Journal of Molecular Liquids 308 (2020) 113042

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Journal of Molecular Liquids

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

Anti-corrosion performance of 8-hydroxyquinoline derivatives for mild

steel in acidic medium: Gravimetric, electrochemical, DFT and molecular
dynamics simulation investigations
Dhaybia Douche a, Hicham Elmsellem b,⁎, El Hassane Anouar c,⁎, Lei Guo d, Baraa Hafez e,f, Burak Tüzün g,
Ahmed El Louzi a, Khalid Bougrin a,h, Khalid Karrouchi i, Banacer Himmi j
a
Equipe de Chimie des Plantes et de Synthèse Organique et Bioorganique-URAC23, GEOPAC, Département de Chimie, Faculté des Sciences, Université Mohammed V, Rabat, Morocco
b
Laboratory of Analytical Chemistry, Materials, and Environment (LC2AME), Faculty of Sciences, University of Mohammed Premier, B.P. 717, 60000 Oujda, Morocco
c
Department of Chemistry, College of Science and Humanities in Al-Kharj, Prince Sattam bin Abdulaziz University, Al-Kharj 11942, Saudi Arabia
d
School of Materials and Chemical Engineering, Tongren University, Tongren 554300, China
e
Dеpartmеnt of Chеmіstry, Collеgе of Scіеncеs, Unіvеrsіty of Sharjah, PO Box: 27272, United Arab Emirates
f
Department of Pharmaceutical Sciences, College of Pharmacy and Health Sciences, Ajman University, PO Box 346, Ajman, United Arab Emirates
g
Science Faculty, Department of Chemistry, Cumhuriyet University, Sivas 58140, Turkey
h
Mohammed VI Polytechnic University, Lot 660, Hay Moulay Rachid, Benguerir, Morocco
i
Laboratory of Analytical Chemistry and Bromatology, Faculty of Medicine and Pharmacy, Mohamed V University, Rabat, Morocco
j
Filière Techniques de Santé, Institut Supérieur des Professions Infirmières et Techniques de Santé de Rabat, Ministère de la Santé, Morocco

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

Article history: The anti-corrosion potency of three synthesized 8-hydroxyquinoline derivatives, namely 5-(azidomethyl)-7-
Received 30 December 2019 (morpholinomethyl)quinolin-8-ol (HM1), 2-(8-hydroxy-7-(morpholinomethyl)quinolin-5-yl)acetonitrile
Received in revised form 28 March 2020 (HM2), 5-(azidomethyl)-7-(piperidin-1-ylmethyl)quinolin-8-ol (HM3) in hydrochloric acid for mild steel was
Accepted 31 March 2020
investigated using weight loss and electrochemical techniques. Potentiodynamic polarization (PDP) data reveal
Available online 02 April 2020
that all three compounds were cathodic inhibitors, with HM3 presentation significant mixed-type effect at high
Keywords:
inhibitor concentrations (10−3 M). Electrochemical impedance spectroscopy (EIS) data reveal better adsorption
8-hydroxyquinoline of compounds species on MS surface at increased inhibitor concentrations with HM1, HM2 and HM3 reaching a
Mild steel maximum efficiency of 90, 89 and 88%. The three compounds HM1, HM2 and HM3 were inclined towards the
Anticorrosion performance Langmuir adsorption-isotherm by spontaneous chemical-physical adsorptions of inhibitors on the mild steel sur-
EIS face. The correlation between the electronic properties and inhibition efficacies of the tilted inhibitors was deter-
DFT mined by using simple linear regression technique. Electronic properties were calculated for neutral and
Molecular dynamics simulation protonated forms in a polarizable continuum model using the DFT method at the B3LYP/6–311 + G (d,
p) level of theory. The active adsorbed sites of HM1-HM3 on the metal surface were determined by analyzing
their corresponding electrostatic surface potentials (ESP). Furthermore, molecular dynamics simulations have
been performed to illustrate the most conceivable adsorption configuration between the inhibitors and metal
surface.
© 2020 Published by Elsevier B.V.

