Journal of Molecular Liquids 338 (2021) 116550

Contents lists available at ScienceDirect

Journal of Molecular Liquids

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

Theoretical and surface/electrochemical investigations of walnut fruit

green husk extract as effective inhibitor for mild-steel corrosion in 1M
HCl electrolyte
A.R. Shahmoradi a, M. Ranjbarghanei b, A.A. Javidparvar c,⇑, L. Guo d,e,⇑, E. Berdimurodov f,
Bahram Ramezanzadeh g,⇑
a
Department of Chemical Engineering, Shahreza Branch, Islamic Azad University, Shahreza, Iran
b
Department of Physics, Plasma Physics Research Center, Science and Research Branch Islamic Azad University, Tehran, Iran
c
School of Material Engineering, College of Engineering, University of Tehran, P.O. Box 11155-4563, Tehran, Iran
d
School of Material and Chemical Engineering, Tongren University, Tongren 554300, PR China
e
School of Oil and Natural Gas Engineering, Southwest Petroleum University, Chengdu 610500, PR China
f
Faculty of Natural Sciences, Karshi State University, Karshi 180100, Uzbekistan
g
Department of Surface Coatings and Corrosion, Institute for Color Science and Technology, P.O. Box 16765-654, Tehran, Iran

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

Article history: The present paper has studied the corrosion inhibition property of Juglone extracted from walnut (Juglans
Received 13 March 2021 regia L.) green husk for mild steel samples exposed to an acid electrolyte (1 M HCl). Besides, via computer
Revised 1 May 2021 modelings, the attraction forces of the inhibitors/metal surface were explored. The corrosion inhibition
Accepted 19 May 2021
efficiency of the organic inhibitor was evaluated using potentiodynamic polarization as well as EIS tech-
Available online 23 May 2021
niques. In addition, XPS, FT-IR, SEM, AFM, and UV–visible spectroscopy have been used to study the inhi-
bition mechanism of the agricultural waste extract in the corrosive media. Quantum chemical
Keywords:
calculations based on DFT theory and molecular dynamic simulations were investigated on the adsorbed
DFT
Green inhibitor
Juglone inhibitors. The obtained results indicated that the efficiency of the used inhibitor was enhanced
Corrosion, Walnut with increasing the concentration of green corrosion inhibitor (GCI) and reached 95% in the presence of
Agricultural waste 800 ppm after 8 h immersion. Moreover, the average roughness of the exposed metal to the corrosive
EIS electrolyte decreased from 68.2 ± 8.3 nm for the blank solution to 3.4 ± 0.3 nm for the solution containing
800 ppm GCI. Furthermore, the Tafel extrapolated polarization results revealed that the extracted GCI
functioned as a mixed-type corrosion inhibitor. Finally, the obtained analysis results are supported by
theoretical data.
Ó 2021 Elsevier B.V. All rights reserved.

1. Introduction by introducing some principles about the utilization of eco-

friendly precursors and procedures [2]. In this way, recycling the
Environmental protection strategies can be summarized in the biodegradable agricultural and industrial wastes and reusing them
protection of soil, water, and air. Burning or landfilling/dumping as eco-friendly chemical precursors for different applications is one
of agricultural wastes can pollute all three cases by the production of the interesting fields in this context [3–5].
of toxic and/or greenhouse gases and waste leachates [1]. Regard- Due to the suitable mechanical and structural properties of
ing the growing worries about the environmental issues in the last steel, these alloys are widely employed in various industries such
three decades in developed and developing countries, green chem- as oil–gas and petroleum sectors, aerospace, marine and automo-
istry has been attracted growing attention. Green chemistry, also tive, underground and submerged pipeline transmission systems,
called sustainable chemistry, is one of the chemistry engineering and military industries [6]. However, the corrosion susceptibility
fields that reduces or eliminates environmental contaminations of the alloys and the direct and indirect costs of the phenomena
are the main challenges ahead of the utilization of them in corro-
sive media. Corrosion inhibitors (CIs) are organic, inorganic, or
⇑ Corresponding authors at: School of Material and Chemical Engineering,
hybrid substances that reduce the immersed metal/alloy corrosion
Tongren University, Tongren 554300, PR China (L. Guo).
rate when introduced in small concentrations into a corrosive solu-
E-mail addresses: Javidparvar@ut.ac.ir (A.A. Javidparvar), cqglei@163.com (L.
Guo), ramezanzadeh-bh@icrc.ac.ir (B. Ramezanzadeh). tion [7]. The widely used organic CIs in the industry are hetero-

https://doi.org/10.1016/j.molliq.2021.116550
0167-7322/Ó 2021 Elsevier B.V. All rights reserved.
A.R. Shahmoradi, M. Ranjbarghanei, A.A. Javidparvar et al. Journal of Molecular Liquids 338 (2021) 116550

cyclic compounds with double and triple bonds and some heteroa- Finally, quantum chemical calculations based on DFT theory and
toms such as O, N, P, and S elements [8]. The organic compounds molecular dynamic simulations were investigated on the adsorbed
adsorb physically and/or chemically on the surface of the metal/al- Juglone inhibitors on the electrode surface.
loy and reduce the rate of cathodic, anodic, or both reactions by
forming a compact layer on the surface of the metal/alloy [9]. In
industrial applications, HCl is generally used for different purposes 2. Experimental
such as chemical pickling of steels [10], oil well acidizing [11], pH
adjustment of solutions [12], leaching processes [13], and regener- 2.1. Materials
ating the ion exchangers [14]. However, the highly corrosive nat-
ure of HCl solutions is an important challenge against the In this study, a diluted hydrochloric acid (37%, Merck Co.) was
employment of the solutions for industrial applications. Although used as the corrosive electrolyte. The used steel electrodes (St-
using CIs is a popular and economical strategy in this field, the 12) were bought from the Foolad Co. with a certain elemental com-
toxic nature of the synthesized organic compounds is the major position [38].
drawback of using the materials in real applications. The GCIs are
introduced to overcome this drawback due to their bio- 2.2. GCI extraction
degradable property [15]. The presence of useful corrosion inhibi-
tive compounds in the plant extracts has made them the effective The walnuts were collected from Tuyserkan, Hamedan, Iran. To
GCIs for acidic solutions [7]. extract the chemical compounds from the walnut green husk, a
Natural residues and bio-wastes are interesting materials to be simple, eco-friendly, and aqueous-based method was employed.
used as GCIs due to their low cost, ease of fabrication, and environ- In this way, according to previous works [21,39], 30 g of the dried
mental friendliness. In addition, recycling of the agricultural bio- (at 60 °C for 12 h) and grounded walnut green husk was mixed by 1
wastes can lead to economic savings as well as reducing environ- lit of deionized water and heated for 6 h at 65 °C to extract the
mental pollutions. Pectin, which is a heteropolysaccharide com- water-soluble compounds from the raw material. Afterward, the
pound extracted from various bio-wastes such as citrus peel mixture was centrifuged at 2500 rpm for 15 min for complete
[16,17], tomato peel [18], and sunflower head [19], has been used removal of the undissolved particles, and then the mixture was
for corrosion inhibition of different alloys in corrosive media. Cel- heated for 24 h at 65 °C to evaporate water solvent and prepare
lulose and lignin are other widely used GCIs that are extracted the extract dry powder.
from the hard shell of some nuts such as walnut [20] and pistachio
[21], Pisum sativum peels [22], and the stem of sunflower [23].
2.3. Preparing the electrode surface
Alkylphenols, L-L-citrulline, Papain molecule, Flavan-3-ol, Sul-
famethazine, sucrose/maltose/folate, and ursolic acid, derived from
The surface of the steel electrodes was cleaned with acetone,
cashew nutshell [24], watermelon seed [25], Papaya peel [26],
and then the specimen surface was abraded with emery papers
Schinopsis lorentzii tree powder [27], Banana peel [28], Chinese
starting from 400 to 1200 grit size. Finally, the coupons were
gooseberry fruit shell [29], and Pomegranate peel [30], respec-
degreased by acetone. To expose a certain area of the steel coupons
tively, are some other chemical compounds used as GCIs in differ-
(1 cm2) to the corrosive solution and seal the edges and back sides
ent corrosive solutions.
of them, a mixture of 3:1 of beeswax-colophony was employed.
The walnut green husk and it’s brown hardshell are the main
by-products of the walnut fruit. Juglone is a well-known allelo-
pathic which is used in different applications such as medicine 2.4. Characterizations
[31], hair care products [32], agricultural uses [33], and antimicro-
bial solutions [34]. After the US, China, and Turkey, Iran is the The morphology of the surface electrodes and the chemical
fourth-largest country in walnut production. Approxi- composition of the deposition were investigated by SEM equipped
mately 50,000 tons per year of walnut are produced in Hamedan with EDX employing a Philips XL30 model instrument. The surface
Province in the central west part of Iran. Regarding the fact that roughness of the exposed coupons was evaluated by the AFM
the green husk shell makes up about 30 %wt. of a walnut, it can model Veeco operating in non-contact mode. To investigate the
be estimated that in this region, approximately 17,000 tons of chemical composition of the extracted compounds, FT-IR and
green husk shell is produced annually [35]. Burning or landfilling/- UV–Vis spectroscopies were utilized. The FT-IR analysis was con-
dumping of this amount of waste can lead to significant environ- ducted by a Perkin Elmer model in the range of 400 to
mental pollution. In this way, a green recycling process of 4000 cm
1. For the FT-IR analysis of the film formed by adsorption
agricultural waste is an important issue, especially in recent years. of the GCI on the electrode surface, after 8 h immersion of the elec-
In the present study, an aqueous extract of the walnut green trode in the electrolyte containing 800 ppm GCI, the electrode was
husk was used as GCI for immersed bare steel in 1 M HCl solution. dried, and the formed film on the electrode surface was collected
In this study, 1 M HCl was considered as the corrosive electrolyte using a steel knife. The UV–Vis spectra were recorded by UV–Vis-
due to the wide employment of this concentration of the acid solu- ible spectrophotometer (Cary 100 UV–Visible) in the wavelength
tion in industrial applications such as acid cleaning, pickling, ore range of 200–800 nm.
production, oil well acidifying, etc. [36,37]. Fourier transform infra- Open circuit potential (OCP) data were measured using a satu-
red and UV–Vis spectroscopies were used to identify the presence rated Calomel electrode (SCE). EIS and polarization analyses were
of the chemical structure in the obtained extract. Impedance and performed to evaluate the inhibition performance of the prepared
polarization analyses were performed to evaluate the anti- GCI. The electrochemical analyses were carried out using a three-
corrosion efficiency of the obtained inhibitor in different concen- electrode configuration including the prepared steel coupons,
trations. AFM and FE-SEM were employed to investigate the rough- SCE, and a piece of platinum, respectively, as the working, refer-
ness and surface morphology of the steel surface exposed to the ence, and counter electrodes. The EIS data were obtained in the fre-
corrosive solution in the presence and absence of the extracted quency range of 10 mHz to 10 kHz at (±)10 mV amplitude
compound. X-ray photoelectron spectroscopy and contact angle sinusoidal potential around OCP. The polarization experiments
analyses were used for chemical surface analysis of the used elec- were done on the same electrochemical cell in the potential range
trode after immersion in the blank and GCI-containing electrolytes. of
200 to + 200 mV vs. OCP at a scan rate of 1 mV/s. To ensure the
2
A.R. Shahmoradi, M. Ranjbarghanei, A.A. Javidparvar et al. Journal of Molecular Liquids 338 (2021) 116550

