Journal of Hazardous Materials 382 (2020) 121029

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Journal of Hazardous Materials

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

Production of an environmentally stable anti-corrosion film based on Esfand T

seed extract molecules-metal cations: Integrated experimental and computer
modeling approaches
⁎
Mehdi Tabatabaei Majda,b, Mohammad Ramezanzadehb, Bahram Ramezanzadehb, ,
⁎
Ghasem Bahlakehc,
a
Department of Materials Engineering, Faculty of Engineering, Tarbiat Modares University, P.O. Box: 14115-143, Tehran, Iran
b
Department of Surface Coatings and Corrosion, Institute for Color Science and Technology (ICST), P.O. 16765-654, Tehran, Iran
c
Department of Chemical Engineering, Faculty of Engineering, Golestan University, Aliabad Katoul, Iran

A R T I C LE I N FO A B S T R A C T

Editor: G. Lyberatos This study aims at finding a suitable alternative for traditional and hazardous organic/inorganic corrosion in-
Keywords: hibitors. In this study, the aqueous extract of Esfand seed (ESE) was used as a unique green source of nitrogen-
Green inhibitor based organic compound with great capability of the steel corrosion inhibition in a saline solution. Surface and
Inhibition efficiency electrochemical analyses were carried out by Ultraviolet-visible spectroscopy (UV), Fourier-transform infrared
organic/inorganic complexes spectroscopy (FT-IR), Grazing incidence X-ray diffraction (GIXRD), field emission scanning electron microscopy
GIXRD (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), atomic force microscopy (AFM), electrochemical im-
Computer modeling pedance spectroscopy (EIS), and polarization methods. Furthermore, the adsorption of inhibitors on the steel
surface was explored by Monte Carlo (MC), molecular dynamics (MD) and quantum mechanics (QM) methods.
The electrochemical studies established the effectiveness of the zinc cations addition to the ESE containing
solution on its inhibition efficiency. The sample inhibited by 300 ppm ESE + 700 ppm Zn showed the highest
anti-corrosion properties. The inhibition efficiency of this sample was reached 98.8% after 264 h which is much
higher than those reported in the previous studies. QM computations proved the formation of complexes via
donor-acceptor action. MC and MD simulations supported the inhibitors adsorption on the steel.

1. Introduction
The low carbon steel is vulnerable in front of chemical attacks.
Application of chemicals as corrosion inhibitors is one of the most cost-
effective and simple ways to prevent or at least lower the corrosion rate
of steel. These chemicals can protect the metal surface via forming
protective barrier films through chemisorption and physisorption pro-
cesses. The real concerns in using typical corrosion inhibitors are their
carcinogenetic properties. The carcinogenetic and toxic consequences
of hazardous compounds such as hexavalent chromium and phosphates
have been proved in a number of studies (N.T. Program, 2011; Costa
and Klein, 2006; Alibakhshi et al., 2018; Dehghani et al., 2019a; Majd
et al., 2019a; Salehi et al., 2017). Hence, authorities have put pressure
on the industries and researchers to find suitable non-toxic alternatives.
Among the last decades, it was found that various parts of medicinal
plants and aromatic herbs are precious sources of the effective organic
compounds. Being biodegradable, eco-friendly, available, cost-effective
and so many other privileges have made the plants as favorable case of
study. This type of inhibitor usually shows desirable performance in the
acidic media (Ramezanzadeh et al., 2018; Bahlakeh et al., 2019;
Hohenberg and Kohn, 1964; Kohn and Sham, 1965; Frisch et al., 2009;
Tomasi et al., 2005; Reed et al., 1988; Asadi et al., 2019; Bahlakeh
et al., 2017a; Olasunkanmi et al., 2015; Verma et al., 2016; Abboud
et al., 2007) but represents poor performance in neutral environments
(Majdi et al., 2017). Moreover, the low carbon steel is very sensitive
against chloride containing solutions due to the pitting corrosion oc-
currence. One way is to use inorganic metal cations besides the plant
extract. As a result, a synergistic impact would occur between the or-
ganic and inorganic species to form insoluble complexes and chelates.
Salehi et al. used the extract of Urtica Dioica (U.D) leaves as the
corrosion inhibitor for the corroding MS sample in 3.5 wt. % NaCl so-
lution. The inhibition efficiencies of about 68% and 45% were calcu-
lated by EIS and polarization tests data in the presence of an optimum
concentration of U.D leaves extract, while in the presence of zinc

⁎
Corresponding author.
E-mail addresses: ramezanzadeh-bh@icrc.ac.ir, ramezanzadeh@aut.ac.ir (B. Ramezanzadeh), gh.bahlakeh@gu.ac.ir (G. Bahlakeh).

