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Understanding imidazole derivatives effect as a corrosion inhibitor for brass

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DOI: 10.1080/1478422X.2022.2119706

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 Corrosion Engineering, Science and Technology
The International Journal of Corrosion Processes and Corrosion Control

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Understanding imidazole derivatives effect as

a corrosion inhibitor for brass in nitric acid:
a combined experimental and theoretical
assessments

A. El-Asri, A. Jmiai, Y. Lin, A. Taoufyq, M. M. Rguiti, H. Bourzi & S. El Issami

To cite this article: A. El-Asri, A. Jmiai, Y. Lin, A. Taoufyq, M. M. Rguiti, H. Bourzi & S. El Issami
(2022): Understanding imidazole derivatives effect as a corrosion inhibitor for brass in nitric acid:
a combined experimental and theoretical assessments, Corrosion Engineering, Science and
Technology, DOI: 10.1080/1478422X.2022.2119706

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CORROSION ENGINEERING, SCIENCE AND TECHNOLOGY
https://doi.org/10.1080/1478422X.2022.2119706

RESEARCH ARTICLE

Understanding imidazole derivatives effect as a corrosion inhibitor for brass in

nitric acid: a combined experimental and theoretical assessments
a a b c
A. El-Asri , A. Jmiai , Y. Lin , A. Taoufyq , M. M. Rguitia, H. Bourzia and S. El Issamia
a
Physical Chemistry and Environment Team, Faculty of Sciences, University of IBN ZOHR, Agadir, Morocco; bAstate Key Laboratory of Oil and Gas
Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, People’s Republic of China; cMaterials and Environment
Laboratory, Faculty of Sciences, Ibn Zohr University, Agadir, Morocco

ABSTRACT ARTICLE HISTORY

This paper presents a new study on imidazole derivatives namely 1H-imidazole (IM), Received 7 July 2022
N-methylimidazole (MIM) and 1H-benzimidazole (BIM) as a corrosion inhibitor for brass in nitric Accepted 18 August 2022
acid medium. Electrochemical results demonstrate that the inhibition increases with a high
KEYWORDS
concentration of imidazole derivatives; the inhibitory efficiency reaches a maximum of 94% at Corrosion; Imidazole
10–2 mol L−1 for BIM. SEM morphology and EDS analysis show that these derivatives are adsorbed derivatives; Inhibitor; Brass;
onto the brass interface, the brass sample is effectively protected and the surface becomes Surface analysis; Quantum
relatively flat, which is more significant in the presence of 1H-benzimidazole. FTIR results confirm chemical calculations and
the retention of BIM on the interface of Cu-Zn alloys. In addition, quantum chemistry calculation MD simulations
manifests that the three derivatives can reveal high anticorrosion properties. Molecular dynamics
simulation data manifest that the three imidazole derivatives can be adsorbed at the brass surface
in a paralleled way, and have large binding energy.

Highlights
. A new action of imidazole derivatives to mitigate brass corrosion was explored in HNO3.
. BIM showed inhibitory efficiency more than 94% in HNO3 solution.
. The inhibition mechanism is studied using SEM/EDS surface analysis and FTIR analysis.
. The calculated adsorption energies are ranked in the following order: BIM > MIM > IM.
. Theoretical and experimental results lead to used imidazole derivatives as potential corrosion
inhibition for brass in HNO3 solution.

Abbreviations: EIS, Electrochemical impedance spectroscopy; SEM, Scanning Electron

Microscopes; EDS, Energy Dispersive Spectroscopy; FTIR, Fourier Transform Infrared
Spectroscopy; DFT, Density-functional theory; MD, Molecular Dynamics; RDF, Radial distribution
function

Introduction
Cu-Zn alloys (Brass) are frequently used to create heating
or cooling systems, such as condensers, evaporators and
fractionating columns, because of their great thermal con-
ductivity and outstanding mechanical workability. How-
ever, during operation, inorganic deposits mixed with
corrosion products generally form on the tube surfaces
of industrial heat exchangers. These deposits reduce the
efficiency of the heat transfer and the fluid-flow mass
[1]. Moreover, these deposits induce a sub-deposit cor-
rosion attack and possibly reduce the lifespan of the equip-
ment. As a result, operating costs in these industries are

CONTACT A. Jmiai jmiai.aziz@gmail.com; A. El-Asri elasriabdallah4@gmail.com Physical Chemistry and Environment Team, Faculty of Sciences,
University of IBN ZOHR, B.P.8106 Cité Dakhla, Agadir, Morocco
Supplemental data for this article can be accessed online at https://doi.org/10.1080/1478422X.2022.2119706.
© 2022 Institute of Materials, Minerals and Mining Published by Taylor & Francis on behalf of the Institute
2 A. EL-ASRI ET AL.
increased and plant shutdown becomes necessary to per-
form frequent descaling operations. Therefore, the main-
tenance of those plants requires periodic cleaning of the
affected parts of heat exchanger. This is currently per-
formed with acid cleaning solutions [2,3]. When brass is
immersed in an acid medium, copper is thermodynami-
cally more stable than zinc. however, zinc tends to dissolve
[4] at specific potentials. Oxidising acids, i.e. nitric acid,
known to be a strong oxidant, tend to corrode copper
and its alloys quite easily. Great progress has been made
in this area; nevertheless, inhibitors for brass in nitric
acid have been much less studied than in other etching
media.
Different methods have been used to inhibit the corrosion
problem, one of the most important of which is the use of
inhibitors. However, generally contain specific characters
such as nitrogen (N), Sulphur (S), oxygen (O) and so on, or
some especial unsaturated functional groups, etc. [5,6],
which act via the creation of an insoluble protective complex,
in an aggressive environment [7–9] Thus, the effective inhibi-
tors the best-known corrosion of copper and these alloys in
several media are the derivatives of imidazoles, benzotriazole
and tetrazoles and their derivatives [10–15]. In addition, imi-
dazole and its derivatives have excellent corrosion inhibition
properties as corrosion inhibitors for acidic media, which
have been reported in previous works [15–19]. Corrosion
inhibitor has the advantages of small dosage, significant cor-
rosion protection effect and simple operation [20].
This work presents the first corrosion inhibition, surface
analytical investigation and quantum chemical study of a
low concentration of imidazole derivatives illustrated in
Figure 1 as anti-corrosion products for brass in
0.1 M HNO3 medium using gravimetric and electrochemi-
cal measurements coupled with morphology and surface
analysis in summer is approached to assess the inhibitory
efficiency of the three derivatives. The choice of these com-
pounds was associated with their molecular structure,
which has -N atoms, and π electrons, the aim of this
paper research was to study the effect of the methyl and
benzene group associated to the imidazole compound on
the inhibition against brass corrosion in 0.1M nitric med-
ium and provide insights for exploring the corresponding
anticorrosion mechanism. In addition, theoretical studies
were carried out to understand the action mode of the com-
pounds tested.
Figure 1. Structural formulas for the three compounds studied IM, MIM and BIM.
Table 1. The brass specimens composition.
Element Cu Zn Fe
Weight % 60.5-63.5 ≤38 ≤0.15
Materials and method
Experimental
The weight loss measurements were carried out in glass
flasks with a capacity of 50 mL and placed in a thermostati-
cally controlled water bath. The volume of the solution was
25 mL. The brass coupons used in its composition identified
in Table 1 had a rectangular shape (length = 1.5 cm, width =
1 cm). The samples were weighed and suspended in 25 mL of
an aerated solution of 0.1M HNO3 containing imidazole
derivatives at the desired concentrations for an exposure
period of 24, 48, 72, 98, 120 h at 298 ± 1 K. At the end of
the tests, the coupons were removed, washed with distilled
water, degreased with acetone, washed again with distilled
water, dried and then weighed using an analytical balance
(accuracy: ±0.1 mg). Two measurements were made in
each case and the average value of the weight loss was
reported. The corrosion rate, W (expressed in g. cm².h−1)
as well as the inhibition efficiency (%Ew ) over the exposure
period were calculated according to the following Equation
(1) & (2) [21]:
DW Dm
W= = (1)
t S ×t