1. Introduction
The economic development of a country depends not only on its in-
dustrial activities and natural resources, but also on the substructure
necessary for the processing, exploitation, and marketing of goods. Air-
ports, land, sea and air transport, roads, buildings, bridges, irrigation
systems, offices, and industrial facilities are subject to corrosion and
therefore allowable to degrade and deteriorate processes [1].
⁎ Corresponding authors.
E-mail addresses: h.elmsellem@gmail.com (H. Elmsellem), anouarelhassane@yahoo.fr
(E.H. Anouar).
Corrosion is considered one of the pivotal problems of the world in-
dustry which gravely destroys industrial and natural environments.
Today, it is mostly recognized that corrosion is a harmful process for
the environment and the economy. It is a pernicious process that affects
the quality of the environment, the efficiency of the sector and the sus-
tainability of infrastructure assets [2–4]. On the other hand, it is
necessary to expand and carry methods and techniques corrosion engi-
neering control. Hence, the use of corrosion inhibitors has been consid-
ered as one of the substantial anti-corrosion methods under different
corrosion conditions. The industry has commonly used the pickling pro-
cess for the treatment of mild steel. Corrosion inhibitors were usually
utilized at low concentrations to acidic solutions to reduce the corrosive

https://doi.org/10.1016/j.molliq.2020.113042
0167-7322/© 2020 Published by Elsevier B.V.
2 D. Douche et al. / Journal of Molecular Liquids 308 (2020) 113042
attack of metallic materials, due to the general corrosion of acid solu-
tions [5,6]. Besides, the anti-corrosion of organic inhibitors is referred
to their adsorption ability on the metal surface through chemisorption
and physical adsorption phenomena [7]. These phenomena are mainly
influenced by the metallic charge of metal, 3D structure of the organic
molecule and the type of electrolyte. The unsaturated organic com-
pounds containing heteroatoms (e.g., O, N and S) and functional groups
(e.g., -NH, -N = N-, –C = N-, –CHO, and OH) showed high inhibition ef-
ficiencies in acid media [8–12].
One of the most important methods of determining the activity of
corrosion inhibitors is the quantum chemical calculations, which are
of great benefit to experimental studies. Recently, DFT calculations
have become powerful computational methods and are considered
the principal tool for linking some experimental notions in corrosion
science with quantum mechanics [13–15]. Furthermore, molecular dy-
namics (MD) simulation is considered another important tool for inter-
pretation and explanation of corrosion inhibition, which demonstrates
to be a very strong tool in this direction [16–18].
In the present paper, we report the synthesis and anti-corrosion in-
hibition for mild steel in 1.0 M HCl solution of three 8-hydroxyquinoline
compounds namely HM1, HM2 and HM3 (Fig. 1). Experimentally, anti-
corrosion efficiency of the tilted compounds is evaluated using weight
loss, potentiodynamic polarization (PDP) and electrochemical imped-
ance spectroscopic (EIS) techniques. The observed results were ratio-
nalized using DFT calculations and molecular dynamics (MD)
simulations in an attempt to determine the relationship between the
anti-corrosion property from one side and the structural and electronic
properties from another side of the synthesized compounds.
2. Materials and methods
2.1. Synthesis of inhibitors
The three compounds HM1–HM3 were synthesized following the
reported procedure [17] (Scheme 1). A mixture of the substrate (1a or
1b) (1 mmol), paraformaldehyde (1 mmol), and morpholine (or piper-
idine) (1 mmol) in EtOH (30 mL) was refluxed for 4 h under controlled
atmosphere (N2). After cooling, the solvent was removed under re-