repeatability of the reported data, all tests were accomplished on rings, respectively [42]. The absorption peaks of C@O and C@C
three replicates. stretching vibration shifted toward lower wavenumbers
(1698 cm
1 and 1564 cm
1) in the FT-IR spectrum of the immersed
2.5. Theoretical details steel sample. This can be due to the formation of chemical bonds
between the oxygen heteroatoms in GCI and Fe ions. The stretching
2.5.1. DFT calculations vibration of C-O and C-OH bonds appears in the range of 1000–
In this study, the Dmol3 module of the Material Studio (MS) pro- 1400 cm
1 [43]. In the wavenumber range of 400–700 cm
1, the
gram developed by BIOVIA Inc was employed to investigate quan- bending vibration of aromatic rings led to the appearance of an
tum chemical calculations (DFT theory). In order to optimize the absorption peak in the spectrum of GCI [44]. The broader and more
structures, a vibrational analysis was used until the potential of intense peak in this wavenumber range in the spectrum of the steel
surface energy reached the minimum values. The convergence surface is due to the overlapping of the peak of aromatic rings with
thresholds for energy was adjusted at 1  10
5 Ha, the maximum the Fe-O stretching vibration absorption peak. These results
force was set at 2  10
3 Ha Å
1, and the maximum atomic dis- demonstrated the formation of an organic–inorganic complex
placement was considered at 5  10
3 Å. The optimized molecular between the Juglone molecules extracted from the walnut green
structure and various quantum chemical descriptors were pre- husk and the metal cations produced through anodic reactions at
sented and discussed. the surface of the immersed electrode. In addition, the presence
of polar groups, i.e. hydroxyl and carbonyl groups in the chemical
2.5.2. Molecular dynamics (MD) simulation structure of the extracted compound leads to the high solubility of
The simulation was done employing the Forcite module of MS the inhibitor in the aqueous solution via hydrogen bonding
software in a simulation box (1.49 nm  1.49 nm  3.11 nm) via interactions.
comprising a lower Fe slab and an upper solvent layer containing To study the adsorption of the extracted Juglone on the surface
one inhibitor and 250 water molecules. In addition, Fe(1 1 0) was of the exposed electrode, UV–Vis spectroscopy was used, and the
considered as the electrode substrate formulated with a five- obtained spectra are shown in Fig. 2.
layer Fe slab with 36 Fe atoms in each layer. Non-bond interactions In the UV–Vis graphs of the HCl solution with 800 ppm GCI a
were concerned as atom-based simulation and electrostatic inter- peak and a shoulder can be seen at around 230 nm and 290 nm,
actions were adjusted as Ewald simulation technique. which are attributed to the p–p* electron transition in the C@C
bonds related to the phenolic rings and the n–p* electron transi-
tion in C@O bonds, respectively [29]. The decrease of both absorp-
3. Results and discussion tion peaks intensity after 8 h immersion of the steel electrode in
the solution indicates that the dissolved juglone molecules reacted
3.1. FT-IR and UV–Vis spectroscopies with the iron cations produced due to the anodic corrosion reac-
tion and precipitated as an organic–inorganic complex on the elec-
To explore the type of functional groups present in the mole- trode surface. As will be seen in the next section, the formed film of
cules of walnut green husk extract and those on the surface of the precipitated complex on the surface of the electrode can act as
the immersed electrode in the 1 M HCl with 800 ppm of the GCI, a protective film to inhibit the steel corrosion reactions.
FT-IR analysis was used (Fig. 1).
The broadband and the peak in the FT-IR spectra centered at 3.2. Electrochemical measurements
3295 cm
1 is related to the O-H stretching vibration [40]. The
bands assigned to the symmetric and asymmetric stretching vibra- Fig. 3 represents the variations of EOCP versus the electrode
tions of the C-H appeared at 2856 cm
1 and 2923 cm
1, respec- immersion time in the HCl solution. According to this figure, it
tively [41]. In the spectrum of GCI, the absorption peaks centered can be seen that the values of EOCP decreased by increasing the
at 1714 cm
1 and 1598 cm
1 are related to the stretching vibration immersion time due to the dissolution of the formed film and
of C@O in carbonyl groups and skeletal C@C vibration in the phenol reached a steady-state condition after about 20 min of immersion.
In addition, it can be observed that the EOCP increased to less neg-
ative values by increasing the concentration of the GCI. The highest
value of EOCP belongs to the solution containing 800 ppm GCI con-
firming the more adsorption of the extracted compound on the
active sites of the electrode surface in this concentration.
The corrosion behavior of the steel coupons immersed in the
corrosive electrolytes with and without the extracted walnut green
husk compound was studied by EIS measurements, and the
obtained Nyquist and Bode graphs are shown in Fig. 4 and
Fig. S1 (in the supporting information), respectively.
According to Fig. 4, a single semicircle loop can be seen in the
Nyquist plots consisting of a single depressed semicircle loop, indi-
cating that the corrosion process of the steel electrodes in the
blank and inhibitor-containing solutions was controlled through
the charge transfer mechanism [45]. Also, the Nyquist loops’ diam-
eter increased by increasing the GCI concentration, confirming that
more concentration of the extracted Juglone led to the increase in
the polarization resistance values. The total resistance obtained
from the impedance data at the lowest frequency (|Z0.01 Hz|) in
the Bode plots (Fig S1) is another indicator of the GCI corrosion
Fig. 1. FT-IR spectra of GCI extracted from walnut green husk and surface products
inhibition performance. In this regard, the higher |Z0.01 Hz| values
generated on the immersed electrode surface in the acid solution containing in more GCI concentrations for all immersion times suggested that
800 ppm of GCI for 8 h. the total resistance against the mild steel corrosion in the elec-
3
A.R. Shahmoradi, M. Ranjbarghanei, A.A. Javidparvar et al. Journal of Molecular Liquids 338 (2021) 116550