https://doi.org/10.1016/j.jhazmat.2019.121029
Received 21 April 2019; Received in revised form 14 August 2019; Accepted 15 August 2019
Available online 16 August 2019
0304-3894/ © 2019 Elsevier B.V. All rights reserved.
M.T. Majd, et al.
Fig. 1. The UV–vis spectra of chloride solutions containing different ratios of ESE:Zn composite before and after immersion of the metallic samples for 72 h.
cations, the inhibition efficiency has reached 92% (Saxena et al., 2018).
Ramezanzadeh et al. applied Nettle leaves extract in a chloride solution
and observed that it can lower the corrosion up to 71%. Adding Ce3+ to
the U.D containing solution have brought about a 95% inhibition effi-
ciency (Liu et al., 2009).
Esfand (often called Syrian/African rue) is a glabrous perennial herb
which belongs to the Zygophyllaceae family (Reed et al., 1988). The
seeds contain effective β-carboline alkaloids and N-based organic
compounds like tetrahydroharmine, harmalol, harmine, vasicinone,
vasicin, harmane, dihydrouridine, harmalin, serotonin, and harmol,
each of which is depicted in Fig. S1.
To the best of our knowledge, there is no report on considering the
synergistic impact between the Esfand seed extract and metal cations. In
this work, we surveyed the synergism impact between the organic
compounds of ESE and the zinc cations in 3.5 wt. % NaCl solution.
Surface characterizations of the low carbon steel were carried out using
FE-SEM, EDX, UV–vis, FT-IR, GIXRD, AFM and contact angle (CA)
measurements. Electrochemical investigations were accomplished by
EIS and polarization analyses. Moreover, to examine the adsorption
properties of the inhibitors on the steel substrate the MC and MD si-
mulations were utilized. The formation of complexes and their re-
activity were assessed by QM computations.
2. Experimental
2.1. Raw material and preparation
Esfand seed was procured from local markets. The extraction process
is graphically illustrated in Fig. S1. Sodium chloride (NaCl) besides zinc
salt (Zn2+) were purchased from Merck Co. (Germany). The steel sheets
(Table S1) provided from Mobarakeh steel Co. (Iran) were abraded by
silicon carbide emery papers up to 1000 grits. The abraded panels were
plunged in an acetone ultrasonic bath. Afterward, they were pulled out
and rinsed off with deionized water. The pre-cleaned sheets were
dipped in the saline solutions containing different concentrations of
inhibitors.
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Journal of Hazardous Materials 382 (2020) 121029
2.2. Characterizations
2.2.1. Surface analysis
The microstructure and morphology of the protected surfaces were
observed by FE-SEM (MIRA3-TESCAN) armed with EDX. The adsorp-
tion/desorption rate of the complexes and organic compounds present
in the structure of ESE was evaluated by UV–vis spectroscopy (Hitachi
U-3010 model spectrophotometer). The presence of different functional
groups from different classes was investigated by FT-IR spectroscopy
(Perkin Elmer model spectrometer). Moreover, the formation of the
crystalline planes and inorganic complexes was studied by GIXRD (X’
Pert Pro Panalytical diffractometer with Cu-Ka radiation source
(λ = 1.54 A˚) and the resulting spectra were analyzed by X’pert high-
score plus software (version 4.8.0). The topography of the inhibited
surfaces was surveyed by a dual scope AFM device (model DS 95–200).
Finally, the level of water repellency was examined by CA measure-
ments (OCA 15 plus device). Hence 1 μL of deionized water was placed
on the protected and unprotected surfaces.
2.2.2. Electrochemical performance
The anti-corrosion function of the constructed films on the samples
containing different ratios of ESE:Zn was investigated by EIS (Ivium
Compactstat). Furthermore, the mechanism of corrosion inhibition was
scrutinized by polarization test (Ivium Compactstat).
2.3. Theoretical characterizations
2.3.1. Equilibration of Zn(II) complexes
The complexes were built by bonding harmaline, harmalol and
harmane molecules to a Zn(II) cation (Fig. S2). The constructed com-
plexes were optimized using density functional theory (DFT) and B3LYP
functional. The 6–311 G(d,p) and Lanl2DZ functions were selected for
light and heavy atoms, respectively (Manov et al., 2000; Salensky et al.,
1986). These functions are available in Gaussian 09 package (Chen and
Browne, 2018). The optimization was done in solution phase by means
of the SCRF and PCM theory (Berry et al., 2006). For the optimized
complexes the following properties were characterized: The highest
occupied molecular orbital (HOMO), the lowest unoccupied molecular
M.T. Majd, et al. Journal of Hazardous Materials 382 (2020) 121029

Fig. 2. (a) The FT-IR spectra of steel samples dipped in chloride solutions containing different ratios of ESE:Zn before and after immersion for 72 h. ESE:Zn=
(300 ppm ESE +700 ppm Zn) (b) GIXRD pattern for steel sample immersed in chloride solutions containing different ratios of ESE:Zn additives for 72 h.

Table 1 2.3.2. Molecular simulations

The details of GIXRD patterns. The adsorption of complexes on the steel was analyzed using MC
Sample Pos.[°2θ.] Intensity/Height [cts] d-spacing [Å] Grain size (nm)
and MD simulations and COMPASS force field (Kang et al., 2009;
Bollermann et al., 2012). In these simulations, steel substrate was de-
Blank 33.1577 45.54 2.70187 31.4 + 2% scribed using iron (110) surface (Bahlakeh et al., 2019; Bollermann
44.7947 262.84 2.02331 et al., 2012; Liu et al., 2017; Abdel-Gaber et al., 2011). The optimized
64.9007 15.52 1.43679
ESE 26.4828 28.23 3.36573 30.6 + 13%
complexes obtained from DFT/B3LYP computations were utilized for
44.6348 293.5 2.03018 molecular simulations. Initially, the adsorption of complexes over Fe
65.1341 39.35 1.43221 (110) surface was analyzed through MC simulation. Subsequently, the
ESE:Zn 26.8264 27.01 3.32341 20.5 + 6% adsorption of Zn(II)-harmaline, Zn(II)-harmalol and Zn(II)-harmane
33.1156 45.92 2.70521
complexes was characterized in liquid phase by using MD simulation.
44.6324 519.83 2.03029
64.9908 46.56 1.43502 To prepare the liquid phase, solvent layer consisting of water mole-
Zn 11.2787 318.44 7.84535 22.9 + 1% cules, sodium cations and chloride anions was placed above the surface.
22.6648 45.98 3.92333 The resulting cell was subjected to 20,000 steps of minimization, which
33.1409 73.94 2.7032 was followed by MD simulation. This simulation was performed for 1 ns
38.39 35.43 2.34481
44.6053 189.08 2.03146
in NVT ensemble. The time step and temperature were set to be 1 fs and
298 K, respectively.