duced pressure and the resulting solid was washed with cold ether
(30 mL), filtered and dried in vacuo.
5-Azidomethyl-7-morpholinomethyl-8-hydroxyquinoline (HM1): Yel-
low solid, Yield = 40%; mp = 133–135 °C; IR (cm−1): 2097 (N3); 1H
NMR (300 MHz, DMSO‑d6, δ(ppm)): 2.63 (s, 4H, H-morpholinyl), 3.77
(s, 4H, H-morpholinyl), 3.88 (s, 2H, –CH2-morpholinyl), 4.63 (s, 2H, –
CH2-N3), 7.34 (s, 1H, H-6 quinoline), 7.49 (dd, J3–4 = 8.7 Hz, H-3 quin-
oline), 8.35 (dd, J2–4 = 1.4 Hz, H-4 quinoline) 8.94 (dd, J2–3 = 4.3 Hz,
H-2 quinoline). EI+-MS: m/z = 257.1 [M-N3]+.
5-Cyanomethyl-7-morpholinomethyl-8-hydroxyquinoline (HM2):
Beige solid, Yield = 77%; mp = 137–139 °C; IR (cm−1): 2307 (C`N);
1
H NMR (300 MHz, DMSO‑d6, δ(ppm)): 2.47 (s, 4H, H-morpholinyl),
3.61 (s, 4H, H-morpholinyl), 3.72 (s, 2H, CH2-morpholinyl), 4.48 (s,
2H, CH2-CN), 7.56 (s, 1H, H-6 quinoline), 8.45 (dd, J2–4 = 1.6 Hz, H-4
quinoline), 7.58 (dd, J3–4 = 8.9 Hz, H-3 quinoline), 8.94 (dd, J2–3 =
4.5 Hz, H-2 quinoline); ESI+-MS: m/z = 283.93 [M + H]+.
Fig. 1. Molecular structures of HM1–HM3.
5-Cyanomethyl-7-piperidinomethyl-8-hydroxyquinoline (HM3):
Brown solid, Yield = 78%; mp = 149–151 °C; IR (cm−1): 2270
(C`N); 1H NMR (300 MHz, DMSO‑d6, δ(ppm)): 1.39 (s, 2H, H-
piperidinyl), 1.48 (s, 4H, H– piperidinyl), 2.42 (s, 4H, H-piperidinyl),
3.72 (s, 2H, CH2-N3), 4.43 (s, 2H, CH2-piperidinyl), 7.56 (dd, J3–4 =
8.7 Hz, H-3 quinoline), 8.97 (dd, J2–3 = 4.3 Hz, H-2 quinoline), 8.38
(dd, J2–4 = 1.4 Hz, H-4 quinoline), 7.49 (s,1H, H-6 quinoline); ESI+-
MS: m/z = 298.1 [M + H]+.
2.2. Preparation of corrosion solutions
The examination aggressive solution 1.0 M HCl was prepared via di-
lution of analytical grade HCl (Sigma Aldrich, 37%) in double-distilled
water. Four different concentrations (10−3 to 10−6 M) of HMs are pre-
pared in a 1.0 M HCl. The MS specimen contain chemical compositions
are: (wt%): C = 0.076, Mn = 0.192, P = 0.012, Si = 0.026, Cr =
0.050, Al = 0.023, and rest Fe was employed for all gravimetric. Electro-
chemical measurements: the test coupons for the electrochemical mea-
surements were cylindrical with a 1 cm2 surface area. The MS
specimens having dimensions 1.5 × 1.5 × 0.5 cm were used for all
weight loss experiment. The examination coupons (mild steel surface)
were ground by papers SiC of different grades (120, 240, 300, and
1200). Behind polishing, the coupons of mild steel were washed in
double-distilled water.
2.3. Weightloss measurements
Weightloss measurements were performed mild steel coupons in
1.0 M HCl with various concentrations of HMs for 6 h at 308 K. During
weight loss measurement, all specimens were weighed preceding to
immersion. Every one gravimetric experiment was triply performed
and the mean value was reported to assure the reproducibility. The per-
centage inhibition efficiency (ηw%) was obtained by the next equation
[18]:
w0 −wi
ηw % ¼  100 ð1Þ
w0
where w0 and wi are the values of weight in uninhibited and inhibited
solutions, respectively.
2.4. Electrochemical-measurements
The anti-corrosion performance of the three inhibitors (HM1–HM3)
on the mild steel (MS) was investigated using electrochemical imped-
ance spectroscopy and polarization potentiodynamic in various concen-
trations (10−6 to 10−3 M) at 308 K. The electrochemical experiment is
carried out using a three electrodes electrolytic cell: the platinum foil
as a counter electrode, saturated calomel electrode as a reference, and
MS as a working electrode of an exposed area of 1.00 cm2. The MS spec-
imen immersed in a test solution for 30 min until a steady-state poten-
tial is achieved using PGZ100 potentiostat. Electrochemical impedance
spectroscopy measurements were carried in a frequency range of 0.1
 D. Douche et al. / Journal of Molecular Liquids 308 (2020) 113042 3

Scheme 1. Synthetic route of HM1–HM3.