2.5
Before immersion
After immersion
2

Absorbance 1.5

0.5

0
200 300 400 500 600 700 800
Wavelength (nm)

Fig. 2. UV–Vis graphs of the solution with 800 ppm GCI extracted from walnut green husk before and after electrode steel immersion for 8 h.

time, as well as the GCI concentration, up to 95% for the steel elec-
trode immersed in the 1 M HCl solution with 800 ppm GCI after 8 h
-100
of immersion. The exchange of water molecules with GCI com-
0 ppm 200 ppm
pounds increases and decreases the thickness and dielectric con-
-150 400 ppm 600 ppm stant of the modeled double-layer capacitance, respectively [46].
800 ppm So, the decrease of Cdl values at higher concentrations of the GCI
-200
molecules is another reason to demonstrate that a protective film
of the adsorbed organic compounds was formed on the electrode
E (V vs. SCE)

-250
surface.
Polarization analysis can be considered as a useful tool for the
-300
explanation of the extracted GCI inhibition mechanism. The polar-
ization curves after 8 h immersion of the electrode in the corrosive
-350 solution are depicted in Fig. 5, and the obtained Tafel extrapolated
electrochemical parameters are tabulated in Table 2.
-400 In Table 2, bc, Ecorr, and icorr are the cathodic Tafel slope, corro-
sion potential, and corrosion current density, respectively. The
-450 anodic branches did not show a Tafel behavior and so the anodic
0 10 20 30 40 50 60
Tafel slope was not reported. The inhibition efficiency (%IE) of
Immersion time (min)
the GCI in different concentrations was computed as:
Fig. 3. The variations of open circuit potential EOCP versus the electrode immersion  
0
time in the HCl solution. %IE ¼ 100  1
icorr =icorr ð3Þ

where icorr and i°corr are respectively the corrosion current density
values in the presence and absence of GCI. As seen in Fig. 5, the cur-
trolyte increased with the increase of the GCI concentration. Based rent density of both cathodic and anodic branches decreased by the
on the Bode-phase angle curves depicted in Fig. S1, a one-time con- addition of GCI into the electrolyte, indicating that both reactions
stant electrical equivalent circuit (Rs(RpQdl)) was used to fit the raw are affected by the organic compounds, and so it can be concluded
EIS data and obtain the electrochemical parameters (Table 1). that the walnut green husk extract behaved as a mixed type inhibi-
In Table 1, Rs, Rp, and CPEdl are uncompensated solution resis- tor for mild steel in HCl solution. The increment of Ecorr values
tance, polarization resistance (charge transfer + film resistances), towards less negative potentials by increasing the GCI inhibitor
and non-ideal capacitance (constant phase element) of the double confirms the OCP analysis results. In addition, the results reported
layer, respectively. The CPE electrical element was used instead of in Table 2 indicated that the icorr and %IE values decreased and
the pure capacitance to model more accurately the EIS experimen- increased in the presence of more GCI concentrations reaching the
tal data. The capacitance of the double layer (Cdl) was calculated minimum and maximum values of about 63.5 lA/cm2 and 89%,
with Eq. (1). respectively, in the presence of 800 ppm of the extracted inhibitor.
The descending trend in icorr values in the presence of more GCI con-
ð1
nÞ=n
C dl ¼ Y 1=n
0dl  ððRs  RpÞ=ð Rs þ RpÞÞ ð1Þ centrations indicates that the adsorption mechanism is the main
process to postpone the corrosion reactions of the electrode
In addition, the corrosion inhibition efficiency (%g) was
immersed in the HCl solution containing the walnut green husk
obtained via Eq. (2).
extract. The thermodynamic adsorption parameters and isotherm
%g ¼ 100  ð1
R p=RpÞ ð2Þ models are important factors to understand the mechanism of the
GCI adsorption process on the immersed electrode surface [47].
where Rp and R°p are the polarization resistance values in the blank Langmuir and Freundlich isotherm models were used to investigate
and GCI-containing electrolyte, respectively. According to Table 1, the adsorption mechanism of the GCI on the electrode surface
the value of Rp for the electrode immersed in the GCI-containing (Fig. 6).
solution was more than the value obtained for the blank sample. Langmuir and Freundlich’s relationships are represented by Eq.
The inhibition efficiency increased by increasing the immersion (4) and Eq. (5), respectively.
4
A.R. Shahmoradi, M. Ranjbarghanei, A.A. Javidparvar et al. Journal of Molecular Liquids 338 (2021) 116550

400 Blank Blank fit 600 Blank Blank fit

350 a 200 ppm 200 ppm fit b 200 ppm 200 ppm fit
400 ppm 400 ppm fit 500 400 ppm 400 ppm fit
300 600 ppm 600 ppm fit 600 ppm 600 ppm fit

-Z" (ohm.cm2)
800 ppm 800 ppm fit

-Z" (ohm.cm2)
800 ppm 800 ppm fit 400
250
f = 0.1 Hz f = 0.1 Hz
f = 0.01 Hz
200 f = 0.01 Hz 300
150
200
100
100
50
0 0
0 50 100 150 200 250 300 350 400 0 100 200 300 400 500 600
Z' (ohm.cm2) Z' (ohm.cm2)

700 Blank Blank fit

c 200 ppm 200 ppm fit
600 400 ppm 400 ppm fit
600 ppm 600 ppm fit
500
-Z" (ohm.cm2)

800 ppm 800 ppm fit

400 f = 0.1 Hz f = 0.01 Hz

300

200

100

0
0 100 200 300 400 500 600 700
Z' (ohm.cm2)

Fig. 4. The Nyquist plots for the steel electrodes exposed to 1 M HCl with and without different concentrations of GCI after (a) 1 h, (b) 4 h, and (c) 8 h immersion time.

Table 1
Electrochemical parameters obtained by EIS raw data modeling with Rs(RctQdl) equivalent circuit for steel coupons immersed in the corrosive electrolytes without and with
different concentrations of GCI at ambient temperature.

Sample Rs (Ohm.cm2) Rct (Ohm.cm2) CPEdl Cdl (nF/cm2) %g

Y0 (lX
1
.cm
2 n
s ) n
Blank- 1 h 1.12 ± 0.08 58.13 ± 0.72 523.21 ± 6.77 0.93 ± 0.02 1.92 ± 0.01 –
Blank-4 h 1.24 ± 0.09 40.12 ± 1.23 598.52 ± 5.82 0.92 ± 0.02 1.87 ± 0.01 –
Blank-8 h 1.79 ± 0.06 29.18 ± 0.89 612.54 ± 6.77 0.90 ± 0.07 1.80 ± 0.03 –
200 ppm-1 h 1.09 ± 0.10 151.91 ± 2.95 151.65 ± 8.76 0.90 ± 0.03 0.51 ± 0.09 61.73 ± 0.28
200 ppm- 4 h 1.77 ± 0.17 195.32 ± 1.86 134.71 ± 7.66 0.88 ± 0.09 0.49 ± 0.09 79.46 ± 0.29
200 ppm- 8 h 1.24 ± 0.09 213.53 ± 1.95 107.98 ± 9.47 0.85 ± 0.06 0.33 ± 0.01 86.33 ± 0.19
400 ppm-1 h 1.26 ± 0.13 252.81 ± 1.54 100.76 ± 1.65 0.83 ± 0.03 0.47 ± 0.05 77.01 ± 0.14
400 ppm- 4 h 1.32 ± 0.77 297.59 ± 3.26 86.11 ± 8.98 0.84 ± 0.05 0.38 ± 0.08 86.51 ± 0.19
400 ppm- 8 h 1.43 ± 0.06 329.11 ± 2.51 31.32 ± 3.32 0.85 ± 0.08 0.25 ± 0.01 91.13 ± 0.05
600 ppm- 1 h 1.98 ± 0.19 303.39 ± 2.90 93.45 ± 9.91 0.81 ± 0.04 0.45 ± 0.06 80.84 ± 0.08
600 ppm- 4 h 1.09 ± 0.23 381.41 ± 2.72 61.88 ± 2.01 0.80 ± 0.03 0.31 ± 0.03 89.48 ± 0.09
600 ppm- 8 h 1.39 ± 0.11 390.33 ± 3.16 29.98 ± 4.44 0.83 ± 0.09 0.22 ± 0.10 92.52 ± 1.12
800 ppm- 1 h 1.98 ± 0.20 375.22 ± 2.13 44.71 ± 3.86 0.82 ± 0.08 0.37 ± 0.04 84.51 ± 0.11
800 ppm- 4 h 1.21 ± 0.18 586.89 ± 4.84 36.09 ± 4.18 0.79 ± 0.11 0.20 ± 0.03 93.16 ± 1.04
800 ppm- 8 h 1.40 ± 0.19 591.30 ± 3.32 26.17 ± 1.92 0.73 ± 0.08 0.16 ± 0.04 95.06 ± 0.03