orbital (LUMO), orbital energies (EHOMO, ELUMO and ELUMO- EHOMO =

3. Results and discussion
ΔEL-H), Fukui functions, atomic charges, and the fraction of shared
electrons (ΔN). The charges were determined by natural bond orbital
3.1. Chemical composition
(NBO) theory (García-Terán et al., 2004). Also, the electronegativity
(χ), hardness (η), ionization potential (I) and electron affinity (A) of
The adsorption/desorption behavior of the chloride solution con-
complexes were computed. The equations of these parameters were
taining different ratios of ESE:Zn was investigated by UV–vis spectro-
mentioned elsewhere (Bahlakeh et al., 2019).
scopy. There are three zones named as A, B, and C in the wavelength

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M.T. Majd, et al. Journal of Hazardous Materials 382 (2020) 121029

Table 2
The details of phases detected by GIXRD analysis. (ESE:Zn = 300 ppm ESE +700 ppm Zn).
Sample Detected compound/phase Chemical formula JCPDS card no 2θ value

Blank Hematite Fe2O3 00-032-0469 33.15

Iron Fe 01-087-0722 44.79, 64.9
Magnetite Fe3O4 96-900-2330 44.79, 64.9
ESE Trans-Diaquabis[5-carboxy-2-(3-pyridyl)-1H-imidazole-4-carboxylato-κ2 N 3,O 4] FeO10N6H16C20 96-222-2604 26.48-44.63
iron(II)
Iron Fe 96-901-3473 44.63-65.13
Zn Iron Chloride Hydroxide Fe6Cl2-x (OH)12+x 00-049-0095 11.27, 22.66, 33.14, 38.39,
44.6
Zinc Hydroxide Chloride Hydrate Zn5(OH)8Cl2H2O 01-077-2311 11.27, 22.66, 33.14, 38.39,
44.6
Iron(III) oxide chloride FeOCl 96-101-0310 11.27, 22.66, 33.14, 38.39
Iron Fe 96-901-3480 44.6
ESE:Zn Catena-aqua(mu-oxalato)adeninezinc(II)-adenine water (1/2/1) C17H19N15O6Zn 96-431-1512 26.82, 33.11
Di aqua bis(2,2′-bi imidazole)zinc(II) 4,4′-di carboxybi phenyl-3,3′- [Zn(C6H6N4)2(H2O)2](C16H8O8) 96-222-1405 26.82, 33.11, 44.63
di carboxyl ate
Hematite Fe2O3 00-039-0238 33.11
Iron Fe 96-901-3473 44.63, 64.99