to 10 MHz and an amplitude of 10 mV with 10 points per decade. The where χ and η are the absolute electronegativity and global hardness.
PDP curves were registered out at a constant scan rate of 2 mV/s. For Fe, χFe is 7 eV and ηFe is zero eV [22]. The adsorbed sites of HM1–
HM3 on the surface of carbon steel were determined by ESPs charges
2.5. Computational details calculations. The solvent effects were taken into consideration implicitly
using the integral equation formalism variant (IEFPCM). In this model,
2.5.1. DFT calculations the inhibitor is embedded into a cavity surrounded by solvent mole-
First, HM1–HM3 compounds have been subjected to conformational cules described by its dielectric constant ε (for water ε = 78.3) [23].
analysis. The identified stable conformers were optimized at the B3LYP/ The protonation is thermodynamically quantified by Proton Affinity
6–311 + G (d,p). The absence of imaginary frequencies confirms that (PA), which is defined as the enthalpy of the reaction:
the optimized geometries are true minima. The corrosion inhibition ef-
þ
ficiencies of HM1–HM3 may strongly depend on the electronic proper- InhH ⟶Inh þ Hþ ð12Þ
ties and the delocalization of the frontier orbitals (HOMO and LUMO).
Thus, a set of electronic properties of HM1–HM3 were calculated in Theoretical calculations and frontier orbitals mapping are performed
their neutral and protonated forms. Among the calculated electronic using Gaussian 16 package [19].
properties frontier orbital energies, ionization potential (I), electronic
affinity (A), gap energy between the HOMO and LUMO (ΔE), electro- 2.5.2. Molecular dynamics (MD) simulations
negativity (χ), chemical hardness (η), softness (S = 1/η), and dipole The strength of the adsorbed inhibitors HM1–HM3 on the metal sur-
moment (μ). These electronic properties were obtained using face was determined using MD simulation as implemented in Materials
Koopman's theorem [20], in which I = −EHOMO and A = −ELUMO. Studio 8.0 software. The stepwise of MD simulation are reported in our
Other properties were calculated using the following formula: previous study [24].


∂E 3. Results and discussions
μ ¼ −χ ¼ ð2Þ
∂N υðrÞ
3.1. Gravimetric measurements
2
!

1 ∂ E 1 ∂μ
η¼ ¼ ð3Þ Inhibitors efficiencies (ηw %) and Corrosion rates (CR) in 1.0 M HCl
2 ∂N2 2 ∂N
υðr Þ with different concentrations of the three synthesized compounds

 (HM1, HM2, and HM3) was calculated with the gravimetric technique.
IþA The inhibitors efficiencies and Corrosion rates are presented in Table 1.
χ ¼ −μ ¼ ð4Þ
2 It is evident from Table 1 that, the corrosion rate significantly decreased
from 0.82 (mg·cm−2·h−1) in the blank acid to0.08, 0.11 and
η¼
I−A
ð5Þ 0.15 mg·cm−2·h−1 respectively, when 10−3 M of the inhibitors
2 (HM1, HM2, and HM3) was added. The ηw additional increased with

σ ¼ 1=η ð6Þ
Table 1

 Corrosion parameters for MS samples following 5 h soaking in 1.0 M HCl solution in the
−EHOMO −ELUMO absence and different concentrations of HMs.
χ ¼ −μ ¼ ð7Þ
2
Inhibitor concentration C CR ηw θ