C inh =h ¼ 1=K L þ C inh ð4Þ The intercept of the plot of Cinh/h versus Cinh (Fig. 6a) is used to
determine the Langmuir constant value. Also, the values of n and KF
Log ðhÞ ¼ 1=n  log C inh

log K F ð5Þ parameters in the Freundlich equation are computed using the
slope and intercept of the plot of log (h) versus log (Cinh), respec-
where Cinh is the GCI concentration and Kl and KF are respectively
tively. The calculated thermodynamic parameters are tabulated
the Langmuir and the Freundlich constants. In these models, the
in Table 3.
surface coverage parameter (h) is given by Eq. (6).
  In Table 3, the free energy of adsorption (DGads) was calculated

h ¼ icorr
icorr =icorr ð6Þ by Eq. (7).

5
A.R. Shahmoradi, M. Ranjbarghanei, A.A. Javidparvar et al. Journal of Molecular Liquids 338 (2021) 116550

-0.1 Langmuir
0.1
-0.2 0.09 a
0.08
-0.3 0.07
E (V vs SCE)

0.06 y = 0.9934x + 0.0128

R² = 0.9958

Cinh/
-0.4 0.05
0.04
Blank
-0.5 0.03
200 ppm
0.02
400 ppm
0.01
-0.6
600 ppm
0
800 ppm 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
-0.7 Cinh (g/L)
-5 -4 -3 -2 -1 0 1 2
Log i (mA/cm2)
Freundlich
Fig. 5. The polarization graphs after 8 h exposure of the electrode in the corrosive -1
electrolytes without and with different GCI concentrations.
b
-1.1

-1.2
K L ¼ 1=55:5 exp ð
DGads =RTÞ ð7Þ
log ( ) -1.3 y = 4.0855x - 0.8574
where R and T are the gas constant and the Kelvin temperature, R² = 0.9249
-1.4
respectively. As is reported in Table 3, the coefficient of correlation
value (R2) is more close to the unity for the Langmuir model as com- -1.5
pared to the Freundlich model, indicating a strong agreement with
the Langmuir adsorption isotherm. According to the Langmuir -1.6
model, it is assumed that the adsorption is in a monolayer form,
-1.7
and the interaction between the inhibitor molecules is negligible.
The negative value of DGads means that the adsorption of the GCI -1.8
on the steel electrode is spontaneously, and the GCI molecules are -0.25 -0.2 -0.15 -0.1 -0.05 0
strongly adsorbed on the electrode surface. It is well known that log (Cinh)
the DGads values of up to
20 kJ/mol are considered to be indicative
Fig. 6. Experimental adsorption data fitted with (a) Langmuir and (b) Freundlich
of physical adsorption, while those more than
40 kJ/mol are for
isotherm models for the GCI adsorption on the mild steel surface in acid solution.
chemical adsorption mechanism [22]. So, going by the free energy
of adsorption value, the GCI adsorption process occurred through
physiochemical adsorption as its value is between
20 kJ/mol
and
40 kJ/mol.
ters sharply decreased by increasing the GCI concentration. In fact,
the smoothness of the electrode surface in more GCI concentra-
3.3. Surface study tions is due to the formation of a nanometric compact layer of
Fe2+-GCI organic–inorganic complex on the steel surface that
SEM and AFM micrographs of the electrode surfaces immersed resulted in the inhibition of the anodic and cathodic corrosion
in the acid electrolyte without and with various concentrations of reactions.
the extracted GCI are depicted in Fig. 7. XPS is a powerful technique to analyze the immersed electrode
Average roughness (Ra), root mean square roughness (Rrms), and surface at a nano-scale and determine the types and amount of
maximum peak to valley height (Ry) parameters for each sample functional groups present on the surface of the understudied sam-
are reported in Table 4. ple. The wide scan XPS spectra and the high-resolution spectra of O
A strongly rough and damaged surface can be seen for the 1s and C 1s signals with their deconvolution for the used metal
immersed electrode in the blank acid solution in Fig. 7 (a and b). exposed to the blank and inhibitor-containing solutions are shown
The surface roughness reduction by adding the GCI compound to in Fig. 8, and the quantitative results are tabulated in Table 5. The
the corrosive electrolyte suggests the formation of a dense layer high-resolution spectra of Fe 2p and Cl 2p signals are given in
on the metal surface. According to Table 4, the roughness parame- Fig. S2 (in the supporting information).
The quantitative data of the element present in the samples
indicated that the atomic percentage of carbon and oxygen in the
Table 2
The obtained Tafel extrapolated parameters from the polarization analysis.
Table 3
%IE icorr (lA/cm2) Ecorr SCE (V) -bc(v.dec
1) Samples Langmuir and Freundlich isotherm parameters for the walnut green husk extract
adsorbed on the immersed electrode surface.
– 579.38 ± 16.3
0.38 ± 0.01 0.457 ± 0.031 Blank
64.29 ± 0.3 206.89 ± 12.4
0.36 ± 0.02 0.37 ± 0.022 200 ppm Langmuir Freundlich
73.57 ± 0.2 153.12 ± 10.0
0.35 ± 0.02 0.348 ± 0.041 400 ppm
DG°ads (kJ/mol) KL (l/mg) R2 1/n ln Kf (mg1-nLn/g) R2
81.77 ± 0.4 105.61 ± 10.2
0.34 ± 0.04 0.329 ± 0.012 600 ppm
89.04 ± 0.2 63.48 ± 5.3
0.33 ± 0.03 0.331 ± 0.018 800 ppm
20.74 78.12 0.99 4.08 0.85 0.92

6
A.R. Shahmoradi, M. Ranjbarghanei, A.A. Javidparvar et al. Journal of Molecular Liquids 338 (2021) 116550

GCI-containing sample was more than the elements detected in the The surface of the corroded steel has a hydrophilic nature due to
blank sample, while Fe and Cl elements in the blank sample were the presence of Fe-OH bonds on it. So, the less water contact angle
more. In fact, the adsorbed GCI molecules on the electrode surface (49.7°) for the unprotected sample compared with other under-
led to the increase in the atomic percentage of C and O elements in studied samples is due to the hydrophilic nature of the oxidized
the inhibitor-containing solution. The formed compact film on the surface. Increasing the hydrophobicity of the electrode surface cov-
steel surface decreased the atomic percentage of the detected Fe of ered with a layer of the organic–inorganic complex led to the
the substrate. In addition, the protective film prevented and/or increasing of the water contact angle values. The highest contact
reduced the adsorption of Cl- ions on the electrode surface. Fur- angle value was obtained for the electrode immersed in the solu-
thermore, the decrease of Fe-O bond atomic percentage and the tion with 800 ppm GCI, suggesting that the formed surface film
increment of the atomic percentage of CAO and CAC/C@C bonds in this sample was thicker and/or compacter than other samples.
in the quantitative results of the GCI-containing solution suggested In order to compare the results obtained in the present study
the inhibition of the iron oxidation reaction by forming an organic with other GCIs extracted from agricultural wastes, some impor-
film on the immersed electrode surface. The physical properties of tant information including the waste type, extracted compound
the protective film covered the electrode surface can be evaluated (s), extracting solvent, and the maximum efficiency, are tabulated
by contact angle measurements (Fig. 9). in Table 6.