Winh
%Ew = 1 − 100 = u × 100 (2)
W
where W and Winh are the corrosion rate without and with
imidazole derivatives, respectively. A cylindrical brass rod
was coated with epoxy resin so that only the circular section
(0.5 cm²) of the rod was exposed to the solution. Before each
experiment, the brass electrode was abraded using emery
papers of different grain sizes up to a grain size of 2000 to
remove corrosion products, then rinsed in acetone and dis-
tilled water, and immediately immersed in the corrosive
solution.
Imidazole derivatives are shown in Figure 1. All of these
compounds were obtained from Sigma Aldrich Chemical
(99%). They were placed in 0.1M HNO3 without pretreat-
ment at concentrations of 5.10−5 , 10−4 , 5.10−4 , 10−3 ,
5.10−3 and 10−2 M. A conventional electrochemical cell of
100 ml capacity was used containing three compartments
for the working electrode, a platinum counter electrode
and the reference electrode. These three electrodes have
been made very close together to minimise the ohmic
P Sb Pb Bi imputed
≤0.01 ≤0.005 ≤0.08 ≤0.002 ≤0.5

drop. The reference electrode was a saturated calomel (SCE)
used directly in contact with the solution. The counter elec-
trode was a platinum wire. The measurements were per-
formed in dynamic and aerated solutions of 0.1M HNO3 at
298 ± 1 K (using a water thermostat ±1°C) without and
with different concentrations (5.10−5 –10−2 M) of imidazole
derivatives, as possible corrosion inhibitors. For each test,
Tafel’s polarisation curves were obtained by automatically
changing the electrode potential from −400 to +300 mV/
SCE with a sweep rate of 1 mV s−1. Impedance measure-
ments were made over a frequency range of 10 kHz to
1 Hz and with an amplitude of 10 mV peak to peak using
AC signals at open circuit potential. All measurements
were performed with a VersaSTAT 3 Potentiostat/
Galvanostat.
Surface morphology analysis and elemental
composition
Before proceeding with the SEM and EDS tests, the brass
samples were cut into small pieces of 1 cm², these were suc-
cessively polished from 600 to 2000 mesh with SiC abrasive
papers, washed with distilled water, followed by 20% nitric
acid pickling, degreased with acetone, washed again with
water distilled. The Cu-Zn samples were immersed in 0.1M
nitric acid HNO3 without and with 10−2 M IM, MIM and
BIM for 24 h at 198 ± K; the scanning electron microscope
model is (JEOL JSM® – 6480 LV).
FTIR analysis
After 15 days of immersion in a 0.1M HNO3 solution with-
out and with 10−2 M BIM, the corrosion product film on the
alloy surface was carefully discarded and subjected to FTIR
analysis. This was performed in attenuated total reflectance
(ATR) mode in the wavenumber range of 4000–400 cm−1
at a resolution of 16 cm−1 using a Shimadzu spectrometer.
Theory and computational details
Quantum chemical calculations
Several descriptors of reactivity have been extracted, such as
highest occupied molecular orbital (HOMO), lowest unoccu-
pied molecular orbital (LUMO), dipole moment (µ) and
energy gap (ΔE gap), etc. Quantum calculations were per-
formed using the Gaussian software package, module version
9.0 [22–24]. The calculations were carried out without geo-
metric constraint until the complete optimisation of the geo-
metry. All calculations were performed with full geometry
optimisation using the B3LYP hybrid functional level with
an upper basis set denoted as 6-31G+(3d,p) in which this
basis set gives better results in terms of the determination
of geometries and electronic properties [25,26]. All quantum
calculations were performed in gas and aqueous phase using
the self-consistent field theory (SCF), with the polarised con-
tinuum model (PCM) [27]. The ionisation energy and elec-
tron affinity were determined by the values of the energies
of the HOMO and LUMO orbitals using Equations (3) &
(4) [19,28,29]:
I = −EHOMO (3)
A = −ELUMO (4)
CORROSION ENGINEERING, SCIENCE AND TECHNOLOGY 3
The values of I and A are exploited in order to find the
values of the electronegativity, the global hardness and the
softness of the inhibitor molecule, Equations (5), (6) & (7)
[29,30]:
1
x=− (ELUMO − EHOMO ) (5)
2
1
h= (ELUMO − EHOMO ) (6)
2
1
s = (7)
h
Molecular dynamic computational
The interactions of the surface and the inhibitors studied
IM, MIM and BIM are investigated using molecular
dynamics implemented in BIOVIA Material Studio 8.0
software from Accelrys, Inc [31]. This method was
used to assess the nature of the adsorption energy inter-
actions between the inhibitors, in their neutral forms
and the metal surface. Since copper is the main com-
ponent of the studied metal (brass), the simulated
adsorption system was carried out on the surface of
Cu (111). This selected crystal surface is the most stable
as reported in the literature [27]. The interactions of the
copper surface and the studied inhibitors are carried out
via the Cu (111) surface model (with Periodic Boundary
Condition) using the size of 15.335 Å × 15.335 Å × 6.260
Å with the inclusion of a vacuum layer 20 Å at the C
axis including 60 water molecules/one inhibitor mol-
ecule/3 hydronium ions +3 nitrate ions. The molecular
dynamics calculations were carried out by applying 5
cycles (2000 steps in each of the cycles) of simulated
annealing. The lowest potential energy configurations
were sampled at low-temperature stages. The MD results
were obtained using a canonical ensemble NVT con-
ditions (fixed number of atoms N, a fixed volume V
and a fixed temperature T) at 298 K and a simulation
time of 150 ps (1 fs time step) for the simulation system
to reach a steady state. Temperature control was
achieved through the use of the Berendsen thermostat
[32,33]. The energy minimisation and MD calculation
processes were performed using a frequently used COM-
PASSII force field [34]. For the calculation of the radial
distribution function (RDF), the total trajectory was used
[35]. Binding and interaction energies are estimated
using the following Equations (8) & (9) [36,37].
Eads = Etotal − (Esurface+solution + Einhibitor+solution )
+ Esolution (8)
Ebind = −Eads (9)
where Etotal is the total energy of the simulation system,
Esurface + solution value represents the total energy of the
system without any molecules of inhibitor, Einhibiteur +
solution represents the total energy of the system without
the copper crystal, and Esolution denotes the total energy
of the solution.
4 A. EL-ASRI ET AL.