ranges of around 202–217, 250–271 and 341–416 nm, respectively
(Fig. 1). Zone A is related to the C]C bonds (π → π* transition)
(Abraham Daniel et al., 2019) while the zones B and C present the at-
tendance of n→ π∗ transition of C]O, OH, NH2 and NH bonds (Sanaei
et al., 2017; Majd et al., 2019b, c). Comparing the absorbance rates of
all curves, it can be conceived that the 1000 ppm ESE concentration has
the lowest absorbance in the solution and the wavelength ranging from
200 to 233 nm, indicating the highest precipitation of ESE:Zn com-
plexes on the steel surface. But after 233 nm, the 500 ppm ESE
+500 ppm Zn ratio showed the highest deposition on the metal surface.
Fig. 2(a) manifests the presence of various bonds from different
classes of functional groups such as alcohols, phenols, alkanes, car-
boxylic acids, amides, amines, alkenes, aromatics, esters, ethers and
alkynes, which are specified in Tables S2 and S3. The presence of vi-
brations around 2850 cm−1 in ESE and ESE:Zn samples, reveals the
construction of CH, OH and CH2 bonds of Fe-ESE protective complexes.
Moreover, the appearance of alkyl halides (C-Cl stretch) in the spectra
of the samples after immersion proves the contribution of the Cl- in
chelates and ligands formation.
Furthermore, the formation of crystalline structures was determined
by GIXRD analysis. The diffraction spectra are plotted in Fig. 2(b).
Moreover, the details of GIXRD patterns are given in Tables 1 and 2.
According to the database, different types of iron oxides were formed
on the surface of the blank sample. Adding 1000 ppm ESE to the
chloride solution resulted in the formation of trans-Diaquabis[5-car-
boxy-2-(3-pyridyl)-1H-imidazole-4-carboxylato-κ2 N 3,O 4]iron(II)
complex (Zhang et al., 2011). These complexes can be constructed
through the sharing of the lone pair electrons of the non-metallic atoms
(O, C, N, and Cl) with the empty orbitals of the iron atoms. Chelation is
the major action in the formation of protective complexes in neutral
environments (Yıldırım et al., 2013; Majd et al., 2019d; Ebenso et al.,
2006). It has been proved that Fe atoms can participate in the chelation
through hexavalent state besides other coordination numbers too
(Ahmadzadeh et al., 2019; Mohammadi et al., 2019). In the presence of
1000 ppm Zn, the zinc hydroxide chloride hydrate was formed. Zinc
hydroxides species can be formed as a result of the reaction between the
Zn2+ cations and the hydroxide anions generated on the cathodic sites.
But in the presence of both ESE and Zn, the organic/inorganic com-
plexes named as Catena-aqua(mu-oxalato)adeninezinc(II)-adenine
water (1/2/1) and Diaquabis(2,2′-biimidazole)zinc(II) 4,4′-dicarbox-
ybiphenyl-3,3′-dicarboxylate were formed (Izadi et al., 2017; Verma
et al., 2015). New valences of zinc in the chelates have been in-
vestigated and proved in the previous studies (Dehghani et al., 2019b;
Majd et al., 2019e; Rajendran et al., 1998a). It can be seen from Table 1
that the lowest grain size belongs to the ESE:Zn sample while both ESE
and Zn samples showed bigger sizes. This indicates that the ESE:Zn
complexes can enhance the nucleation of the subsequent formed com-
pounds and particles which results in the lower grains size (Rajendran
et al., 2001). For better conception, the 2D structures of the detected
crystalline compounds were depicted in Fig. S3. After all, the results
indicate the contribution of the steel surface in the complexation pro-
cess and the formation of chelates between the zinc cations and the
organic compounds of ESE.
3.2. Microstructure and morphology
FE-SEM and AFM/CA analyses were carried out to investigate the
morphology of the constructed protective films over the samples im-
mersed in the chloride solutions containing different ratios of ESE:Zn.
Figs. 3 and 4 present the micrographs of the protected and unprotected
samples in the low and high magnifications (AFM/CA was carried out
only on the optimum sample). According to the results, in the absence
of any additive, the surface of the substrate was extremely corroded, so
that the porous corrosion products have fully covered the entire surface.
In the attendance of 1000 ppm ESE, a protective film covered the whole
area which seems to be the ESE-Fe complexes due to the previous si-
milar studies (Chauhan et al., 2018; Saha et al., 2016; Musa et al.,
2012). But in this case, the surficial film has low thickness. Adding
1000 ppm Zn to the chloride solution resulted in the deposition of the
zinc cations in the form of Zn(OH)2 crystals with tinsel shaped mor-
phology. In the presence of both ESE and Zn cations in different ratios,
similar microstructures to 1000 ppm ESE sample have obtained. In
700 ppm ESE +300 ppm Zn sample the complexes seem to be unable to
cover the whole area. Plenty of cracks can also be observed in this
sample. In the equal concentration of ESE:Zn composite, although the
complexes have formed on all over the surface area, they had low ad-
hesion to the metallic substrate, in a way that they were disbonded in
every spot. This microstructure seems to be as a result of the trapped
water evaporation which has brought about severe stress releasement
(Bahlakeh et al., 2017b; Singh and Bockris, 1996). The combination of
300 ppm ESE and 700 ppm Zn seems to have the best morphology
where the substrate was covered by Fe-ESE-Zn thick film. The protec-
tive nano-complexes are clear in the higher magnification. Also, a lower
amount of cracks have appeared which also possess lower sizes.
Adding 1000 ppm ESE to the solution resulted in the increment of Sa
value around 44%, while in the presence of zinc cations, the roughness
augmented up to 60% (Table S4). The formed ESE-Fe complexes and
the Zn(OH)2 increased the surface area of the metallic samples. But in
the presence of an optimized concentration of both ESE and Zn, the
roughness parameters did not change much.
EDX results are exhibited in Figs. 5 and 6. In the blank sample, C, O
and Fe content found to be around 3.3, 37.3 and 59.4 wt. %,

4
M.T. Majd, et al.
Fig. 3. FE-SEM/AFM micrographs besides CA of steel samples dipped in chloride solutions for 72 h containing 0 ppm inhibitor, 1000 ppm ESE and 1000 ppm Zn.
respectively. The high content of oxygen is due to the presence of iron
oxides and hydroxides in a large amount. Similarly, the amounts of total
oxygen contents detected from the metal surfaces protected by corro-
sion inhibitors were lower than the blank values, indicating the lower
formation of corrosion products. Considering the fact that ESE has
oxygen atoms in its structure, it can be perceived that a very low
amount of iron oxides and hydroxides were formed on the samples. The
700 ppm ESE +300 ppm Zn sample has the most content of Fe, which
reveals the highest contribution of the metal substrate in the
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Journal of Hazardous Materials 382 (2020) 121029
construction of the protective film among the other samples. Moreover,
it was observed in this sample that the oxygen amount was in its lowest
values among other ones, which is the best sample from an elemental
composition standpoint.
As shown, the blank sample showed the highest CA of around 65.3°.
In the presence of ESE, the CA decreased to the lowest value among all
other samples which was 2.3° while adding 1000 ppm Zn to the saline
solution has brought about CA around 40.7°. But in the presence of
300 ppm ESE +700 ppm Zn, the CA reached 37°. The presence of
M.T. Majd, et al. Journal of Hazardous Materials 382 (2020) 121029