2 m

c d

2 m

e
f

2 μm

Fig. 7. SEM and AFM micrographs of the electrode surfaces immersed in the HCl solution in the (a,b) absence of the GCI and the presence of (c,d) 200 ppm, (e,f) 400 ppm, (g,h)
600 ppm, and (i,j) 800 ppm of the organic GCI extracted from the green husk after 8 h immersion.

7
A.R. Shahmoradi, M. Ranjbarghanei, A.A. Javidparvar et al. Journal of Molecular Liquids 338 (2021) 116550

g
h

2 μm

2 μm

Fig. 7 (continued)

Table 4
concentrated on oxygen atoms due to the formation of covalent
Roughness parameters for the electrode surface immersed in the corrosive solutions bonds with Fe 3d orbitals, which can also be confirmed by the
with and without GCI. Fukui function distribution. As can be seen in the solvated
GCI concentration (ppm) Ra (nm) Rrms (nm) Ry (nm)
COSMO-cavity for the studied inhibitor, and as described in the
sigma-profile, the overlapping regions between GCI and H2O mole-
0 68.2 ± 8.3 79.8 ± 7.1 668.3 ± 54.1
200 49.6 ± 5.1 68.3 ± 4.6 604.2 ± 39.6
cules indicate that the Juglone molecules have a significant hydro-
400 23.8 ± 4.6 33.5 ± 4.9 345.8 ± 23.1 philic nature or excellent water solubility.
600 14.9 ± 3.3 16.8 ± 3.8 155.5 ± 12.2 The obtained quantum chemical descriptors are summarized in
800 3.4 ± 0.3 4.7 ± 0.9 28.7 ± 1.3 Table 7. Eq. (8) gives the fraction of electrons (DN) shared between
GCI and the steel surface.
vFe
vinh
DN ¼ ð8Þ
From Table 6, it can be clearly observed that the inhibition effi- 2ðgFe þ ginh Þ
ciency of walnut green husk is more than most other GCIs. It can be
In this equation, the work-function (vFe) was considered equal
due to the presence of concentrated inhibitive compounds in the
to a theoretical value (7 eV). ginh is the GCI hardness, and gFe
walnut green husk extract. Furthermore, the employment of an
was considered equal to zero, assuming I = A for the bulk substrate.
inexpensive and eco-friendly solvent (DIW) for the extraction pro-
If DN > 0, electrons transferred from the Juglone molecules to the
cess is another advantage of this extraction method compared to
steel surface. Therefore, according to Table 7, the positive value
the researches which used ethanol, acetone, and HCl as the process
of DN indicates that the GCI can donate electrons to the surface
solvent.
of mild steel. Furthermore, it is generally acknowledged dipole
moment (m) estimates the polarity of bonds in any molecule that
3.4. Theoretical considerations is associated with the electron distribution on the molecular struc-
ture [58]. Due to the low value of dipole moment, it can result that
3.4.1. DFT calculations the Juglone molecules accumulated on the steel surface, which
The optimized geometry and chemical activity characteristics of causes an increment in the inhibition efficiency. The obtained
GCI are depicted in Fig. 10. The HOMO and LUMO region are mainly low dipole moment value (0.947 Debye) explains well its excellent
distributed on aromatic rings and oxygen atoms. One of the most corrosion inhibition performance.
useful outputs from DFT theory is the electrostatic potential
(ESP) distribution due to its helping to achieve a graphical mean 3.4.2. MD simulation
about the electrophilic (red area in Fig. 10) and nucleophilic (blue MD simulations were used to determine the interactions
area) sites of the GCI. We can see that the red sites are significantly between the GCI inhibitor and the substrate. By balancing the tem-
8
A.R. Shahmoradi, M. Ranjbarghanei, A.A. Javidparvar et al. Journal of Molecular Liquids 338 (2021) 116550

Fig. 8. (a) The wide scan XPS spectra and the high-resolution spectra of (b, d) O 1s and (c, e) C 1s signals with their deconvolution for the used metal exposed to the blank and
inhibitor-containing solutions after 8 h.

perature and energy, the whole investigated system reached an tend to be adsorbed on Fe(1 1 0) substrate in a parallel configura-
equilibrium condition. Fig. 11a displays the most stable adsorption tion. From the density field map of GCI on the iron surface
configurations of GCI on Fe(1 1 0) surface. Obviously, the highest (Fig. 11b), it can be seen that a hydrophobic layer protected the
coverage degree was obtained due to the fact that the inhibitors metal surface from the corrosive electrolyte. Fig. 11c that the most

9
A.R. Shahmoradi, M. Ranjbarghanei, A.A. Javidparvar et al. Journal of Molecular Liquids 338 (2021) 116550

Table 5
The quantitative results obtained from the deconvolution of C 1s, O 1s, Cl 2p, and Fe 2p signal for the used metal exposed to the blank and inhibitor-containing solutions after 8 h.

Sample Peak Atomic percentage Formula Peak position (eV) Peak area (CPS.eV) Atomic percentage
2+
Blank Fe 2p 52.56 Fe 2p3/2 718.16 2348.51 35.97
Fe3+ 2p3/2 720.17 2768.12 42.40
Fe2+ 2p1/2 731.27 340.03 5.21
Fe3+ 2p1/2 732.95 1072.32 16.42
O 1s 25.25 FeAO 528.03 8704.19 57.78
CAO 529.61 5066.72 33.63
OAH 530.79 1294.42 8.59
C 1s 18.27 CAC 292.30 3657.86 78.73
CAO 293.82 389.92 8.39
COO- 295.48 598.26 12.88
Cl 2p 3.91 Cl 2p3/2 200.46 24503.27 53.48
Cl 2p1/2 201.56 21311.51 46.51
800 ppm Fe 2p 32.27 Fe2+ 2p3/2 710.67 2199.71 31.69
Fe3+ 2p3/2 712.96 3026.00 43.59
Fe2+ 2p1/2 724.40 985.85 14.20
Fe3+ 2p3/2 726.38 730.09 10.52
O 1s 41.70 FeAO 529.97 1958.11 29.21
CAO 531.66 3630.79 54.16
OAH 533.21 1115.22 16.63
C 1s 24.23 CAC/C@C 284.70 2704.05 64.51
CAO 286.50 909.34 21.69
COO- 288.32 578.49 13.80
Cl 2p 1.79 Cl 2p3/2 200.49 18848.6 53.48
Cl 2p1/2 201.53 16393.4 46.52

90

80

70
Contact angle (degree)

60

50

40

30

20

10

0
0 200 400 600 800
GCI concentration (ppm)

Fig. 9. Water contact angle test results for the steel electrode immersed in the acid electrolyte with different concentrations of GCI (after 8 h immersion and drying at 65 °C).

intensive peak of the GCI relative concentration was near the sur- GCI, Einh+solu is the sum of the inhibitor and the solution energies,
face (about 2.995 Å). Generally, the length of the links can be and Esolu stands for the solvent potential energy. It is well known
obtained from the radial distribution function (RDF). In this way, that the adsorption strength between an adsorbed molecule and
a chemisorption process caused a peak between 1 and 3.5 Å, while the surface of a substrate has inversely proportional to the value
the peaks larger than 3.5 Å are related to physisorption [59]. of Eads indicates [61]. The calculated Eads value, obtained from the
According to Fig. 11d, the bond length of the Fe atom and GCI equilibrium configurations, is
338.5 kJ/mol for the GCI inhibitor.
molecules (2.958 Å) is less than 3.5 Å, which manifests that This negative value indicates that the adsorption was stable and
chemisorption is dominant in the investigated adsorption system. spontaneously. Overall, our theoretical results account for the
The adsorption energy (Eads) parameter determines the adsorp- experimental findings satisfactorily.
tion strength of the GCI on the steel surface (Eq. (9)) [60].