 (mol/l) (mg.cm−2 h−1) (%)
ELUMO −EHOMO
η¼ ð8Þ
2 1.0 M HCl – 0.82 – –
HM1 10−6 0.23 72 0.72
10−5 0.17 79 0.79
ω ¼ μ 2 =2η ¼ χ 2 =2η ð9Þ 10−4 0.12 85 0.85
10−3 0.08 90 0.90
ε ¼ 1=ω ð10Þ HM2 10−6 0.25 70 0.70
10−5 0.21 74 0.74
10−4 0.16 80 0.80
The fraction of the transferred electrons (ΔN) is obtained using the 10−3 0.11 87 0.87
following formula [21]: HM3 10−6 0.29 65 0.65
10−5 0.22 73 0.73
χ Fe −χ Inh 10−4 0.19 77 0.77
ΔN ¼ ð11Þ 10−3 0.15 82 0.82
2ðχ Fe þ χ Inh Þ
4 D. Douche et al. / Journal of Molecular Liquids 308 (2020) 113042
increasing inhibitors (HM1, HM2, and HM3) concentration until an op-
timum concentration was reached (10−3 M). Efficiencies of 90%, 87%,
and 82% were achieved at a 10−3 M concentration of HM1, HM2, and
HM3 respectively. This can be attributed to the interaction of the HM
molecules and the active sites on the MS. Metal atoms (MS) at the active
sites form coordination bonds with pairs electron isolated from elec-
trons π of nitrogen can also be given to the surface of MS by nitrogen
atoms leading to increased adsorption and thus increased efficiency.
It is generally accepted that, at a given inhibitors concentration, the
efficiency decreases with increasing concentration of the acid (1.0 M
HCl). Similar works on compounds organic in 1.0 M HCl by different au-
thors showed ηw values between 79 and 95% [25]. From Table 1, it was
also observed that for all inhibitors (HM1, HM2, and HM3) acted as
corrosion inhibitors in1.0 M HCl with the following order
HM1 N HM2 N HM3.
3.2. Adsorption isotherms
The adsorption isotherm study of organic inhibitors on mild steel in
1.0 M hydrochloric acid solution was warranted by the substitution ef-
fects of the type of inhibitors which leads to the formation of a water
blocking matrix [26].
To examine the adsorbent behavior of HM1, HM2 and HM3 on a
mild steel surface, various adsorption isotherms such as Langmuir and
Freundlich were explored to determine the potential link between in-
hibitor concentration (C) and the surface coverage (θ is shown in
Table 2). We noticed that the adsorption of HM1, HM2, and HM3 fa-
vored the Langmuir isotherm of the form [27]:
C 1
¼ þC
θ Kabs
The values of Gibb's free adsorption energy (ΔG °ads) were calculated
using equation [28]:
ΔGads ¼ −RT ln ð55:5 K Þ
where R is the universal gas constant, T is the absolute temperature and
the value of 55.5 is the approximate concentration (mol·L−1) of water
in the solution.
The adjustment lines in Fig. 2 illustrate the Langmuir isotherm with
slope values, intersections and linear correlation coefficients (R2) of the
studied inhibitors HM1, HM2, and HM3.
The selection of the Langmuir isotherm on the remainder was
founded on the values of R2 close to the unit and the interception at 0
[29]. As a result, the Kads values were obtained from the slopes of the
lines. The Kads values of HM1, HM2, and HM3 are as follows 3.74 105,
2.79 105 and 3.21 105 M−1, respectively. A higher Kads value indicates
a great interaction between adsorbent and adsorbent [30]. The recorded
values ΔG°ads are as follows: −42.24, −41.51 and −41.86 kJ·mol−1,
which respectively represent HM1, HM2, and HM3. The ΔG°ads values
obtained above the −40 kJ·mol−1 threshold propose a spontaneous
process indicated by the chemical and physical adsorption of inhibitory
species on a mild steel surface [31].
Table 2
Values of Kads and free energy of adsorption (ΔGads) of HMs for MS in1.0 M HCl at 308 K.
Inhibitors Kads(M−1) ΔGads(Kj·mol−1)
HM1 3.74E+05 −42.24
HM2 2.79E+05 −41.51
HM3 3.21E+05 −41.86
0.0014
HM1
0.0012 HM2
HM3
0.0010
0.0008
0.0006
0.0004
0.0002
0.0000
0.0000 0.0002 0.0004 0.0006 0.0008 0.0010
C(M)
Fig. 2. Langmuir isotherm plot for the adsorption of HMs on mild steel (MS) surface in
1.0MHCl.
3.3. Potentiodynamic polarization (PDP)
Anodic and cathodic polarization curves of mild steel presented in
Fig. 3 was determined to define the effect of the three synthesized com-
pounds HM1, HM2 and HM3 and variation in concentration on the
global behavior of mild steel in1.0 M HCl solution [32]. The inhibition ef-
ficiency of various inhibitors concentrations (HM1, HM2, and HM3) was
calculated and grouped in Table 3. The electrochemical parameters,
such as Icorr, Ecorr, Tafel slopes (βa; βc) and the percent inhibition effi-
ð13Þ ciency (IE %) were calculated using the following equation:
Icorr−I0corr
IE% ¼ ð15Þ
Icorr
where Icorr and I'corr are the corrosion current densities without and
with various inhibitors concentrations, respectively.
ð14Þ The compounds HM1, HM2 and HM3 exhibit cathodic effects on the
corrosion of mild steel in a solution of1M HCl [33]. Further examination
demonstrates mixed leverage is better pronounced in HM3 at a maxi-
mum concentration (10−3 M). Indeed, HM1, HM2, and HM3 were all
types of cathodic corrosion inhibitors but the cathodic effect is more
pronounced for all the inhibitors tested at high concentrations [34].
This led to a more significant reduction of the current density recorded
in this study. The values of the anode slopes (βc, βa) Tafel recorded in
Table 3 corroborate the effect observed on the anodic and cathodic
arms of Fig. 3.
The minor offset of the Ecorr values indicates that the newly synthe-
sized compounds HM1, HM2 and HM3 delays the dissolution of the
mild steel by the development of a protective layer without modifying
the reaction mechanism [35]. Nevertheless, HM1 registered the smallest
corrosion current density (icorr) value at 10−3 M nominate that HM1 is a
greater corrosion inhibitor the undermost concentration evaluated.
Nevertheless, based on the results obtained, the obvious trend in the ef-
ficiency of the inhibition obtained from the average values in% of HMs is
such that HM1 ˃ HM2 ˃ HM3.
3.4. Electrochemical impedance spectroscopy (EIS) study
Mild-steel corrosion behavior in an acidic solution (1.0 M HCl), in
the presence of the compounds (HM1, HM2, and HM3), was studied
R2
by EIS at 298 K, after half-hour of immersion at the corrosion potential.
0.99998 Nyquist mild-steel plots, in uninhibited and inhibited acid solutions
0.99996 containing different HMs concentrations, are regarded as one part of a
0.99996
semicircle, are shown in Fig. 4. The impedance diagrams obtained are
 D. Douche et al. / Journal of Molecular Liquids 308 (2020) 113042 5

