Journal of the Taiwan Institute of Chemical Engineers 150 (2023) 105044

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Journal of the Taiwan Institute of Chemical Engineers

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Insight into the anti-corrosion mechanism of Chinese mahonia leaves as a

green and bio-degradable against copper corrosion in sulfuric acid medium
Zhixiong Xu a, Bochuan Tan b, *, Jida Chen a, 1, Jie Liu c, Xingwen Zheng d, Lei Guo e, Fan Zhang f,
Nabil Al-Zaqri g, Ruilai Zhang h, Wenpo Li a, 1
a
School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China
b
School of Metallurgy and Materials Engineering, Chongqing University of Science and Technology, Chongqing 401331, China
c
School of Chemistry and Chemical Engineering, Yantai University, Shandong 264005, China
d
School of Materials Science and Engineering, Sichuan University of Science & Engineering, Zigong 643000, China
e
School of Material and Chemical Engineering, Tongren University, Tongren 554300, China
f
Department of Engineering and Design, School of Engineering and Informatics, University of Sussex, Brighton BN1 9RH, United Kingdom
g
Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh11451, Saudi Arabia
h
Chongqing Academy of Metrology and Quality Inspection, Chongqing 401331, China

A R T I C L E I N F O A B S T R A C T

Keywords: Background: Metal corrosion not only leads to significant economic losses for the country but also poses a
Plant extract considerable threat to human safety. The majority of corrosion inhibitors available in the market today fail to
Green inhibitors meet the demand of industrial production for green and sustainable development. Therefore, it is the pursuit of
Quantum chemical
numerous researchers to find efficient, eco-friendly and low-cost methods for metal protection.
Eco-friendly
Molecular dynamics simulation
Methods: In this work, the information on the main components in extracts of Chinese mahonia leave (MLE) was
determined by liquid chromatography-mass spectrometry (LC-MS). The functional groups of MLE were inves­
tigated using Fourier transform infrared spectroscopy (ART-FTIR). X-ray electron spectroscopy (XPS) was
selected to detect bonding information between MLE and the surface of copper. The mechanism of the anti-
corrosion in the Cu/H2SO4 system has been explored by theoretical calculation and electrochemical
measurement.
Significant findings: The electrochemical results showed that MLE could prevent corrosion of copper in the H2SO4
system, and the inhibition efficiency (IE) was 91% at 300 mg/L, MLE predominantly forms a protective film on
the copper surface by employing both weak interactions (electrostatic adsorption) and strong interactions
(chemical coordination). These interactions effectively isolate the copper substrate from the corrosive medium,
resulting in a reduction in the corrosion rate. Combining molecular dynamics simulations with theoretical cal­
culations, we have further confirmed that the N, O, and other heteroatoms in MLE molecules play a crucial role in
their corrosion inhibition performance.

1. Introduction significant challenges to industrial production and equipment reli­

The use of copper by humans dates back to the Shang Dynasty, which
has been around for thousands of years [1]. Copper, a metal with perfect
ductility, toughness and electrical, is mainly used in power plant and
aerospace industries [2]. However, the issue of copper corrosion,
particularly in sulfuric acid environments, demands attention. Copper
corrosion is widely prevalent in industries such as heat exchanger
pipelines, power plant cooling systems, and copper smelting, posing
ability. Therefore, the addition of suitable corrosion inhibitors has
become a crucial strategy in engineering practice to ensure the reliable
operation and long-term stability of copper materials in various appli­
cation environments [3,4].
The protection of the environment is the theme of development in
the world today [5]. Numerous inhibitors, including N, N ’-di (o-tolyl)
thioure, dipropyl sulfide, chromate and dichromate, have been
commercialized. The extensive use of organic corrosion inhibitors can

* Corresponding author.
E-mail address: bochuantan@cqust.edu.cn (B. Tan).
1
These author are co-corresponding authors.