Eads ¼ Etotal
ðEsurf þ Einh 4. Conclusion

þ solu þ solu Þ þ Esolu ð9Þ

where Etotal is the total system’s energy, Esurf+solu represents the sum In this work, Juglone extracted from walnut (Juglans regia L.)
of Fe(1 1 0) surface energy and the energy of the solution without green husk was used as a GCI for the mild steel immersed in an
10
A.R. Shahmoradi, M. Ranjbarghanei, A.A. Javidparvar et al. Journal of Molecular Liquids 338 (2021) 116550

Table 6
The waste type, extracted compound(s), extracting solvent, and the maximum efficiency of various GCIs obtained from different studied.

Agricultural Extracting solvent Extracted compounds Maximum inhibition efficiency at the Ref.
waste optimum concentration
Walnut green husk DIW Juglone 95% The
present
study
Pistachio shell DIW Cellulose and lignin 92.7% [21]
Borassus DIW Cyclohexene, 1,3-Dimethyl Phenol 2-Cyclopenten-1-one Phenol, 2- 82.59% [48]
Flabellifer Linn. Methoxy-, Acetate 1,5-Cyclo octadiene
Shell
Orange peel Ethanol/water Neohesperidin, naringin, ascorbic acid 95% [49]
(80% ethanole)
Musa paradisica Acetone/water Gallocatechin 89% [50]
peel (70% acetone)
Garlic peel DIW Allyl methyl disulphide, 2-Thiophenecarboxaldehyde, Diallyl disulphide, 98% [51]
Methyl allyl trisulphide, Diallyl trisulphide
Potato peel DIW Chlorogenic acid, caffeic acid, p-coumaric acid, ferulic acid, salicylic acid 84% [52]
and vanillic acid
Cucumis Sativus 1 M HCl – 82.7% [53]
Peel
Brown onion peel DIW 3(2H)-Furanone, 2-hexyl-5-methyl, 5-Octadecyl-pyrimidine-2,4,6- 96.8% [54]
trione
Chinese DIW Sucrose, Maltosw, Folate 91.9% [29]
gooseberry
Fruit shell
Punica granatum DIW Ellagic acid, Tannic acid 94.2% [30]
peel
Pomelo peel Ethanol Auraptene, naringenin 40 -O-glucoside, and naringin 84.07% [55]
Sweet melon peel 1 M HCl – 81.26% [56]
Jujube shell DIW Ascorbic acid, Linoleic acid, Oleanolic acid and Triterpenoic acid 90.04% [57]

Fig. 10. (a) A Juglone molecule, (b) HOMO, (c) LUMO, (d) ESP, (e) Fukui function, (f) COSMO-cavity, and sigma-profile for the GCI inhibitor.

Table 7
. Quantum chemical variables for GCI at GGA/BLYP/DNP/COSMO level.

Inhibitor EHOMO (eV) ELUMO (eV) DE (eV) I (eV) A (eV) l (D) v (eV) g (eV) DN
GCI
6.018
4.182 1.836 6.018 4.182 0.947 5.101 0.918 1.034

acidic electrolyte (1 M HCl). The corrosion inhibition characteris- surface, which protected it from the corrosive attacks. The altering
tics of the GCI were evaluated by EIS and polarization techniques of the immersed steel surface chemistry in the presence of 0, 200,
and computational methods. The electrochemical test results clar- 400, 600, and 800 ppm of GCI was demonstrated by contact angle
ified that the GCI inhibition efficiency significantly increased in the measurements.
presence of more inhibitor concentrations reaching the maximum
value of 95% in the presence of 800 ppm after 8 h immersion of the
working electrode in the HCl solution with a mixed-type inhibition
CRediT authorship contribution statement
behavior. The SEM and AFM investigations demonstrated that the
adsorption of the Juglone-based compounds on the immersed elec-
A.R. Shahmoradi: Writing - review & editing. M. Ran-
trode surface formed a protective film on the working electrode
jbarghanei: Writing - review & editing. A.A. Javidparvar: Writing
11
A.R. Shahmoradi, M. Ranjbarghanei, A.A. Javidparvar et al. Journal of Molecular Liquids 338 (2021) 116550

Fig. 11. (a) Configuration in equilibrium condition, (b) map of density field map, (c) relative concentration, and (d) radial distribution function plots for the GCI/Fe(1 1 0)
system.

- review & editing. L. Guo: Writing - review & editing. E. Berdimur- [8] D.E. Arthur, A. Jonathan, P.O. Ameh, C. Anya, A review on the assessment of
polymeric materials used as corrosion inhibitor of metals and alloys, Int. J. Ind.
odov: Writing - review & editing. Bahram Ramezanzadeh: .
Chem. 4 (2013) 2, https://doi.org/10.1186/2228-5547-4-2.
[9] B. El Ibrahimi, A. Jmiai, L. Bazzi, S. El Issami, Amino acids and their derivatives
as corrosion inhibitors for metals and alloys, Arabian J. Chem. (2017), https://
Declaration of Competing Interest
doi.org/10.1016/j.arabjc.2017.07.013.
[10] B. Ramezanzadeh, M. Mehdipour, S.Y. Arman, Application of electrochemical
The authors declare that they have no known competing finan- noise to investigate corrosion inhibition properties of some azole compounds
cial interests or personal relationships that could have appeared on aluminum in 0.25 M HCl, Prog. Color Colorants Coat 8 (2015) 69–86.
[11] M. Finšgar, J. Jackson, Application of corrosion inhibitors for steels in acidic
to influence the work reported in this paper. media for the oil and gas industry: A review, Corros. Sci. 86 (2014) 17–41,
https://doi.org/10.1016/j.corsci.2014.04.044.
[12] H.-J. Lee, M.A. Halali, T. Baker, S. Sarathy, C.-F. de Lannoy, A comparative study
Acknowledgements of RO membrane scale inhibitors in wastewater reclamation: antiscalants
versus pH adjustment, Sep. Purif. Technol. 240 (2020), https://doi.org/10.1016/
This work was partially sponsored by the National Natural J.SEPPUR.2020.116549 116549.
[13] A.P. Paiva, O. Ortet, G.I. Carvalho, C.A. Nogueira, Recovery of palladium from a
Science Foundation of China (21706195, 22062022). spent industrial catalyst through leaching and solvent extraction,
Hydrometallurgy 171 (2017) 394–401, https://doi.org/10.1016/J.
HYDROMET.2017.06.014.
Appendix A. Supplementary material [14] M.B. Mansur, S.D.F. Rocha, F.S. Magalhães, J. dos S. Benedetto, Selective
extraction of zinc(II) over iron(II) from spent hydrochloric acid pickling
effluents by liquid–liquid extraction, J. Hazardous Mater. 150 (2008) 669–678.
Supplementary data to this article can be found online at
doi:10.1016/J.JHAZMAT.2007.05.019..
https://doi.org/10.1016/j.molliq.2021.116550. [15] D. Kesavan, M. Gopiraman, N. Sulochana, Green Inhibitors for Corrosion of
Metals : A Review Correspondence, Chem. Sci. Rev. Lett. 1 (2012) 1–8.
[16] M.M. Fares, A.K. Maayta, M.M. Al-Qudah, Pectin as promising green corrosion
References inhibitor of aluminum in hydrochloric acid solution, Corros. Sci. 60 (2012)
112–117, https://doi.org/10.1016/J.CORSCI.2012.04.002.
[1] M. Duque-Acevedo, L.J. Belmonte-Ureña, F.J. Cortés-García, F. Camacho-Ferre, [17] M.V. Fiori-Bimbi, P.E. Alvarez, H. Vaca, C.A. Gervasi, Corrosion inhibition of
Agricultural waste: Review of the evolution, approaches and perspectives on mild steel in HCL solution by pectin, Corros. Sci. 92 (2015) 192–199, https://
alternative uses, Global Ecol. Conserv. 22 (2020), https://doi.org/10.1016/J. doi.org/10.1016/J.CORSCI.2014.12.002.
GECCO.2020.E00902 e00902. [18] A.N. Grassino, J. Halambek, S. Djaković, S. Rimac Brnčić, M. Dent, Z. Grabarić,
[2] K. Kümmerer, J. Clark, Green and Sustainable Chemistry, in: Sustainability Utilization of tomato peel waste from canning factory as a potential source for
Science, Springer Netherlands, Dordrecht, 2016: pp. 43–59. doi:10.1007/978- pectin production and application as tin corrosion inhibitor, Food
94-017-7242-6_4.. Hydrocolloids 52 (2016) 265–274, https://doi.org/10.1016/J.
[3] H. Nguyen, M. Jamali Moghadam, H. Moayedi, Agricultural wastes preparation, FOODHYD.2015.06.020.
management, and applications in civil engineering: a review, J. Mater. Cycles [19] X. Ma, J. Wang, J. Xu, J. Jing, J. Li, H. Zhu, et al., Sunflower Head Pectin with
Waste Manage. 21 (2019) 1039–1051, https://doi.org/10.1007/s10163-019- Different Molecular Weights as Promising Green Corrosion Inhibitors of
00872-y. Carbon Steel in Hydrochloric Acid Solution, ACS Omega 4 (2019) 21148–
[4] P.N. Omo-Okoro, A.P. Daso, J.O. Okonkwo, A review of the application of 21160, https://doi.org/10.1021/acsomega.9b02570.
agricultural wastes as precursor materials for the adsorption of per- and [20] S. Haddadi, M. Mahdavian, Walnut shell extract as sustainable, eco-friendly
polyfluoroalkyl substances: A focus on current approaches and methodologies, and cost-effective green corrosion inhibitor for fabrication of active protective
Environ. Technol. Innovation 9 (2018) 100–114, https://doi.org/10.1016/J. nanocomposite coating based on mesoporous carbon hollow nanospheres,
ETI.2017.11.005. Composites at Lake Louise 2019 (2019) (accessed November 15, 2020) https://
[5] N. Asim, Z. Emdadi, M. Mohammad, M.A. Yarmo, K. Sopian, Agricultural solid dc.engconfintl.org/composites_all_2019/5.
wastes for green desiccant applications: an overview of research [21] A.R. Shahmoradi, N. Talebibahmanbigloo, A.A. Javidparvar, G. Bahlakeh, B.
achievements, opportunities and perspectives, J. Cleaner Prod. 91 (2015) 26– Ramezanzadeh, Studying the adsorption/inhibition impact of the cellulose and
35, https://doi.org/10.1016/J.JCLEPRO.2014.12.015. lignin compounds extracted from agricultural waste on the mild steel
[6] M. Morcillo, I. Díaz, B. Chico, H. Cano, D. de la Fuente, Weathering steels: From corrosion in HCl solution, J. Mol. Liq. 304 (2020), https://doi.org/10.1016/
empirical development to scientific design, Rev. Corrosion Sci. 83 (2014) 6–31, j.molliq.2020.112751 112751.
https://doi.org/10.1016/J.CORSCI.2014.03.006. [22] M. Srivastava, P. Tiwari, S.K. Srivastava, A. Kumar, G. Ji, R. Prakash, Low cost
[7] S.A. Umoren, M.M. Solomon, I.B. Obot, R.K. Suleiman, A critical review on the aqueous extract of Pisum sativum peels for inhibition of mild steel corrosion, J.
recent studies on plant biomaterials as corrosion inhibitors for industrial Mol. Liq. 254 (2018) 357–368, https://doi.org/10.1016/j.molliq.2018.01.137.
metals, J. Ind. Eng. Chem. 76 (2019) 91–115, https://doi.org/10.1016/j. [23] K.K. ALANEME, S.J. OLUSEGUN, Corrosion Inhibition Performance of Lignin
jiec.2019.03.057. Extract of Sun Flower (Tithonia Diversifolia) on Medium Carbon Low Alloy