Fig. 3. Polarization curves for MS in the absence and presence of HMs in1.0 M HCl at 308 K.

not perfect semicircles as predicted by the EIS theory. This could be at- the metal [38]. Also, the decrease of Cdl values with the addition of in-
tributed to the frequency dispersion and non-ideal behavior of the dou- hibitors (HM1, HM2, and HM3) is due to the adsorption of the mole-
ble layer as a capacitor [36]. Luckily, this would effectively indicate that cules of the compound, replacing water at the mild steel-solution
the white charge transfer resistance in all the systems studied was interface and leading to a decrease in the local dielectric constant and/
lower than that of the inhibited samples [37]. The impedance parame- or an increase of the thickness of the electrical double layer [39].
ters derived from this study are given in Table 4. It was found that as To further analyze changes in various parameters in electrochemical
the concentration of inhibitors increased, the Rct values also increased, impedance spectroscopy, impedance spectroscopy at different concen-
but the values tended to decrease. According to the study carried out trations was adjusted using the equivalent circuit diagram in Fig. 5,
by EIS, it can be established that the higher the resistance to charge where Rs is the solution resistance, Rct is the load transfer and CPE is a
transfer, the greater the adsorption of the adsorbent on the surface of constant phase element.
At concentrations between 10−6 M and 10−3 M, the values of Rct
followed the order: HM1 N HM2 N HM3, which resulted in the order
Table 3
of inhibition efficiency HM1 N HM2 N HM3, and the maximum percent-
Potentiodynamic polarization parameters for MS in 1.0 M HCl in the absence and presence
of inhibitors HMs at 308 K. age of EEIS is 90, 89 and 88% for HM1, HM2 and HM3, respectively.
These results reassure the fact that the three quinolines have good
Inhibitor Concentration Ecorr -βc βa Icorr EI
corrosion inhibition properties for mild steel in 1 M HCl solution.
(M) (mV/ECS) (mV/dec) (mV/dec) (μA/cm2) %

Blank 1 −448 142 185 1381 – 3.5. DFT calculations

HM1 10−6 −448 142 185 1381 –
10−5 −441 183 200 452 67
10−4 −439 167 193 305 78 To explore the inhibition mechanism and the observed inhibition ef-
10−3 −451 161 174 192 86 ficiencies of HM1, HM2 and HM3 inhibitors, a set of their electronic
HM2 10−6 −445 142 227 125 91 properties were calculated in neutral and protonated forms (Table 5).
10−5 −453 173 196 491 64
Simple linear regression between the maximum corrosion inhibition ef-
10−4 −449 142 187 373 73
10−3 −457 159 175 201 85 ficiency (ηexp) obtained at 10−3 M and the electronic parameters of
HM3 10−6 −446 135 168 167 88 HM1, HM2 and HM3 are performed. The SLR outputs showed that the
10−5 −459 146 183 507 63 best correlations were found for the ionization potential (IP) in neutral
10−4 −450 168 165 399 71 and protonated forms with correlation coefficients (R2) of 99.87 and
10−3 −447 129 158 253 82
98.40%, respectively. The correlation between the dipole moment and
6 D. Douche et al. / Journal of Molecular Liquids 308 (2020) 113042

Fig. 4. Impedance spectra for MS in 1.0 M HCl without and with different concentrations of HM1, HM2, and HM3.