ring that may have favourable adsorption sites. The standard

deviation (the method was supplied in detail in the Support-
ing Information Text 1) reported in Table 2, show good con-
sistency between all the mass losses measured. In addition,
the standard deviation (σ) of the inhibition efficiency calcu-
lated using WL method means that the results of corrosion
rate measured are in good agreement with experiments
data [35,38].

Potentiodynamic polarisation measurement

Potentiodynamic polarisation measurements were used to
evaluate the effects of various concentrations of IM, MIM
and BIM on the corrosive behaviour of brass in 0.1M
HNO3 . Figure 3 and Table 3 show the potentiodynamic
polarisation curves and electrochemical parameters derived
from PDP experiments such as corrosion current intensity
Figure 2. The evolution of weight loss with immersion time of brass in 0.1M
(Icorr), corrosion potential (Ecorr), inhibition efficiency (IE
HNO3 with and without 10−2 M of IM, MIM and BIM. %), anodic and cathodic slopes βa and βc respectively. The
figure shows the polarisation curves of IM, MIM and BIM
at 298 K with a variety of inhibitor concentrations. The cor-
Results and discussion rosion current densities Icorr in the presence of IM, MIM and
Weight loss method BIM decrease with increasing concentration, providing good
efficiency at the concentration of 10−2 M. where the best inhi-
The corrosion rate and inhibition efficiencies obtained from bition efficiency was 84.71% for BIM compound at the temp-
gravimetric experiments at an inhibitor concentration of erature of 298 K, followed by MIM, and finally by IM
10−2 M in 0.1M HNO3 at different immersion times are compound. This indicates that the adsorption behaviour of
shown in Table 2. The results show that the brass corroded the three inhibitors does not vary during the polarisation
strongly in the uninhibited 0.1M HNO3 solution, while the period, the Icorr in the presence of the BIM decreases with
presence of inhibitors considerably reduced the dissolution increasing concentration, Increasing the concentration of
rate. It can be seen from Table 2 and Figure 2 that the the inhibitor leads to the formation of multilayers which
addition of IM, MIM and BIM led to a decrease in the cor- further reduces the rate of corrosion due to the attack of
rosion rate, and the corresponding increase in efficiency, active corrosion ions in the acid medium, with the best per-
which was particularly significant in the presence of the com- formance at 10−2 mol L−1. Based on the results discussed
pound BIM (94%) after 72 h of immersion time which shows above and Table 3, BIM performs best among the inhibitors
that the dissolution of brass decreased with time and gener- tested. In general, the shifts or displacements in Ecorr values
ally became stable after 48 h, this can be explained by the when the results in the blank acid solution are compared
adsorption of the BIM compound on the surface of the with the inhibited ones are generally less than 85 mV. This
brass resulting in a blockage reaction sites. Indicating a for- suggests that these studied compounds inhibit both anodic
mation of the protective film on the surface. The significant and cathodic reactions involved in the corrosion of brass
efficiency of BIM is explained by the presence in the mol- in nitric acid, and they are therefore mixed-type inhibitors
ecule at the same time of the imidazole ring and the aromatic [39]. The Tafel slopes were found to vary in an irregular
manner, indicating that the inhibitory effect of the studied
compounds was not only due to adsorption alone but due
Table 2. Effect of adding organic imidazole compounds at 10−2 M on corrosion to a mixed effect of blocking active sites as well as involve-
of brass in 0.1M HNO3 after different immersion times at 298 K.
ment of some other anions present in the solutions. How-
Time Δm V Standard Standard
(h) (mg) (g cm−².h) deviation error E%
ever, the values of the slopes of the anodic and cathodic
Blank 24 4.55 0.000063 0.000005 0.000003 –
Tafel lines (βa and βc) are changed with the presence of
48 17.70 0.000123 0.000019 0.000013 – three inhibitors, which reflects the influence of the imidazole
72 33.35 0.800400 0.006364 0.004500 – derivatives on the kinetics of the anodic and cathodic mech-
96 32.20 1.030000 0.009051 0.006400 –
120 28.85 1.154000 0.144250 0.102000 –
anism. These results confirm that IM, MIM and BIM exhib-
IM 24 1.40 0.000019 0.000012 0.000008 69.2 ited both cathodic and anodic inhibition effects [36,40,41].
48 6.95 0.000048 0.000008 0.000006 60.7
72 17.80 0.427200 0.038042 0.026900 46.7
96 12.85 0.411200 0.395980 0.180000 60.1 Electrochemical impedance diagram
120 13.00 0.520000 0.412950 0.192000 54.9
MIM 24 1.05 0.000015 0.000005 0.000003 76.9 Figure 4 shows the results of the impedance spectroscopy of
48 5.10 0.000035 0.000016 0.000011 71.2
72 11.20 0.269000 0.006152 0.004350 66.5
brass under different concentrations of imidazole derivatives
96 10.55 0.338000 0.328098 0.132000 67.2 in a 0.1M HNO3 at 298 K. As can be seen from the figure, the
120 14.50 0.580000 0.175362 0.124000 49.7 diameter of the impedance arc of the inhibited solutions is
BIM 24 0.65 0.000009 0.000005 0.000003 85.7
48 1.20 0.000008 0.000003 0.000002 93.2
significantly larger than that of the blank, indicating that
72 2.70 0.065000 0.000212 0.000150 91.9 the tested inhibitors IM, MIM and BIM have a strong inhi-
96 1.75 0.056000 0.006788 0.004800 94.6 bition effect on brass corrosion. The Bode diagram shows a
120 2.90 0.116000 0.028284 0.020000 89.9
time constant which is a surface double layer at low
 CORROSION ENGINEERING, SCIENCE AND TECHNOLOGY 5