Fig. 4. FE-SEM/AFM micrographs besides CA micrographs of steel samples dipped in chloride solutions for 72 h containing different ratios of ESE:Zn additive.
AFM and CA are only obtained for the optimum sample.

hydrophilic compounds like amine, hydroxyl, carboxylic and etc., in the
structure of ESE, can lead to the construction of the protective film with
hydrophilic nature (Sanyal, 1981; Stupnišek-Lisac et al., 1994).
Therefore it seems that the inhibition mechanism in these samples is
mostly based on the formation of a barrier isolating film rather than
displacing water molecules. Moreover, the results presented by AFM
analysis have proved the increase in the surface roughness of the ESE
and Zn samples which have helped the water droplet to be spread easily
on the metal surface (U.P.H. Service, 1989).
After all, the results show the better performance of the ESE:Zn
composite in countering the chemical attacks toward the metal surface.
3.3. Impedance investigation
The resistive function of the steel samples dipped in the chloride
solutions containing different ratios of ESE:Zn was evaluated by EIS

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M.T. Majd, et al.
Fig. 5. The results of EDS besides the map analyses obtained from the surface of the steel sample dipped in chloride solution in the presence and absence of different
inhibitors. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article).
Red: Oxygen, Green: Iron, Yellow: Carbon, Orange: Zinc.
analysis. Fig. S4 and Fig. 7 show the Bode and Nyquist plots of the blank
and the differently protected metal substrates. As specified in the Ny-
quist spectra, the impedance data were fitted using different equivalent
electrical circuits. In the corresponding EECs, Rct, Rf, and Rs are the
resistance against charge transfer, film resistance, and solution re-
sistance, respectively. Since the surficial constructed layers were
porous, the constant phase element (CPE) was used instead of the ideal
capacitance. The impedance parameters are reported in Table 3. In this
table, Y0 and n are the admittance and exponent which are the con-
stituents of the CPE. Looking at the shape of Bode-phase plots, it can be
perceived that at longer immersion times (192 and 264 h) another time
constant (second film) appeared at high frequencies which is very rare
in this field of study, while in other times, samples have shown only
two-time constants (double layer and first film).
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Journal of Hazardous Materials 382 (2020) 121029
Moreover in order to have a clear perception from the performance
of each concentration and different ratios of ESE:Zn, the inhibition ef-
ficiency values were calculated through Eq. (1) and reported in Fig. S5
(Sanaei et al., 2019; Ramezanzadeh et al., 2019; Mehdipour et al.,
2015; Jokar et al., 2016; Majd et al., 2019f; Dehghani et al., 2019c, d,
e).
Rt − RtBlank ⎞
η = ⎜⎛ Inhibited ⎟ × 100
RtInhibited (1)
⎝ ⎠
According to the results (Fig. S5), the 1000 ppm ESE and 1000 ppm
Zn possess the lowest efficiencies, while in the presence of both com-
pounds in different ratios, the efficiency promoted so that in the case of
300 ppm ESE +700 ppm Zn, the efficiency reached a remarkable value
M.T. Majd, et al. Journal of Hazardous Materials 382 (2020) 121029

Fig. 6. The results of EDS besides the map analyses obtained from the surface of the steel sample dipped in chloride solution containing different ratios of ESE:Zn
compounds. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article).
Red: Oxygen, Green: Iron, Yellow: Carbon, Blue: Zinc.

of around 98.8%. This is the highest efficiency value recorded for a
green corrosion inhibitor in the chloride solution in all studies done
until now. Protection in neutral chloride solutions is based on the in-
herent oxide layer stabilization. In this case, it seems that the Fe2+-ESE-
Zn2+ constructed complexes are in charge of this fabulous resistive
performance. Complexation can lead to the construction of a structure
with a higher molecular weight and longer chain length (Dehghani
et al., 2019d, e; Saha et al., 2015; Kumawat et al., 2017; Petrey and
Werner, 1972). All results and calculations indicate the successful
promotion in the inhibition potential of the ESE containing solution
through complexation with Zn cations and the final Fe-ESE-Zn chelates
formation.
3.4. Polarization measurements
The inhibition mechanism of the steel samples dipped in different
saline solutions was investigated using polarization experiment. Fig. 8
and S6 represent the Tafel curves of the steel samples dipped in the
blank and additive containing chloride solutions after 24 and 288 h.
Moreover, in order to compare the performance of each sample, the
related curves were extrapolated and the corrosion parameters were
reported in Table 4. In this table, Ecorr, Icorr, Rpol, ba, bc and C. rate are
defined as the corrosion potential, corrosion current density, polariza-
tion resistance, anodic Tafel slope, cathodic Tafel slope, and the cor-
rosion rate, respectively. The comparison between the Ecorr values of

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M.T. Majd, et al. Journal of Hazardous Materials 382 (2020) 121029

Fig. 7. The Nyquist spectrum for steel samples dipped in chloride solution containing different concentrations of ESE for different immersion times.