the inhibition efficiency of HM1-HM3 shows that the inhibition de-
creases with the polarity. For instance, the higher inhibition efficiency
of HM2 compared with HM1 may refer to the lower polarity and higher
proton affinity of the former compared with the latter. The fraction of
electron transfers (ΔN) is a measure of a relative quantity of electron
transfer between the inhibitor and the vacant d-orbital of Fe atoms dur-
ing metal inhibitor. The positive values of ΔN show the electron transfer
from the inhibitor to metal and vice versa. The positive ΔN values of
HM1–HM3 indicates that in the neutral from the inhibitors have the
proneness to transfer its electrons to the vacant d-orbital of Fe atoms
during metal inhibitor interactions. However, in the protonated form
of HM1–HM3, the negative sign of ΔN indicates the transfer of electrons
from the vacant d-orbital of Fe atoms to the protonated inhibitors dur-
ing the metal inhibitor interactions.
Frontier molecular orbitals (HOMO and LUMO) and ESP of HM1–
HM3 are shown in Fig. 6. As can be seen from Fig. 6, HOMO orbitals of
theHM1 and HM3 inhibitors are mainly delocalized over the central
part of quinolin-8-ol and azidomethyl group, while in HM3 the HOMO
is delocalized morphilinomethyl group ring. However, the LUMO

Table 4
Electrochemical parameters determined from EIS plots for MS in 1.0 M HCl in the absence
and presence of HM1, HM2 and HM3 at different concentrations.

Іһіbіtοr Cοncеntratіοn (M) Rxt (Ω·cm2) Cdl (μF/cm2) ЕEis %

Blank 1 14.57 200 –

10−6 67 109.46 78
10−5 93 84.79 84
HM1
10−4 102 62.67 86
10−3 142 49.23 90
10−6 31 113.91 53
10−5 74 89.17 80
HM2
10−4 101 67.94 86
10−3 131 52.21 89
10−6 34 58.41 57
10−5 50 54.36 71
HM3
10−4 96 52.87 85
10−3 122 56.38 88
Fig. 5. Equivalent circuit diagram.
 D. Douche et al. / Journal of Molecular Liquids 308 (2020) 113042 7

Table 5 solution, the adsorption energy can be calculated using the following
Electronic properties of HM1–HM3 calculated at the B3LYP/6–311 + G (d, p) level of equation:
theory.
 
I (eV) A (eV) ΔE (eV) χ η S ΔN μ (Debye) Eads ¼ Etotal − Esurf þwater þ Einhþwater þ Ewater ð16Þ
HM1 6.26 2.00 4.26 4.13 2.128 0.2350 0.675 2.63
HM2 6.29 2.04 4.26 4.17 2.129 0.2349 0.666 3.52 where Etotal is the total potential energy of the system (iron crystal, the
HM2 6.13 1.98 4.15 4.06 2.074 0.2411 0.709 2.60 adsorbed inhibitor molecule, and solution); Esurf+water and Einh+water are
the potential energies of the system without the inhibitor and the sys-
tem without the iron crystal, respectively; Ewater is the potential energy
of the water molecules.
orbitals of HM1, HM2 and HM3 are mainly delocalized over the
The adsorption energies were calculated from the average adsorp-
quinonilin-8-ol. The inhibition efficiency of the adsorbed inhibitors is ef-
tion energy of the obtained equilibrium configurations. The obtained
ficient for the inhibitor that possesses (i) donating electrons groups
Eads values are −626.2, −618.5, and −612.8 kJ/mol for HM1, HM2,
(Nucleophilic attack) to d orbital of the metal, and (ii) accepting elec-
and HM3, respectively. Negative adsorption energies indicate spontane-
trons sites from the metal surface(Electrophilic attack) [39]. The
ous adsorption of HMs on the iron metal surface. The bigger is the abso-
HOMO and LUMO orbitals delocalization clearly indicate that the
lute value of Eads, the stronger is the adsorption of the inhibitor on the
HM1-HM3 may have donor/acceptor electron of atom sites in 8-
metal surface. From Eads energies, it appears that HM1 and HM2 have
hydroxyquinoline moieties to/from the d-orbitals of the iron metal.
slightly higher absolute values of Eads than HM3, and therefore they
The calculated proton affinities of HM1, HM2 and HM3 are 374, 342
present a better inhibiting property for carbon steel, consistent with
and 333 kcal/mol, respectively.
the experimental results.