Figure 3. Potentiodynamic polarisation curves of Cu-Zn in 0.1M HNO3 without and with imidazole derivative at different concentrations.

frequency [42,43]. All Nyquist and Bode diagrams were
simulated using the most suitable equivalent circuit diagram
EEC shown in Figure 5. The Nyquist diagrams in Figure 4
show a capacitive round at high frequency (HF) and an
inductive round at low frequency (LF). The capacitive loop
at HF might be due to the charge transfer resistance of the
oxide layer on the Brass interface, the inductive loop at LF
to the H+ ion relaxation route, and the adsorption relaxation
of intermediates, which cover the reaction surface. But, the
LF inductive loop was attributed to the Brass dissolution
and/or the re-dissolution of the interface oxide film [44].
Inductive performance could be ascribed to the inflection
of surface area [44].
RS is the resistance from the solution, CPE is the constant-
phase element (CPEdl related to the double layer), Rct is the
charge transfer, L signifies an inductive element, and RL
denotes the inductive resistance. Owing to the dispersion
effect caused by surface heterogeneities, adsorption of inhibi-
tors, formation of porous layers, etc., the behaviour of elec-
tric double layer capacitor is not equivalent to pure
capacitance, so that the CPE is used instead of the capacitor
[42]. The impedance of the CPE is defined by the following
Equation (10) [42]:

Table 3. Polarisation parameters of Cu-Zn in 0.1M nitric acid without and with ZCPE = Q−1 (iv) – n (10)
various concentrations of inhibitors at 298K.
where Q is a proportionality coefficient, ω is the angular fre-
Ecorr/SCE Icorr (mA/ βa (mv/ -βc (mv/ IEpp
Mol L−1
(mV) cm2) dec) dec) (%) quency for which the imaginary part of the impedance
Blank – −116.006 34.311 70.6 131.4 – reaches its maximum [43], i is the imaginary unit and n is
IM 5.10−5 −118.311 25.418 56.8 85.4 25.9 a measure of the surface irregularity. For the integer of n =
−4
10 −122.657 23.916 55.9 91.8 30.3 −1, 0, 1, CPE represents inductance (L), resistance (R) and
5.10−4 −123.736 21.411 55.6 87.1 37.6
10−3 −125.337 19.184 61.7 99.7 44.1 capacitance (C), respectively. In this case, the values of the
5.10−3 −123.130 17.084 59.3 97.5 50.2 double layer capacitance (Cdl ) are obtained using the follow-
10−2 −118.283 16.406 50.0 68.4 52.2 ing relationship (11) [45]:
MIM 5.10−5 −107.589 24.089 60.9 116.3 29.8
10−4 −107.164 21.669 61.5 85.8 36.8 
5.10−4 −109.363 16.969 52.5 85.8 50.5 Cdl = Q × R1−n
n
(11)
10−3 −108.815 14.890 48.6 79.6 56.6 dl
5.10−3 −99.3720 11.419 46.4 83.3 66.7
10−2 −91.4260 8.9830 48.2 106.7 73.8 On the other hand, the corrosion inhibition performance
BIM 5.10−5 −112.595 22.702 59.4 94.8 33.8 was discussed based on the Rct values. Thus, the more the
10−4 −110.299 17.355 48.1 75.2 49.4
5.10−4 −107.603 15.287 47.7 79.7 55.4
Rct value increases, the more the anticorrosion performance
10−3 −93.5890 10.754 51.1 117.5 68.7 of the brass increases. As can be seen in the table, the resist-
5.10−3 −91.8320 6.7700 48.3 101 80.3 ance of the RS solution rarely changes, indicating that the
10−2 −75.3230 5.2430 38.1 84.5 84.7
addition of the corrosion inhibitor does not significantly
6 A. EL-ASRI ET AL.

Figure 4. Nyquist and Bode diagrams of Cu-Zn in 0.1M HNO3 without and with imidazole derivative at different concentrations.

Figure 5. The equivalent electrochemical circuit used to fit the impedance spectra.

change the properties of the entire electrolyte. The results sign of the low corrosion resistance and the ion diffusion
displayed in Table 4 indicate that the brass electrode rate is large under the condition of vacuum since the charge
immersed in HNO3 has the lowest Rct value, which is a transfer resistance is low. This leads to the formation of
 CORROSION ENGINEERING, SCIENCE AND TECHNOLOGY 7

Table 4. EIS parameters of Cu-Zn in 0.1M nitric acid with and without different concentrations of inhibitors at 298K.
Mol L−1 Rs (Ω.cm²) CPEdl (μF cm2) n Rct (Ω.cm²) RL (Ω.cm²) L (H.cm²) IEEIS(%)
Blank 14.68 166.8 0.7667 128 – – –
IM 5.10−5 16.87 73.6 0.843 174.5 – – 26.6
10−4 16.28 52.51 0.862 185.3 – – 30.9
5.10−4 15.41 76.23 0.832 250.0 1065 48.8 48.8
10−3 16.56 69.4 0.826 250.7 1070 48.94 48.9
5.10−3 16.69 73.74 0.811 298.9 1083 61.86 57.2
10−2 16.68 73.82 0.811 299.7 1115 61.45 57.3
MIM 5.10−5 15.07 106.5 0.792 192.5 851.7 27.81 33.5
10−4 15.44 77.17 0.828 218.1 1185 45.30 41.3
5.10−4 15.48 99.69 0.779 259.5 1126 58.21 50.7
10−3 15.67 58.98 0.821 302.8 1158 58.66 57.7
5.10−3 15.62 58.16 0.83 384.1 1510 76.16 66.8
10−2 16.80 51.57 0.823 403.4 1556 84.06 68.3
BIM 5.10−5 15.50 84.41 0.812 229.9 791.3 28.73 44.3
10−4 15.29 57.38 0.839 310.5 1252 51.18 58.8
5.10−4 14.64 65.41 0.835 367.6 1396 59.76 65.2
10−3 15.87 57.45 0.835 464.2 1919 87.85 72.4
5.10−3 16.73 50.61 0.856 873.4 3277 261.8 85.3
10−2 18.51 40.14 0.8796 997.6 – – 87.2