https://doi.org/10.1016/j.jtice.2023.105044
Received 13 April 2023; Received in revised form 3 July 2023; Accepted 11 July 2023
Available online 25 July 2023
1876-1070/© 2023 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Z. Xu et al.
Table 1
Relevant references of plant extracts as copper corrosion inhibitors recently.
Years Raw materials concentration η reference
/ Chinese mahonia leaves 300 mg/L 91.23% This work
2021 Davidia involucrata leaf 300 mg/L 89% Ref. [8]
2021 Luffa cylindrica roem 600 mg/L 89.7% Ref. [9]
2019 4-Aminosalicylic acid 50 mg/L 84.7 Ref. [14]
2022 Gardenia jasminoides fruits 400 mg/L 92.3% Ref. [23]
2022 Passiflora edulia Sims 800 mg/L 95% Ref. [28]
result in their discharge into water bodies as wastewater, infiltration or
leakage into the soil, and volatilization into the air during usage, causing
pollution and potential ecological risks to water bodies, soil, air, and
ecosystems. This imposes irreversible harm to the environment [6]. As a
consequence, it is pressing to find an eco-friendly inhibitor with good
corrosion inhibition efficiency (IE) [7–9]. Plant extracts have received a
lot of attention recently as potential inhibitors, Qiang et al. prepared a
ginkgo leaf extract (GLE) corrosion inhibitor using 80% ethanol as the
solvent through a reflux method and investigated its corrosion inhibition
performance on X70 steel in 1 M HCl. The results demonstrated that at
298 K, GLE exhibited a corrosion inhibition efficiency of 89% [10], Wu
et al. (2019) employed a reflux method to prepare an orange peel extract,
which was found to effectively protect AZ91D magnesium alloy from
corrosion in NaCl solution, as confirmed by electrochemical techniques
and morphology analysis [11], and Shahini et al. immersed the leaves of
Stachys byzantina in anhydrous ethanol for 3 h to obtain an extract.
Through analysis of theoretical calculations and experimental results,
they concluded that the presence of O-H, C=C, C=O, and aromatic ring
structures in the Stachys byzantina leaf extract made a significant
contribution to the protection of steel against corrosion by hydrochloric
acid [12]. In conclusion, plant extracts contain aromatic ring com­
pounds with heteroatoms (N, O, S) [13,14], These compounds possess
abundant lone pairs of electrons, which can react with metal ions and
form a protective film on the metal surface. This protective film effec­
tively isolates the metal substrate from the corrosive medium, resulting
in a significant reduction in the corrosion rate of the metal [15–21].
However, organic solutions are commonly selected for plant extraction,
and the extraction procedure is complicated and costly, which may
cause harm to the environment or the body. Hence, the development of
eco-friendly and efficient inhibitors is extremely challenging [22–24].
The relevant literature on copper corrosion inhibitors is presented in
Table 1, comparing the findings of this study with previous reports. In
this work, Chinese mahonia leaves as the raw material and deionized
water as the solvent have the following advantages [25,26]. Chinese
mahonia leaves are widely distributed in Anhui, Hunan and Sichuan
Fig. 1. Major substances in MLE.
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Journal of the Taiwan Institute of Chemical Engineers 150 (2023) 105044
provinces, so it’s easy to get them. Deionized water was used as a sol­
vent, which was not only eco-friendly but also low-cost. This study
aimed to investigate the corrosion inhibition performance of MLE on
copper in a sulfuric acid environment using electrochemical testing. The
experimental results demonstrated a corrosion inhibition efficiency of
91.23% at a concentration of 300 mg/L. Furthermore, scanning electron
microscopy and atomic force microscopy were utilized for the analysis of
both the metal and its surface corrosion products. The electrochemical
data were employed to develop an adsorption model of MLE on the
copper surface. To gain a more comprehensive understanding and pre­
dict the protective behavior of MLE on copper, a combined approach
incorporating experimental investigations, quantum chemical calcula­
tions, and molecular dynamics simulations was employed.
2. Experiment method
2.1. Chemicals and materials
Sulfuric acid (H2SO4, 98% wt%), copper block (1 × 1 × 1 cm3,
99.8%), ultra-pure water (12.85 mΩ), Chinese Mahonia leaves, also
known as Huang Bo Shu Ye, are plants belonging to the Berberidaceae
family in the order Ranunculales. They are known for their medicinal
properties, including heat-clearing, nourishing deficiency, and cough-
suppressing effects, as well as the ability to dispel phlegm, Chinese
mahonia leaves were picked from Anhui province in summer, all ma­
terials can be used directly without any processing.
2.2. The extraction procedure of the Chinese mahonia leaves
The Chinese mahonia leaves were picked from Anhui province on a
sunny summer day. First, dried the leaves of Chinese mahonia and
grinded into a powder, add 50 g of powder to 2 L of deionized water,
boiled for 12 h, filtered and concentrated, cooled to room temperature,
and then frozen for 48 h. Eventually, get yellow and black solids.
2.3. Preparation of working electrodes and corrosion inhibitor
Blank solution was diluted by adding H2SO4 (98%) to deionize water.
MLE of different masses were dissolved in blank solution to obtain MLE-
H2SO4 solution in different concentrations. Copper block with a size of 1
× 1 × 1 cm3 and purity of over 99.9%, was used in the experiment.
2.4. Characterization of MLE
The components in the MLE were identified using the LC-MS. We
Z. Xu et al. Journal of the Taiwan Institute of Chemical Engineers 150 (2023) 105044