the protected samples with the blank samples can reveal the inhibition
mechanism in this immersion time. It has been said that the │ Ecorr °
- branches indicate no significant change in the mechanisms of anodic
blank
Ecorr │ < 85 mV values reveal the mixed type inhibition while│ Ecorr °
- and cathodic reactions (U.P.H. Service, 1989). Fig. S6(b) demonstrates
blank
Ecorr │ > 85 mV values, depending on the Ecorr shift, indicate the
anodic or cathodic based inhibition (U.P.H. Service, 1989; Prochowicz
et al., 2014; Kurniawan and Pradana, 2014; Naderi et al., 2014; Chou,
2018; Izadi et al., 2019a, b; Izadi et al., 2019c). In this case, after 24 h
from immersion, except 1000 ppm ESE sample, which showed mixed-
type inhibition, the inhibition mechanism in other samples was anodic
type. While after 288 h, all of the samples represented mixed-type in-
hibition. The precipitation of protective complexes and the stabilization
of the inherent oxide layer on the anodic sites are responsible for the
anodic type inhibition while this action together with the formation of
Zn(OH)2 and other iron hydroxides on the cathodic regions are in
charge of the mixed type.
Fig. S6(a) illustrates that in the presence of inhibitors, the corrosion
current density of the cathodic and anodic slopes reduced. After 24 h,
the 300 ppm ESE +700 ppm Zn sample has the lowest icorr value among
all other samples which is around 0.359 μA/cm2. The shapes of both
a descending trend in the corrosion current densities of both branches
for all inhibitor-containing samples. The ESE:Zn containing samples
and particularly the 500 ppm ESE +500 ppm Zn sample belong the
lowest icorr values after 288 h from immersion. Looking at the shape of
both branches for all samples, it can be perceived that except 1000 ppm
Zn sample, there is another anodic reaction taking place on the surface
of all samples (Naderi et al., 2014). All of the results corroborate each
other and indicate the effectiveness of the ESE:Zn composition in short
and long immersion times.
3.5. Inhibition mechanism and the role of zinc cation in the inhibition
synergism
In the previous sections, the high inhibition performance of the
ESE:Zn samples was demonstrated. The reason was attributed to the

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M.T. Majd, et al. Journal of Hazardous Materials 382 (2020) 121029

Table 3
Electrochemical parameters obtained through EIS plots fitting for steel samples dipped in 1 M HCl solutions containing different ratios of ESE:Zn composites.
a
Sample Immersion time (h) R f 1 (Ω. cm2) CPE f 1
b
R f 2 (Ω. cm2) CPE f 2
c
R ct (Ω. cm2) CPE dl

−1 −1
d
Y0 (μΩ 2 n
cm s ) e
n d
Y0 (μΩ 2 n
cm s ) e
n Y0 (μΩ−1 cm2sn)
d e
n

Blank 1h – – – – – – 939 627 .80

9h – – – – – – 1595 366 0.77
24 h – – – – – – 1232 470 0.72
72 h – – – – – – 630 308 0.78
192 h – – – – – – 880 229 0.84
264 h – – – – – – 1338 275 0.83
1000 ppm ESE 1h – – – 12.9 76 0.55 1637 284 0.85
9h – – – 57.5 124 0.48 1921 360 0.85
24 h – – – 8.2 200 0.54 2377 191 0.84
72 h – – – 6.8 53 0.62 5749 168 0.88
192 h – – – 16 67 0.81 8262 124 0.82
264 h – – – 11 52 0.81 10956 114 0.80
700 ppm ESE+300 ppm Zn 1h – – – 9.4 35 0.73 12510 166 0.80
9h – – – 9.1 2.7 0.85 8306 109 0.80
24 h – – – 6.8 5.8 0.86 6344 86 0.84
72 h – – – 4.7 1.2 0.85 9068 66.5 0.64
192 h 33.5 20 0.76 10302 37 .085 42176 91 0.68
264 h 42.3 36.6 0.86 7583 35 0.88 24152 211 0.72
500 ppm ESE+500 ppm Zn 1h – – – 7.2 28 0.76 8535 132 0.80
9h – – – 11 32 0.73 12118 143 0.82
24 h – – – 10.7 78 0.68 9858 118 0.85
72 h – – – 12.8 108 0.61 13531 33 0.92
192 h 48 41 .77 3366 51 0.87 13558 106 0.68
264 h 86 50 0.67 15749 43 0.88 20721 268 0.77
300 ppm ESE+700 ppm Zn 1h – – – 12 63 0.75 9404 105 0.81
9h – – – 29 85 0.71 20291 152 0.75
24 h – – – 21 44 0.72 26704 177 0.76
72 h – – – 13.7 81 0.58 25360 43 0.92
192 h 19 17 0.74 1975 43 0.90 59735 90 0.55
264 h 18 11.4 0.79 8284 34 0.87 100960 68 0.50
1000 ppm Zn 1h – – – 8 80 0.62 2698 92 0.85
9h – – – 13 81 0.52 2933 200 0.81
24 h – – – 21 128 0.63 10844 437 0.76
72 h – – – 23 123 0.61 5321 764 0.61
192 h – – – 66 96 0.51 10859 824 0.71
264 h – – – 7 133 0.30 13581 698 0.70

a
The standard deviation range for Rf1 values is between 1.1% and 3%.
b
The standard deviation range for Rf2 values is between 2% and 5.4%.
c
The standard deviation range for Rct values is between 2.3% and 8.5%.
d
The standard deviation range for Y0 values is between 0.1% and 2.5%.
e
The standard deviation range for n values is between 0.2% and 5.5%.