corrosion products on the surface of the brass. After adding

corrosion inhibitors. The Rct values (which is a measure of
electron transfer across the surface, and inversely pro-
portional to the corrosion rate.) of brass in the presence of
the imidazole derivative are very high compared to blank
and these values are significant for the BIM compound com-
pared to the other two inhibitors IM and MIM. This suggests
that these compounds ensure effective protection of the brass
electrode, thus obstructing the diffusion of ions; and when
the concentration of the derivative compounds increases,
the corrosion resistance gradually increases and the cor-
rosion inhibition rate increases. On the other hand, it should
be mentioned that there is no strong correlation between
inhibition performance and Cdl values. This is in contrast
to what is usually observed in the corrosion inhibition of
steels. For steels and copper, Cdl values decrease with Figure 6. Lungmuir adsorption isotherm model for BIM on the brass surface in
increasing inhibitor concentration due to decreasing dielec- 0.1M HNO3.
tric constant or increasing surface film thickness. Obviously,
this is not always the case for brass alloys which is mentioned
by M. Ebrahimzadeh et al. 2015 [40]. As observed in this
conducts at ΔG °ads = −27.968 KJ mol−1. The negative
work, it seems that there is no close correlation between
value of ΔG °ads is indicative that BIM is strongly adsorbed
the concentrations of inhibitors on the one hand and the
on the surface of the lattice. This value and compression
values of the dielectric constant and the thickness of the
between −20 and −40 KJ mol−1 indicating a competition
double layer on the other hand. This behaviour is mainly
between the chemisorption and the physisorption of the
due to the difference between the surface states of the brass
BIM molecules.
alloys in terms of the effect of the structure and the rough-
ness of the substrate on the corrosion resistance. At the
same concentration, a greater increase in the inhibition Temperature effect and kinetic parameters
efficiency can be observed after the addition of 10−2 M
inhibitors, which is consistent with the results of the poten- Temperature plays an important role in studying corrosion
tiodynamic polarisation tests. phenomena and inhibitor performance in a corrosive
environment. Table 5 summarises the stationary electroche-
mical parameters (Ecorr, Icorr, βa and βc) and % IEpp the inhi-
bition efficiency obtained by the temperature effect (298–
Adsorption isotherm
333 K) on the corrosion of brass in the 0.1 M HNO3 solution
The fraction of surface area covered by the adsorbed mol- with and without a concentration 10−2 M of BIM. The results
ecules (θ) has been determined by the ratio E%/100. The indicate that the Ecorr corrosion potential goes to negative
data have been tested graphically to adapt to various iso- values and the corrosion current density increases with the
therms. The C/θ path as a function of the inhibitor concen- increase of temperature in medium (inhibited and uninhib-
tration (C) gives a straight line with an equal correlation ited). This increase was explained by the activation reactivity
coefficient to the unit (Figure 6) and a point of 0.998. The of corrosive medium [47]. We noticed that the inhibitory
strong correlation is such that the BIM is adsorbed on the efficiency decreases as the temperature increases; this is
electrode in one straight line according to Langmuir’s attributed to the shift from adsorption to desorption equili-
model [35,46]. The equilibrium constant calculated from brium at the brass surface by increasing temperature [48–
the adsorption reaction is 4045.127 dm3 /mol, which 50].
8 A. EL-ASRI ET AL.

Table 5. Corrosion parameters obtained for brass in 0.1M HNO3 without and of 10−2M of BIM. From this figure the correlation line plot
with a concentration of 10−2 M of BIM after immersion at different
temperatures.
for the two cases showed correlation coefficients 0.83
T Ecorr/SCE Icorr Βa (mV/ -βc (mV/ IEpp
(Blank) and 0.92 (Inhibitor), respectively, so all points are
(K) (mV) (μA cm−2) dec) dec) (%) almost linear. Ea calculated from the slope [−Ea/2.303R]
Blank 298 −116.0 34.3 70.6 131.4 - has a value of 48.33 KJ mol−1 for the blank and 69.33 KJ
303 −117.5 36.3 48.7 121.6 - mol−1 for the inhibitor respectively, it is found that the
313 −119.2 50.7 52.1 90.40 - apparent activation energy value for the inhibited solution
323 −127.9 73.1 56.3 118.90 -
333 −134.9 327.7 76.0 85.80 - was higher than of the uninhibited solution, this suggests
BIM 10−2 M 298 −75.3 5.2 38.1 84.50 84.7 that the corrosion process has been modified and corrosion
303 −81.0 8.6 44.9 75.40 76.3 inhibition of brass occurs primarily through a physical
313 −85.7 17.1 42.9 61.10 66.3
323 −78.0 35.6 26.0 34.80 51.4 adsorption mechanism [51,54]. The plots of Log (Icorr /T)
333 −80.0 192.6 46.5 54.70 41.2 versus (1000/T) for the two solutions (Blank and in the pres-
ence of BIM) are shown in Figure 7(b). The determined
values of ΔH° and ΔS° energies are listed in Table 6. Exam-
The Arrhenius diagram study makes it possible to deter- ination of the data in this table revealed that the enthalpies
mine other thermodynamic parameters such as; activation ΔH° (ΔH° = 45.72 KJ mol−1 for white and ΔH° = 66.74 KJ
energy (Ea), standard entropy (ΔS°) and standard enthalpy mol−1 in the presence of BIM) are positive sign energies,
(ΔH°), the latter is to explain the process of corrosion and which reflect the endothermic nature of the adsorption and
inhibition occurring at the metal surface. dissolution process of the brass electrode in an acid medium.
The activation energy and the standard enthalpy and It is clear from this table that the ΔS° values in the absence
entropy of activations are calculated according to the follow- and in the presence of the inhibitor have a negative sign.
ing Arrhenius Equations (12) & (13) [51–53]: This suggests that the activated complex is in the rate-deter-

 mining step and represents an association rather than a dis-
Ea
Icorr = A exp (12) sociation step, indicating an increase in order and a decrease
RT in disorder moving from reactant to activator complex