Fig. 2. The ART-FTIR spectrum of MLE (a) and the ART-FTIR spectrum of copper block after treated by MLE H2SO4 solution for 12 h (b).

used ART-FITR to collect the functional group information of MLE and GView, uses the Gaussian 09 W, as shown in Fig. 1. Then, using Gaussian
copper blocks soaked in MLE-H2SO4 solution. XPS was used to charac­ 09 W to optimize the molecular structure with DFT-B3LYP, the base
terize the binding information between the MLE and surface of copper. group selected 6–311++g (d, p) to complete the computation. The
Gaussian calculation was completed to obtain the following relevant
2.5. Electrochemical testing parameters the highest occupied orbital energy (EHOMO), lowest unoc­
cupied molecular orbital energy (ELUMO) and dipole moment (μ).
The CHI604D workstation used in this experiment was selected for ΔE = ELUMO − EHOMO (1)
the electrochemical measurement. It was decided to use a three-
electrode system, with a platinum counter electrode, saturated 1
χ=− (ELUMO + EHOMO ) (2)
calomel electrode for the reference electrode, and copper electrode for 2
the working electrode. During testing, the working electrode was soaked
in the H2SO4 media for 1800 s, so that the potential on the copper sur­ 1
η = (ELUMO − EHOMO ) (3)
face could reach a stable value. The electrochemical impedance (EIS) 2
test was then carried out, and the signal was a sine wave with an 1
amplitude of 5 mV and frequency of 1,00,000 Hz − 0.01 Hz. Finally, the σ= (4)
η
initial and final potentials were obtained by adding and subtracting
0.25 V from the opening circuit potential [27]. The value of ΔE represents the ELUMO minus the EHOMO. To a certain
degree, the value of ΔE could represent the strength of the bonding
between the molecules and the copper surface [28].
2.6. Surface analysis
The MLE adsorption on the copper surface was simulated using the
Forcite module of Materials Studio (MS) software. In the process of
The copper surface was observed by SEM and AFM. All copper
simulation, the Cu (1 1 1) surface was selected because of its lowest and
samples have been polished, before the SEM and AFM tests, the copper
most stable Milligan index. An inhibitor molecule was placed in 30 Å
were submerged in H2SO4 solution (with or without MLE) for 16 h.
vacuum layer, 4 H3O+, 300 H2O, and 2SO2+ 4 . The MS force field was set
as COMPASS, and the ensemble was set as NVT, The total simulation
2.7. Theoretical calculation time and the time step are 500 ps and 10 fs, respectively [29].

The theoretical part of the experiment included molecular dynamics

simulation (MD) and quantum chemical calculation (QC). The quantum
chemical calculation, which created the molecular structure with

Fig. 3. Nyquist plots and Bode plots of copper electrodes in H2SO4 solution at a temperature of 298 K (with or without MLE).

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Fig. 4. The electrochemical impedance of copper electrodes at 298 K, 303 K and 308 K when immersed in a blank H2SO4 solution and H2SO4 solution with 300 mg/
L MLE.

3. Results and discussion
3.1. ART-FTIR characterization
The information about the functional groups can be probed using
ART-FIRT spectroscopy. At 3234.04 cm− 1, there is a broad peak repre­
senting the characteristic stretching vibration peak of O-H or N-H [1], a
sharp peak at 1588.51 cm− 1 is attributed to the peak of C = C in the
aromatic ring. There is a shoulder peak on the left side corresponding to
the C = O stretching vibration peak. There are C-N stretching vibrations
at 1378.44 cm− 1, 1031.32 cm− 1 [30,31], And at 1258.86 cm− 1 signifies
the C-O, the value of peaks below 1000 cm− 1 are attributed to stretching
vibration of C-H on the aliphatic or aromatic groups [32].
Fig. 2(b) showed the Infrared spectrum of the copper block surface
treated with MLE sulfuric acid solution. The broad peak at 3091.11 cm− 1
is attributed to the stretching vibrations of O-H and N-H. At 1670.57
cm− 1, the characteristic absorption peak corresponding to C = O, the
MLE was adsorbed on the copper surface, which weakened the vibration
of double bonds of the benzene ring. In addition, it can be observed that
the C-N peak appears at 1043.09 cm− 1. the surface of copper submerged
in MLE H2SO4 solutions showed the Infrared spectrum characteristic
peak of MLE, which can be explained to some extent that MLE adsorbed
on the surface of copper.

Fig. 5. Equivalent circuit diagram.