synergism impact of the organic/inorganic moieties. Adding Zn ions to process has faced disruption which resulted in several uncovered and
the ESE containing saline solution, the ESE-Zn complexes would be disbonded areas (FE-SEM micrographs, Fig. 4). While in the 300 ppm
constructed in the first place through the chelation of the ligands. ESE +700 ppm Zn a perfect morphology was obtained and the corro-
Dipping the metal samples, the steel surface would be corroded and a sion inhibition was in its highest level. The entire statements are
weak and porous oxide layer will cover the entire surface. The ESE-Zn schematically illustrated in Fig. S7.
complexes will be transferred from the bulk solution to the metal/
electrolyte interface. Following typical anodic and cathodic reactions
3.6. Theoretical investigation
happening on the metal surface, Fe2+ and OH− would be formed as a
result of the anodic and cathodic reactions. In the presence of iron
3.6.1. Molecular simulations
cations, the Zn atoms of the ESE-Zn complexes would experience a
The adsorption of complexes over the steel was characterized by
cation exchange process which results in the conversion of ESE-Zn
using MC and MD simulations. The final cells obtained from molecular
complexes to the ESE-Fe ones and the formation of zinc hydroxides.
simulations were presented in Fig. 9. It is apparent that all three
These compounds would precipitate on the anodic and cathodic sites,
complexes localized over the surface with a flat arrangement. Such an
respectively (Izadi et al., 2018; Akhavan et al., 2018; Singh et al., 2016;
alignment is attributed to the vdW and electrostatic interactions. Var-
Ramezanzadeh et al., 2014; Dehghani et al., 2019f, g; Rajendran et al.,
ious energetic parameters related to MC cells were provided in Table 5.
1998b; Rao et al., 2011; Rajendran et al., 1999; Pech-Canul and
It is seen that the adsorption energy of all three complexes is negative,
Bartolo-Perez, 2004). This deposition would enhance the barrier
which proves the adsorption of chosen complexes on the iron surface.
properties of the primarily formed oxide layer on the surface by low-
The adsorption was also inspected in solution phase by performing MD
ering the porosity of the surficial films. One important issue is to pro-
simulations. The top and side views of the last snapshots obtained from
vide a situation in which the ESE-Zn complexes can undergo the cation
MD simulations were shown in Fig. 9. The top view demonstrates that
exchange process. Otherwise, ESE-Fe complexes besides zinc hydro-
the complexes localized near the metallic substrate even in the presence
xides would not be formed. This is feasible by changing the ratio of the
of solvent molecules. The side view reflects that the dissolved com-
organic/inorganic additive. In the 700 ppm ESE +300 ppm Zn and
plexes adsorbed to surface, which further points to the emergence of
500 ppm ESE +500 ppm Zn samples, it seems that the cation exchange
anti-corrosive film over the surface. The quantitative analysis of MD

10
M.T. Majd, et al. Journal of Hazardous Materials 382 (2020) 121029

Fig. 8. PDS spectra obtained for steel samples immersed in chloride solutions containing various ratios of ESE:Zn composite after 24 h from immersion. (b) The PDS
spectra shifted to Ecorr of the blank sample.

Table 4
The Electrochemical parameters of PDS extracted from the steel samples immersed in chloride solutions containing 0 ppm, 500 ppm, 700 ppm, 1000 ppm, and
2000 ppm ESE after 96 and 288 h immersion.
24 hours

Sample Ecorr. (V) icorr. (μA/cm2) Rpol (Ω. cm2) ba (V/dec) -bc (V/dec) C. Rate mm/y

Blank −0.684 4.07 4730 0.061 0.161 0.01332

1000 ppm ESE −0.701 4.222 8741 0.128 0.252 0.01381
700 ppm ESE +300 ppm Zn −0.580 1.957 13040 0.079 0.229 0.006404
500 ppm ESE +500 ppm Zn −0.537 1.432 17570 0.074 0.264 0.004685
300 ppm ESE +700 ppm Zn −0.587 0.359 53820 0.069 0.125 0.001175
1000 ppm Zn −0.564 1.922 10240 0.064 0.155 0.00629

264 hours

Sample Ecorr. (V) icorr. (μA/cm2) Rpol (Ω. cm2) ba (V/dec) -bc (V/dec) C. Rate mm/y

Blank −0.656 8.981 2204 0.058 0.213 0.02939

1000 ppm ESE −0.724 2.026 12930 0.097 0.161 0.006629
700 ppm ESE +300 ppm Zn −0.683 0.2441 74430 0.089 0.079 0.0007986
500 ppm ESE +500 ppm Zn −0.661 0.1999 87810 0.083 0.079 0.0006542
300 ppm ESE +700 ppm Zn −0.650 0.237 93040 0.133 0.082 0.0007754
1000 ppm Zn −0.580 2.199 9068 0.068 0.141 0.007195

11
M.T. Majd, et al. Journal of Hazardous Materials 382 (2020) 121029

Fig. 9. The final snapshots of Zn(II)-Harmaline (first column), Zn(II)-Harmalol (second column) and Zn(II)-Harmane (third column) complexes compounds over iron
surface obtained from molecular simulations.