12
A.R. Shahmoradi, M. Ranjbarghanei, A.A. Javidparvar et al. Journal of Molecular Liquids 338 (2021) 116550

Steel Immersed in H2SO4 Solution, Leonardo Journal of Sciences . 20 (2012) [43] F. Nawaz, L. Wang, L. Zhu, X. Meng, F.-S. Xiao, Ascorbic acid assisted green
59–70. file:///C:/Users/ali/Downloads/OlusegunandAlaneme.pdf. (accessed route for synthesis of water dispersible carbon dots, Chem. Res. Chin. Univ. 29
November 15, 2020).. (2013) 401–403, https://doi.org/10.1007/s40242-013-2339-9.
[24] L.B. Furtado, R.C. Nascimento, P.R. Seidl, M.J.O.C. Guimarães, L.M. Costa, J.C. [44] A.A. Javidparvar, R. Naderi, B. Ramezanzadeh, G. Bahlakeh, Graphene oxide as a
Rocha, et al., Eco-friendly corrosion inhibitors based on Cashew nut shell pH-sensitive carrier for targeted delivery of eco-friendly corrosion inhibitors
liquid (CNSL) for acidizing fluids, J. Mol. Liq. 284 (2019) 393–404, https://doi. in chloride solution: Experimental and theroretical investigations, J. Ind. Eng.
org/10.1016/J.MOLLIQ.2019.02.083. Chem. 72 (2019), https://doi.org/10.1016/j.jiec.2018.12.019.
[25] N.A. Odewunmi, S.A. Umoren, Z.M. Gasem, Watermelon waste products as [45] A. Dehghani, G. Bahlakeh, B. Ramezanzadeh, M. Ramezanzadeh, Potential of
green corrosion inhibitors for mild steel in HCl solution, J. Environ. Chem. Eng. Borage flower aqueous extract as an environmentally sustainable corrosion
3 (2015) 286–296, https://doi.org/10.1016/j.jece.2014.10.014. inhibitor for acid corrosion of mild steel: Electrochemical and theoretical
[26] N. Chaubey, V.K. Singh, M.A. Quraishi, Papaya peel extract as potential studies, J. Mol. Liq. 277 (2019) 895–911, https://doi.org/10.1016/
corrosion inhibitor for Aluminium alloy in 1 M HCl: Electrochemical and j.molliq.2019.01.008.
quantum chemical study, Ain Shams Eng. J. 9 (2018) 1131–1140, https://doi. [46] A. Dehghani, G. Bahlakeh, B. Ramezanzadeh, M. Ramezanzadeh, A combined
org/10.1016/J.ASEJ.2016.04.010. experimental and theoretical study of green corrosion inhibition of mild steel
[27] H. Gerengi, H.I. Sahin, Schinopsis lorentzii Extract As a Green Corrosion in HCl solution by aqueous Citrullus lanatus fruit (CLF) extract, J. Mol. Liq. 279
Inhibitor for Low Carbon Steel in 1 M HCl Solution, Ind. Eng. Chem. Res. 51 (2019) 603–624, https://doi.org/10.1016/j.molliq.2019.02.010.
(2012) 780–787, https://doi.org/10.1021/ie201776q. [47] A.A. Javidparvar, R. Naderi, B. Ramezanzadeh, G. Bahlakeh, Graphene oxide as a
[28] N.R. Rosli, S.M. Yusuf, A. Sauki, W.M.R.W. Razali, Musa sapientum (banana) pH-sensitive carrier for targeted delivery of eco-friendly corrosion inhibitors
peels as green corrosion inhibitor for mild steel, Key Eng. Mater. 797 (2019) in chloride solution: Experimental and theroretical investigations, J. Ind. Eng.
230–239, https://doi.org/10.4028/www.scientific.net/KEM.797.230. Chem. 72 (2019) 196–213, https://doi.org/10.1016/j.jiec.2018.12.019.
[29] A. Dehghani, G. Bahlakeh, B. Ramezanzadeh, A detailed electrochemical/ [48] P.R. Vijayalakshmi, R. Rajalakshmi, S. Subhashini, Inhibitory Action of Borassus
theoretical exploration of the aqueous Chinese gooseberry fruit shell extract as Flabellifer Linn. (Palmyra Palm) Shell Extract on Corrosion of Mild Steel in
a green and cheap corrosion inhibitor for mild steel in acidic solution, Elsevier Acidic Media, 2010. http://www.e. (accessed April 24, 2021)..
B.V. (2019), https://doi.org/10.1016/j.molliq.2019.03.011. [49] N. Behrooz, A. Ghaffarinejad, R. Salahandish, Effect of orange peel extract on
[30] H. Ashassi-Sorkhabi, S. Mirzaee, T. Rostamikia, R. Bagheri, Pomegranate (Punica the corrosion of mild steel in 1 M HCl solution, in: 2016 6th Conference on
granatum) peel extract as a green corrosion inhibitor for mild steel in Thermal Power Plants (CTPP), IEEE, 2016: pp. 64–68. doi:10.1109/
hydrochloric acid solution, Int. J. Corros. 2015 (2015) 1–6, https://doi.org/ CTPP.2016.7483055..
10.1155/2015/197587. [50] G. Ji, S. Anjum, S. Sundaram, R. Prakash, Musa paradisica peel extract as green
[31] S.C. Saling, J.F. Comar, M.S. Mito, R.M. Peralta, A. Bracht, Actions of juglone on corrosion inhibitor for mild steel in HCl solution, Corros. Sci. 90 (2015) 107–
energy metabolism in the rat liver, Toxicol. Appl. Pharmacol. 257 (2011) 319– 117, https://doi.org/10.1016/J.CORSCI.2014.10.002.
327, https://doi.org/10.1016/J.TAAP.2011.09.004. [51] S.S. de Assunção Araújo, M.M. Pereira, T.L. Pêgas, M. Fernández, T.G.
[32] M. Khajeh Mehrizi, M. Hadizadeh, Z. Shahi, M.K. Mehrizi, M. Hadizadeh, A Magalhães, D.C. Lago Schöntag, et al., Inhibitory action of aqueous garlic peel
Review of the Natural Resources Used to Hair Color and Hair Care Products, extract on the corrosion of carbon steel in HCl solution, Corros. Sci. 65 (2012)
2017. https://www.researchgate.net/publication/318795653 (accessed 360–366, https://doi.org/10.1016/J.CORSCI.2012.08.038.
November 24, 2020).. [52] T.H. Ibrahim, Y. Chehade, M.A. Zour, Corrosion Inhibition of Mild Steel using
[33] A.K.M.M. Islam, J.R. Widhalm, Agricultural uses of juglone: opportunities and Potato Peel Extract in 2M HCl Solution, Int. J. Electrochem. Sci. 6 (2011) 6542–