◦
◦ [52,55,56].
RT DS DH
Icorr = exp exp (13)
Nh R RT
where Icorr is the current density, A is Arrhenius factor, R is FTIR studies
the molar gas constant, T is the absolute temperature, Ea is
The interaction of an organic molecule with a metal surface
apparent effective activation energy, N is the Avogadro’s
can lead to a shift in the number of infrared absorption waves
number, ΔS° and ΔH° are the standard entropy and enthalpy
and a decrease in the absorption intensity [57]. To confirm
of activation. The thermodynamic values obtained are
the adsorption of BIM on the alloy surface after exposure
grouped in Table 6. Figure 7(a) shows the natural logarithm
to an acidic solution inhibited by BIM for 15 days and to
of the corrosion current density (log(Icorr)) as a function of
identify the interaction centres between the inhibitor and
the temperature inverse 1000/T in the absence and presence
the alloy surface, the FTIR spectra of adsorbed inhibitor
film from the alloy surface were compared with the FTIR
Table 6. The values of the activation parameters Ea, ΔH* and ΔS* for brass in spectrum of pure BIM Figure 8. The FTIR spectrum of
0.1M HNO3 in the absence and in the presence of 10−2 M of BIM, respectively. pure BIM exhibits multiple absorption bands, especially in
Ea (KJ mol−1) ΔH* (KJ mol−1) ΔS* (J.K−1 .mol−1 ) the low wavenumber region. For clarity, the low wavenum-
Blank 48.338439 45.722451 −64.3027 ber region has been enlarged. In the zoomed spectrum, the
BIM 10−2 M 69.335316 66.740934 −5.9001
weak peaks at 1602.84 cm−1 are assigned to N−H bending

Figure 7. (a) Arrhenius plot for brass corrosion in 0.1 M HNO3 in the absence and presence of 10−2 M BIM, (b) Transition state plot of log (Icorr/T) versus 1000/T for
copper corrosion in 0.1M HNO3 in the absence and presence of 10−2 M concentration of BIM.

Figure 8. FTIR spectra for pure BIM and corrosion products formed on the Cu-Zn alloy surface after 15 days of immersion in a 0.1M HNO3 solution containing 10−2
M of BIM.
[58,59]. The bands at 1587.41, 1550.76 and 1408.03 cm−1 are,
respectively, assigned to the C=C stretching band of the aro-
matic ring, to the C–C stretching of the aromatic ring and to
the vibrational C–N stretching. However, the sharp bands at
1012.92 and 748.38 cm−1 emanated from the C−H stretching
of the imidazoline ring and from the wrinkling of the ring,
respectively [58,59]. The absorption bands in the spectra of
the extracted films are identical to those of the pure BIM
spectrum. This confirms the statement that the corrosion
protection observed on the alloy surface Figure 9 is due to
the adsorption of BIM molecules. However, the position of
the bands and the intensity of absorption are changed in
the extracted film spectra compared to that of the pure
BIM spectrum. For example, the C–N stretching and N−H
bending bands shifted by about 1382.96, 1600.91 cm−1,
respectively, in the film spectra. While 650 cm−1 was desig-
nated for Cu–N stretching vibration [60,61]. This shows
that the inhibitor molecule interacts with the alloy surface
and that the N heteroatom, the imidazoline ring and the
benzyl ring serve as the interaction centres [58].
Surface morphology analysis SEM and elemental
composition EDS
The morphological study of the surface of brass sample
Figure 9(b) is markedly attacked by the aggressive solution
and the surface showed a very rough morphology with
many cavities. Corrosion products and pitting that spread
across the surface of brass are due to the dezincification pro-
cess, which begins with the selective dissolution of zinc and
continues with simultaneous dissolution of copper and zinc.
It is observed in the SEM Figure 9(b) image of the corroded
brass that there are localised regions where the dezincifica-
tion process is more pronounced. On the other hand, the
heterogeneity of the surface of the brass samples is weakly
CORROSION ENGINEERING, SCIENCE AND TECHNOLOGY 9
decreased in the presence of IM but it is strongly decreased
in the presence of MIM and BIM, this improvement in the
morphology of the surface is mainly due to the inhibition
effect of inhibitors on the surface of brass. Elemental studies
of the surface of brass removed from immersion in 0.1 M
HNO3 without and with different inhibitors after 24 h are
shown in Figure 9. Tabulated elemental analysis obtained
by EDS (expressed in % by weight) of brass is shown in
Table 7. The EDS spectrum of the sample immersed in nitric
acid Figure 9(b) revealed the presence of an O peak (7.33%).
The presence of oxygen in the sample is mainly due to the
corrosion products formed on the surface of the brass
(ZnO and CuO). While the inhibited test solution Figure 9
(c) revealed that the oxygen peak decreased in the presence
of IM (3.01%) and disappeared in the presence of MIM
and BIM. There is also an increase in Cu and Zn peaks com-
pared to the EDS spectrum of brass in the absence of inhibi-
tors, suggesting the adsorption of molecules onto the brass
surface, thus indicating the successful prevention of the sur-
face against a direct attack by corrosive media.
Quantum chemical study
The efficiency of a corrosion inhibitor is based on spatial and
electronic molecular structure [62]. Theoretical calculations
prevent the classification of these three derivatives of imida-
zole as a function of their corrosion inhibitors. The struc-
tures of these optimised molecules, EHOMO and ELUMO , are
presented in Table 9. The descriptors of quantitative chem-
istry such that the energy of the highest occupied molecular
orbital (EHOMO ), energy gap (ΔE), chemical hardness (η) and
total negative charge (TNC) were determined and summar-
ised in Table 8 [63]. The step of optimising the structure of
the studied molecules was carried out in gaseous and aqu-
eous phases in order to determine the geometric structure
10 A. EL-ASRI ET AL.