Table 5
The energetic outputs and descriptors (all in kcal/mol) obtained from Monte Carlo simulations of Zn (II)-harmaline, Zn (II)-harmalol and Zn (II)-harmane complexes
over the metallic surface of Fe (110).
Molecule Total energy Adsorption energy Rigid adsorption energy Deformation energy dEads/dNi

Zn (II)-Harmaline −454.98 −495.60 −262.15 −233.44 −495.60

Zn (II)-Harmalol −568.41 −425.91 −238.42 −187.49 −425.91
Zn (II)-Harmane −51.20 −502.52 −223.81 −278.70 −502.52

simulations declared that the Zn(II)-harmaline, Zn(II)-harmalol and Zn
(II)-harmane complexes adsorbed with adsorption energies of -432.88,
-401.92 and -366.74 kcal/mol, respectively. The negative energies
further highlight the adsorption of Zn(II) complexes on the substrate
(Vijaya et al., 2013; Manivannan and Rajendran, 2011). All these the-
oretical observations support the experimental results.
3.6.2. DFT results
The interactions of the complexes were fundamentally analyzed
using DFT method. At electronic scale the adsorption of inhibitors can
occur via donor-acceptor interactions (Rao and Rao, 2010). The elec-
tron-rich sites give their electrons to electron-poor regions, leading to
formation of coordination bond between inhibitors and metal surface.
The electron donation and acceptance ability can be described by
HOMO and LUMO, respectively (Bahlakeh et al., 2019). These orbitals
were analyzed for optimized complexes (Fig. 10). It is observed that the
HOMO and LUMO of complexes distributed over organic molecules
bonded to Zn(II) atom. The resulting pictures illustrate that the ni-
trogenous rings and the oxygen atoms behaved as HOMO locations. As a
consequence, the π and lone-pair electrons can be donated to iron

12
M.T. Majd, et al.
Fig. 10. The molecular orbitals of optimized Zn(II)-Harmaline (first row), Zn(II)-Harmalol (second row) and Zn(II)-Harmane (third row) complexes.
Table 6
The computed values of different electronic properties of Zn (II)-harmaline, Zn (II)-harmalol and Zn (II)-harmane complexes. The energy values are in eV.
Adsorbate EHOMO ELUMO ΔE
Zn (II)-Harmaline −5.051 −1.119 3.932
Zn (II)-Harmalol −5.009 −1.133 3.876
Zn (II)-Harmane −5.467 −1.155 4.312
atoms, which give rise to donor-acceptor interactions. The LUMO dis-
tributed mostly on the carbon atoms of the aromatic rings. This ob-
servation suggests that the aromatic backbone of complexes can accept
the electrons given by metal atoms (Bahlakeh et al., 2019). Table 6
presents the energies of HOMO and LUMO and the fraction of trans-
ferred charge. It is noted that the ΔN value is positive, which reflects the
electron transfer from complexes to metal atoms (Anbarasi and
Rajendran, 2012). In addition, it is seen that the ΔN of Zn(II)-harmaline
and Zn(II)-harmalol is higher than that of Zn(II)-harmane. This ob-
servation is likely due to the absence of O atoms in the structure of Zn
(II)-harmane complex.
The reactive sites of complexes were also examined by using Fukui
functions. The pictures of these functions were provided in Fig. 11. It is
found that the entire aromatic backbone of complexes and heteroatoms
showed electrophilic attacks. Accordingly, these regions can give elec-
trons (π and lone pair) to an electrophile and thereby participate in
donor-acceptor interactions. On the other hand, the central cation and
its adjacent heteroatoms proved nucleophilic manner. This outcome
manifests the fact that these centers are most vulnerable to nucleophilic
attacks and can receive electrons of metal atoms. It may be concluded
that the whole geometry of complexes can involve in donation and/or
acceptance of electrons and emerge as adsorption centers. Such out-
comes strongly support the planar alignment of complexes over the
metallic surface.
13
Journal of Hazardous Materials 382 (2020) 121029
A I χ η ΔN
1.119 5.051 3.085 1.966 0.4412
1.133 5.009 3.071 1.938 0.4512
1.155 5.467 3.311 2.156 0.3499
4. Conclusion
The impact of Zn cations addition to the ESE containing chloride
solution on the corrosion inhibition performance of steel samples was
studied by several approaches. The FT-IR spectra and GIXRD patterns
prove the formation of different functional groups and the inorganic
protective chelates and complexes through the donor-acceptor me-
chanism. FE-SEM micrographs demonstrated the formation of surficial
complexes which have covered the whole surface area and it was found
that the 300 ppm ESE +700 ppm Zn sample had the lowest number of
formed cracks. It was found that adding ESE and Zn cations to the
chloride solution resulted in the formation of protective films which
have brought about a rough surface. The electrochemical investigations
using EIS analysis established the formation of another time constant at
higher frequencies. The 300 ppm ESE +700 ppm Zn sample has shown
the highest inhibition efficiency of around 98.8% and the synergism
index of 84.8. The polarization experiment exhibited that the inhibition
mechanism after 24 h in the 1000 ppm ESE sample is a mixed type,
while all other additives containing samples have anodic based in-
hibition. The curves after 288 h have unveiled mixed-type inhibition for
all samples. DFT computations proved the formation of complexes via
donor-acceptor interactions between extract molecules and Zn(II) ca-
tion. Molecular simulations confirmed the adsorption of complexes over
the steel.
M.T. Majd, et al.
Fig. 11. The Fukui indices of Zn(II)-Harmaline (first row), Zn(II)-Harmalol (second row) and Zn(II)-Harmane (third row) complexes.
Acknowledgment
The present study was supported by Golestan University, Gorgan,
Iran.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jhazmat.2019.121029.
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