challenges, Agronomy. 10 (2020) 1500, https://doi.org/10.3390/ 6556. www.electrochemsci.org (accessed April 24, 2021)..
agronomy10101500. [53] G.M. Al-Senani, Corrosion Inhibition of Carbon Steel in acidic chloride medium
[34] T. Zmantar, H. Miladi, B. Kouidhi, Y. Chaabouni, R. Ben Slama, A. Bakhrouf, by Cucumis Sativus (cucumber) Peel Extract, Int. J. Electrochem. Sci. 11 (2016)
et al., Use of juglone as antibacterial and potential efflux pump inhibitors in 291–302. www.electrochemsci.org. (accessed April 24, 2021)..
Staphylococcus aureus isolated from the oral cavity, Microb. Pathog. 101 [54] K.C.R. Ferreira, R.F.B. Cordeiro, J.C. Nunes, H. Orofino, M. Magalhães, A.G.
(2016) 44–49, https://doi.org/10.1016/J.MICPATH.2016.10.022. Torres, et al., Corrosion Inhibition of Carbon Steel in HCl Solution by Aqueous
[35] M. Naderi, M. Vesali-naseh, Hydrochar-derived fuels from waste walnut shell Brown Onion Peel Extract, 2016. www.electrochemsci.org (accessed April 24,
through hydrothermal carbonization : characterization and effect of 2021)..
processing parameters, Biomass Convers. Biorefin. (2019), https://doi.org/ [55] Y.P. Yee, S.N. Saud, E. Hamzah, Pomelo peel extract as corrosion inhibitor for
10.1007/s13399-019-00513-2. steel in simulated seawater and acidic mediums, J. Mater. Eng. Perform. 29
[36] A. Karimi, I. Danaee, H. Eskandari, M. RashvanAvei, Adsorption isotherm and (2020) 2202–2215, https://doi.org/10.1007/s11665-020-04774-1.
inhibition effect of a synthesized di-(m-Formylphenol)-1,2-cyclohexandiimine [56] M.T. Saeed, M. Saleem, S. Usmani, I.A. Malik, F.A. Al-Shammari, K.M. Deen,
on corrosion of steel X52 in HCl solution, Journal of Central South University. Corrosion inhibition of mild steel in 1 M HCl by sweet melon peel extract, J.
23 (2016) 249–257, https://doi.org/10.1007/s11771-016-3068-2. King Saud Univ. Sci. 31 (2019) 1344–1351, https://doi.org/10.1016/J.
[37] L. Li, X. Zhang, J. Lei, J. He, S. Zhang, F. Pan, Adsorption and corrosion inhibition JKSUS.2019.01.013.
of Osmanthus fragran leaves extract on carbon steel, Corros. Sci. 63 (2012) 82– [57] A. Jmiai, A. Tara, S. El Issami, M. Hilali, A new trend in corrosion protection of
90, https://doi.org/10.1016/j.corsci.2012.05.026. copper in acidic medium by using Jujube shell extract as an effective green and
[38] P. Najmi, N. Keshmiri, M. Ramezanzadeh, B. Ramezanzadeh, Synthesis and environmentally safe corrosion inhibitor: Experimental, quantum chemistry
application of Zn-doped polyaniline modified multi-walled carbon nanotubes approach and Monte Carlo simulation study, Article in J. Mol. Liquids. 322
as stimuli-responsive nanocarrier in the epoxy matrix for achieving excellent (2020), https://doi.org/10.1016/j.molliq.2020.114509.
barrier-self-healing corrosion protection potency, Chem. Eng. J. 412 (2021), [58] Y. El Aoufir, J. Sebhaoui, A. Chaouiki, H. Lgaz, R. Salghi, A. Guenbour, et al., Two
https://doi.org/10.1016/J.CEJ.2021.128637 128637. novel benzodiazepines as corrosion inhibitors for carbon steel in hydrochloric
[39] S. Pour-Ali, C. Dehghanian, A. Kosari, Corrosion protection of the reinforcing acid: experimental and computational studies, J. Bio- Tribo-Corros. 4 (2018)
steels in chloride-laden concrete environment through epoxy/polyaniline– 54, https://doi.org/10.1007/s40735-018-0169-5.
camphorsulfonate nanocomposite coating, Corros. Sci. 90 (2015) 239–247, [59] E. Berdimurodov, A. Kholikov, K. Akbarov, L. Guo, Inhibition properties of 4,5-
https://doi.org/10.1016/j.corsci.2014.10.015. dihydroxy-4,5-di-p-tolylimidazolidine-2-thione for use on carbon steel in an
[40] F. Hajipour, S. Asad, M.A. Amoozegar, A. Asghar Javidparvar, J. Tang, H. Zhong, aggressive alkaline medium with chloride ions: Thermodynamic,
et al., Developing a Fluorescent Hybrid Nanobiosensor Based on Quantum Dots electrochemical, surface and theoretical analyses, J. Mol. Liq. 327 (2021),
and Azoreductase Enzyme forMethyl Red Monitoring, Iranian Biomedical https://doi.org/10.1016/J.MOLLIQ.2020.114813 114813.
Journal. (n.d.). doi:10.29252/ibj.25.1.8.. [60] S.S. Han, S.H. Lee, J.K. Kang, H.M. Lee, High coverage of hydrogen on a (10,0)
[41] A.A. Javidparvar, R. Naderi, B. Ramezanzadeh, L-cysteine single-walled boron nitride nanotube, Phys. Rev. B. 72 (2005), https://doi.org/
reduced/functionalized graphene oxide application as a smart/control 10.1103/PhysRevB.72.113402 113402.
release nanocarrier of sustainable cerium ions for epoxy coating anti- [61] R. Melian, M. Radi, M. Galai, M. Ouakki, E. Ech-chihbi, N. Dkhirche, et al.,
corrosion properties improvement, J. Hazard. Mater. 389 (2020), https://doi. Anticorrosion properties of 5,50 -dithiobis-(2-nitrobenzoic acid) and sodium
org/10.1016/J.JHAZMAT.2020.122135 122135. sulfite compounds for aluminum alloy 2024–T3 in saline solution:
[42] M. Ramezanzadeh, B. Ramezanzadeh, M. Mahdavian, G. Bahlakeh, Electrochemical, characterization and theoretical investigations, J. Mol. Liq.
Development of metal-organic framework (MOF) decorated graphene oxide 331 (2021), https://doi.org/10.1016/J.MOLLIQ.2021.115661 115661.
nanoplatforms for anti-corrosion epoxy coatings, Carbon 161 (2020) 231–251,
https://doi.org/10.1016/j.carbon.2020.01.082.

13