Figure 9. SEM Micrographs and EDS Analysis with Brass Surface Element Mapping, (a) without immersion, (b) after immersion in 0.1 M HNO3, (c) after immersion in
0.1M HNO3 + 5.10−3 BIM, MIM and IM. Immersion time = 24 h, at 298 K.

with a local minimum on the conformational. Namely, the energy gap, ΔE, between the HOMO and the LUMO con-
precise theoretical determination of the geometry of chemi- cerned, the greater the interaction between the two reactive
cals IM, MIM and BIM were studied at the minima of their species. The table clearly shows that BIM is the best inhibitor
potential energy, according to the theory of Frontier Molecu- compared to the other two with the lowest energy gap. Simi-
lar Orbital Chemical Reactivity (FMO), the formation of a larly, MIM is more efficient than IM (which have 6.277,
transition state is due to the interaction between HOMO 5.666, 5.5735 eV in gas phase and 6.7853, 6.4889,
and LUMO of the reacting species. The smaller the orbital 5.5947 eV in water, respectively). As is known, both softness
[64] and hardness are given based on HOMO and LUMO
orbital energies as a result of Tjalling Koopman’s theorem.
Table 7. Elemental composition of different brass samples with and without Hard molecules, which have high HOMO–LUMO energy
inhibitors. gap, cannot act as good corrosion inhibitor. However, soft
Points Cu Zn C O molecules, which have low HOMO–LUMO energy gap, are
Pure brass (reference) 61.02 38.98 – – good corrosion inhibitors because they can easily give elec-
Blank 55.46 33.92 3.29 7.33
5.10−3 M of IM 56.93 34.43 5.62 3.01 trons to metals. It is clear that we can write the same cor-
5.10−3 M of MIM 60.68 37.15 2.18 – rosion inhibition ranking considering these three chemical
5.10−3 M of BIM 61.60 36.20 2.20 – properties. From the light of the results given in the related
 CORROSION ENGINEERING, SCIENCE AND TECHNOLOGY 11

Table 8. Calculated molecular electronic structure parameters of the tested imidazole derivative using the DFT/B3LYP method with a basis set 6-31 + G (3d, p).
ELUMO (eV) EHOMO (eV) Energy (eV) ΔE (eV) I (eV) A (eV) η σ TNC
Gaz IM −0.2272 −6.5042 −6156.1641 6.277 6.5042 0.2272 3.138 0.3186 −1.124
MIM −0.5218 −6.1878 −7225.9231 5.666 6.1878 0.5218 2.833 0.3529 −1.485
BIM −0.8241 −6.3976 −10336.895 5.5735 6.3976 0.8241 2.7867 0.3588 −2.225
Aqueous IM 0.1975 −6.5878 −6156.461 6.7853 6.5878 −0.1975 3.3926 0.2947 −1.205
MIM 0.1708 −6.3181 −7226.2223 6.4889 6.3181 −0.1708 3.2444 0.3082 −1.725
BIM −0.9256 −6.5203 −10337.220 5.5947 6.5203 0.9256 2.7973 0.3574 −2.507

tables, one can write the corrosion inhibition ranking of
studied molecules based on their hardness, softness and
HOMO–LUMO energy gap values as: BIM > MIM > IM.
The sum of all negative charges in a molecule, denoted
TNC, is a popular global descriptor that can be associated
with the inhibitory effect. Molecules carrying the highest
negative value of TNC will have a great tendency to be
adsorbed on the metal surface. The TNC values are listed
in Table 9 for the three molecules studied. As shown in the
table, the TNC increases from IM to BIM, which exhibits
the best inhibition efficiency among the studied compounds.
These results are in agreement with the experimental results,
which show that BIM has a better ability to inhibit brass cor-
rosion in nitric acid medium.
Molecular dynamic simulations; adsorption energy
calculations
MD simulations have been performed to understand the cor-
rosion inhibition performance of imidazole derivatives IM,
MIM and BIM on copper in 0.1 M nitric acid medium
[28,65]. The modeled adsorption of each inhibitor com-
pound IM, MIM and BIM on the studied Cu(111) surface
[66,67] is carried out in a system containing 60 water mol-
ecules, 3 nitrate ions and 3 hydronium ions. The visual
results at the top, side 1 and 2 of the optimised inhibi-
tor@Cu(111) surface configurations are presented in Figure
10. The presentation of these optimised systems containing
the inhibitor molecules IM, MIM and BIM aims to model
the configuration and the positioning adsorption at equili-
brium. For the studied inhibitors at the Cu (111) surface,
MD simulations were performed until the studied system
reached equilibrium and the temperature reached equili-
brium towards the value of 298 K as shown in Figure S1
(Supporting Information). Through a simulation that
achieves equilibrium, we have shown side view 1 to get an
overview and general information about a comparison of
the absorption trend of different media elements. Therefore,
it can be seen that IM, MIM and BIM inhibitors have ten-
dencies in the studied systems to adsorb on Cu (111) in

Table 9. Optimised structures, HOMOs, LUMOs and electrostatic potential structures (regions of negative (positive) potental are red (blue)) of inhibitory
molecules using DFT/B3LYP/6-31 + G(3d, p).
12 A. EL-ASRI ET AL.

Figure 10. Side and top views of the stable adsorption of Cu (111)/IM, MIM and BIM/60 H2O system configurations.

comparison to water molecules, nitrate ions and hydronium

ions. To take a closer look inside, side view 2 where the
inhibitor compounds IM, MIM and BIM lie parallel to the
surface of Cu (111). This optimal positioning is due to the
optimal distance of the active sites in these inhibitors such
as nitrogen atoms and the Cu(111) metal surface, such that
these nitrogen atoms differ in their negative charges depend-
ing on their position in the structures of the inhibitors. These
nitrogen atoms as active sites are specific factors that influ-
ence the reactivity of the inhibitors [68], and therefore
their adsorption on the studied metal surface Cu (111).
Regarding the top view, all the molecules appeared flat on
the copper surface.