3.6. Molecular dynamics simulation 3.7. The 8-hydroxyquinoline derivatives (HMs) inhibition mechanism

It is generally recognized that through MD simulations, it is feasible
to generate deep insight into the way in which the inhibitor molecule
adsorbs and how much change in an inhibitor would constitute an im-
portant difference in corrosion inhibition. Therefore, the molecular dy-
namics process was performed and the whole system reached
equilibrium until both the temperature and energy of the system were
balanced. The low energy adsorption configurations of three inhibitor
molecules adsorbed onto Fe(110) surface are shown in Fig. 7.
Fig. 7 reveals that the adsorption centers of HMs inhibitors on the Fe
(110) surface belong to the electrons of aromatic rings, oxygen and ni-
trogen heteroatoms. Almost, HMs adsorbed flat orientation on the iron
surface to maximize surface coverage and contact, which ensures a
strong interaction for the adsorbate/substrate system.
The strength of HMs adsorbed on the iron surface may be expressed
in terms of their adsorption energies (Eads) on the iron surface. In the
The anti-corrosion efficiency of organic inhibitors for mild steel in
1.0 M HCl may strongly depend on many factors including their concen-
tration, the numbers of active sites and their corresponding charges,
molecular mass and their stability in corrosive environments. Further,
the presence of heteroatoms with lone pairs of electrons (N, O) in
these compounds may increase their ability to inhibit the corrosion of
the metal surface (MS). Previous studies reported that the exposure of
mild steel to the HCl acid solution made its surface charge positively
and adsorption of chloride ions (Cl−) on its surface.
HMs and their protonated forms may be adsorbed on the surface of
the metal via electrostatic adsorption mechanism. As shown in Scheme
1, the 8-hydroxyquinoline derivatives (HMs) molecules consist of oxy-
gen heteroatoms, which may donate their free electron to the un-
filled steel atom orbitals, resulting in the 8-hydroxyquinoline deriva-
tives (HMs) adsorption on the mild steel surface (Fig. 8). The electrons

Fig. 6. Structures of HOMO, LUMO, and ESP of studied inhibitors.

8 D. Douche et al. / Journal of Molecular Liquids 308 (2020) 113042
Fig. 7. Side and top views of most stable adsorption configurations for three HMs on Fe(110) surface.
flow from the HMs electron ɾich centers to electɾon deficient centers of
the metal (MS) inhibiting the electrochemical process responsible for
corrosion. Increase in inhibitive peɾformance of 8-hydroxyquinoline de-
rivatives (HMs) observed with incɾease in concentɾation, implies ad-
sorption of 8-hydroxyquinoline derivatives (HMs) on the steel surface.
4. Conclusions
In the present work, three 8-hydroxyquinoline derivatives have
been synthesized and characterized by different spectroscopic tech-
niques. The newly synthesized compounds HM1, HM2 and HM3 were
evaluated for their anti-corrosion performance against MS in 1.0 M hy-
drochloric acid solution and we concluded that:
• HM1, HM2 and HM3 retard MS corrosion in 1.0 M HCl solution with
their E (%) enhanced at increased inhibitors concentrations.
• The polarization and impedance electrochemical data showed that
the three compounds (HM1-HM3) are cathodic type corrosion inhib-
itors;
• The adsorption of corrosion inhibitors HM1, HM2 and HM3 on MS
surface was spontaneous, labeled by chemical and physical
Fig. 8. Proposed schematic for the adsorption mechanism of inhibitors HMs on mild steel
surface under hydrochloric acid medium.
interactions, and favors the Langmuir adsorption isotherm.
• Quantum chemical study indicated that electrons of aromatic rings,
oxygen, and nitrogen heteroatoms were the major absorption centers
for donor/acceptor interactions with the unoccupied d-orbital of MS.
CRediT authorship contribution statement
Dhaybia Douche: Methodology, Validation. Hicham Elmsellem:Con-
ceptualization, Invetsigation. El Hassane Anouar:Conceptualization, Soft-
ware, Writing - original draft, Writing - review & editing, Visualization. Lei
Guo: Software, Methodology, Invetsigation. Baraa Hafez: Resources,
Invetsigation. BurakTüzün:Resources, Software, Invetsigation. Ahmed
El Louzi:Conceptualization, Supervision. Khalid Bougrin:Writing - origi-
nal draft, Validation. Khalid Karrouchi: Project administration, Data
curation, Writing - review & editing.Banacer Himmi:Conceptualization,
Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
This research was partially supported by UM5R, the National Natural
Science Foundation of China (21706195), the Science and Technology
Program of Guizhou Province (QKHJC2016-1149), the Guizhou Provin-
cial Department of Education Foundation (QJHKYZ2016-105) and
TUBITAK ULAKBIM, High Performance and Grid Computing Center
(TR-Grid e-Infrastructure).
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