for the reactivity of the studied Schiff base and its metallic
complexation against carbon steel are highly correlated. In an
acidic solution (1 M HCl), FSC and its transition metal complexa-
tions adsorb onto the surface of XC38 carbon steel by physisorp-
tion, chemisorption, and back-donation. These findings are highly
significant in demonstrating the efficacy of the metallic complex
inhibitors in protecting metal surfaces, pipelines, storage tanks,
and other industrial equipment that are exposed to corrosive envi-
ronments. The versatility of these inhibitors to be incorporated into
various materials such as paint and plastic makes it possible to sig-
nificantly improve their resistance to corrosion, thus leading to a
longer lifespan of industrial equipment and reduced maintenance
costs for industries. Overall, the outcomes of this study have
immense potential to contribute to the development of advanced
inhibitors with improved efficacy and the creation of new materi-
als and coatings specifically designed to withstand corrosive envi-
ronments in the transportation and energy sectors.
CRediT authorship contribution statement
Chérifa Boulechfar: Conceptualization, Investigation, Method-
ology, Formal analysis. Hana Ferkous: Conceptualization, Investi-
gation, Methodology, Formal analysis. Amel Delimi:
Conceptualization, Investigation, Methodology, Formal analysis.
Malika Berredjem: Conceptualization, Investigation, Methodol-
ogy, Formal analysis. Abdesalem Kahlouche: Conceptualization,
Investigation, Methodology, Formal analysis. Anis Madaci: Con-
ceptualization, Investigation, Methodology, Formal analysis. Souad
Djellali: Conceptualization, Investigation, Methodology, Formal
analysis. Sihem Boufas: Conceptualization, Investigation, Method-
ology, Formal analysis. Amel Djedouani: Conceptualization, Inves-
tigation, Methodology, Formal analysis. Abdelhamid Errachid:
Conceptualization, Investigation, Methodology, Formal analysis.
12
Journal of Molecular Liquids 378 (2023) 121637
Azmat Ali Khan: Conceptualization, Investigation, Software, Writ-
ing – review & editing. Abir Boublia: Conceptualization, Investiga-
tion, Software, Writing – review & editing. Tarek Lemaoui:
Conceptualization, Investigation, Software, Writing – review &
editing. Yacine Benguerba: Conceptualization, Investigation, Soft-
ware, Writing – review & editing.
Data availability
No data was used for the research described in the article.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Funding
This work was funded by the Researchers Supporting Project
Number (RSP2023R339) King Saud University, Riyadh, Saudi
Arabia.
Acknowledgments
The authors are grateful for the support received from the Min-
istry of Higher Education and Scientific Research, Laboratoire de
Génie mécanique et Matériaux, Faculté de Technologie, University
20 Août 1955-Skikda, Skikda, 21000, Algeria, Laboratoire de Bio-
pharmacie Et Pharmacotechnie (LPBT), University Ferhat Abbas
Sétif 1, 19000, Sétif, Algeria, and the Directorate General for Scien-
tific Research and Technological Development (DGRSDT), Algeria.
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