Radial distribution function

The RDF has been used to calculate the interatomic distance
between atoms in a molecule and brass. The probability of
finding particle B in the range (r + dr) around particle A is
described by the function g(r). RDF is calculated as follows
Equation (14);
1 1 
NA NB
d(rij − r)
gAB (r) =  
r local NA teA teB 4pr2
With 〈ρ〉 local means the particle density of B averaged
over all shells around particle A. The interatomic bond
length values allow us to conclude on the nature or types
of bonds formed. In general, if these values are between 1
and 3.5 Å, the chemical bonds are present. If not, we have
physical connections [69] Figure 11 shows the variation of
RDF as a function of link lengths (r) for IM, MIM and
BIM. The RDF results of the active sites in the studied
atoms show that the shortest copper bond length is estimated
Figure 11. Radial distribution function of IM, MIM and BIM on the surface of Cu
(111) in solution.
from 2.87 for IM to 2.75 and 2.73 for MIM and BIM, respect-
ively. The results obtained in this figure show that the nat-
ures of the bonds are of chemical types.
The determination of the adsorption energy distribution
(14) on Cu (111) for each IM, MIM and BIM inhibitor was
made in comparison with water molecules, nitrate ions and
hydronium ions in the studied system. The adsorption
energy distribution values for Cu (111)/IM/60 H2 O, Cu
(111)/MIM/60 H2 O and Cu (111)/BIM/60 H2 O in nitric
acid medium modeled by 3 nitrate ions and 3 hydronium
ions is shown in Figure 12. Moreover, the adsorption energy
distribution shows that compounds IM, MIM and BIM are
good inhibitors, where they appear as competing elements
for the elements leading to the corrosion such as hydronium
ions and water molecules in nitric acid medium. Figure 12

Figure 12. Distribution of adsorption energies for IM, MIM and BIM molecules
on the Cu (111) surface.
indicates that the adsorption power on the metal surface of
IM, MIM and BIM almost reached values of −36.712,
−44.120 and −51.853 Kcal mol−1 as good inhibitors, respect-
ively. Not all compounds in our study showed the same
efficacy; this action results from the difference in the charac-
teristics of the guiding molecular structure, the BIM com-
pound gives the highest binding energy, then the MIM
comes next, and the least efficient compound in the simu-
lation study was the IM. The inhibition tendency remains
unchanged in which the adsorption energy increases in the
following order: IM < MIM < BIM in both phases. Owing
to the greater electron donating ability of the benzene
group, providing greater stability for the BIM compound.
Although the CH3 group in MIM has an inductive donor
effect, yet it acts as a strong active adsorption centre.
Mechanism of corrosion
The anodic dissolution behaviour of brass in nitric acid con-
sists of dissolution of both zinc and copper. Generally, the
anodic reaction for Cu is considered as follows Equations
(15) & (16);
Cu  Cu+ −
ads + 1e ( fast step)
Cu+ + 1e− (slow step)
ads  Cu
2+
Meanwhile, the adsorption of copper ions, Cu (II), on the
surface due to its reduction in the presence of Zn should be
Figure 13. Simplified schema of some interaction modes of imidazole derivatives with metallic surface in inhibition process.
CORROSION ENGINEERING, SCIENCE AND TECHNOLOGY 13
considered. In addition, the anodic dissolution of Zn is con-
sidered according to the following Equation (17);
Zn  Zn2+ + 2e− (17)
It should be noted that the cathodic reaction is not a hydro-
gen evolution reaction at all, since the corrosion potential in
all experiments is much higher than the redox potential of
hydrogen evolution in this medium. In this way, the predo-
minant mechanism of the cathodic reaction has been
reported according to the following Equation (18);
NO− +
3 + 4H + 3e
−
 NO + 2H 2 O (18)
Based on previously displayed facts, the imidazole deriva-
tives compounds have shown a good ability to control cor-
rosion of brass metal in nitric media. Similar to most
organic corrosion inhibitors, the inhibitive effect of those
compounds was attributed to the accumulation of the inhibi-
tor molecules by ‘direct’ or/and ‘indirect’ adsorption onto the
brass surface, which reduces the contact of the metal with the
corrosive agents in solution (Figure 13). The charge (nature
and magnitude) and chemical nature of surface and the
inhibitor nature and protonation statue are the main factors,
which influence the mode of adsorption. Generally, two
modes of adsorption could be considered. In one mode,
the neutral inhibitor may be adsorbed on the surface through
a chemisorption mechanism, and in another mode, the
charged inhibitor can be interacted electrostatically with
charged metal surface. The adsorbed anions on metal surface
make it negatively charged which increases the adsorption
ability of protonated imidazole derivatives. Such behaviour
has been noted, especially, in acidic medium. However, if
metal surface charge becomes zero, none of cations or anions
will be adsorbed on the surface. It is probable; in this case,
that the molecule is chemically adsorbed.
Imidazole derivatives are the electron donor’s species and
the metallic atoms on the surface are electron acceptors.
Another mode can be exhibit; it is ‘donor–acceptor’ inter-
actions, which unshared electron pairs of heteroatoms (N)
and/or the p electrons of the imidazole and aromatic ring
transfer to vacant ‘d’ orbital of surface metal atoms. In the
other side, the inhibiting effect of some Imidazole derivatives
(15) on brass corrosion was attributed to the formation of insolu-
ble complex between the metallic ions present on surface and
(16)
the Imidazole derivatives via heteroatoms. For instance, this
mode has been reported for imidazole and benzimidazole on
copper by Natasa Kovacevic and Anton Kokalj [70,71],
14 A. EL-ASRI ET AL.
which the inhibitor molecules form the complex with Cu(I)
species via nitrogen atoms.
Conclusions
The following are the findings from studying the corrosion
inhibition characteristics of imidazole derivatives organic
compounds on corrosion of brass in 0.1 M HNO3 medium:
- Imidazole derivatives are efficient corrosion inhibitors for
brass in the studied medium.
- Polarisation measurements showed that the tested com-
pounds are mixed-type inhibitors.
- Reasonably good agreement was observed between the
obtained measures from weight loss, potentiodynamic
polarisation curves and electrochemical impedance spec-
troscopy techniques.
- The study of morphology of the surface brass by SEM
coupled with the EDS & FTIR shows the existence of a
stable and insoluble adherent deposit, which limits the
access of the electrolyte to the surface of the metal
- The BIM compound has the highest reactivity in compari-
son to MIM and IM, and would therefore likely interact
strongly with the metal surface.
- Quantum chemical calculation proved very informative to
correlate the experimental findings.
Acknowledgements
Authors are thankful for the financial assistance provided by the Natu-
ral Science Foundation of China (No. 52074232).
Disclosure statement
The authors declare that they have no known competing financial inter-
ests or personal relationships that could have appeared to influence the
work reported in this paper.
Funding
Authors are thankful for the financial assistance provided by the Natu-
ral Science Foundation of China [No. 52074232].
ORCID
A. El-Asri http://orcid.org/0000-0003-1173-2904
A. Jmiai http://orcid.org/0000-0003-2310-5940
Y. Lin http://orcid.org/0000-0002-3667-8054
A. Taoufyq http://orcid.org/0000-0002-4894-505X
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