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Table 2
Impedance fitting data from different concentrations of MLE.
T C(mg/L) Rf(Ωcm2) Rct(Ωcm2) Rp(Ωcm2) Cf(μFcm− 2) Cdl(μFcm− 2) WY0(× 10− 3) η(%) SD (%)

298 Blank 6.57 622.9 629.5 16.77 77.6 9.357 – –

50 79.56 3176 3255.56 15.2 17.80 2.84 80.66 2.45
100 224.4 4211 4435.4 11.68 11.81 3.506 85.81 1.15
200 168.9 5387 5555.9 11.27 10.85 2.54 88.67 0.79
300 377.4 6800 7177.4 9.955 9.41 2.37 91.23 0.54
303 Blank 11.69 533.4 545.09 16.22 42.12 6.241 – –
300 58.02 3938 3996.02 10.12 11.69 3.676 86.36 1.34
308 Blank 5.362 331.6 336.962 21.19 24.77 9.492 – –
300 52.76 3020 3072.76 10.42 13.18 3.954 89.03 0.75

SD, the standard deviation of 3η.

3.2. EIS measurements
The EIS spectra were investigated at different concentrations of
H2SO4 solution with or without MLE at 298 K. Fig. 3 depicts the Nyquist
and Bode diagrams. The Nyquist diagram (Fig. 3a) consisted of a
depressed semi-circle capacitor loop and the Warburg impedance [33],
the depressed capacitor loop showed that the corrosion of copper in
MLE-H2SO4 solution was dominated by the charge transfer process. It
was related to the charge transfer resistance (Rct) and the electric
double-layer capacitance (Cdl) in the high-frequency region. In addition,
the radius of the capacitor loop increased with the increase of the con­
centration of MLE. This behavior showed that the reaction of MLE with
the copper surface prevented additional corrosion of copper, which
made the Rct value of the Cu/H2SO4 system increase. The warburg
impedance is due to the adsorption of dissolved oxygen in the H2SO4
medium on the copper surface or the transfer of Cu2+ on the copper
surface into H2SO4 medium [34]. It can be clearly seen from the Bode
diagram in Fig. 3(b) that the impedance modulus and phase angular
frequency tend to increase with the increase of MLE concentration.
Moreover, the slopes of log f and log |Z| are close to − 1, and the phase
angle is close to 90◦ , which indicates that MLE adsorption on copper
surface is an ideal capacitive behavior.The MLE-H2SO4 solution has a
wider phase angle compared to the blank solution of sulfuric acid. This
showed that there were two time constants, one of which was deter­
mined by the Cdl. The other was the relaxation process.
The electrochemical impedance of copper electrodes at different
temperatures when immersed in a blank H2SO4 solution and H2SO4
solution with 300 mg/L MLE is shown in Fig. 4. As shown in the Nyquist
diagram (Fig. 4a), under the same conditions, the diameter of the
capacitor loop decreases with increasing temperature, suggesting that
the charge transfer process at the interface between copper and H2SO4
becomes easier because the rate of Cu conversion to Cu2+ increases with
increasing temperature, as shown in the Bode diagram (Fig. 4b), the
impedance modulus decreases as the temperature increases, and the
maximum frequency range of the phase angle narrows [35].
We choose the equivalent circuit diagram to analyze and discuss the
EIS data, as shown in Fig. 5. The related fitting data are shown in
Table 1. According to the results presented in Table 2, it can be observed
that the value of Warburg impedance decreases with increasing MLE
concentration. This observation suggests that higher MLE concentra­
tions facilitate the attachment of more molecules to the surface of cop­
per, thereby slowing down the rate of material exchange between the
copper and the solution. The Warburg impedance is a parameter related
to interfacial diffusion, and its decrease signifies a reduction in the rate
of substance transfer during the corrosion process. These findings indi­
cate that the addition of MLE has a positive effect on mitigating the
corrosion rate of copper by decelerating the material transport process.
As the concentration of MLE increases, the impedance modulus in­
creases and the maximum phase angle frequency increases, this in­
dicates that the absorption of MLE on copper can hinder the erosion of
corrosive particles. The Cf and Cdl correspond to reflect film capacitance
and double-layer capacitance.
The ZCPE formula is as follows [36–41]:
1
ZCPE = (5)
Y0 (jω)n
ω stands for the angular frequency, Y0 is CPE constant, j represents the
imaginary root, and n denotes the deviation index, the different values
of n have different meanings, such as n = − 1 (inductance), n =
0 (inductor) and n = 0.5 (Warburg impedance), in this study, n1 = 1, CPE
exhibited a pure capacitance behavior, indicated that the copper surface
was relatively smooth and MLE adsorption is relatively uniform on it.
The Cf and Cdl are calculated by the following formula [42,43]:

Fig. 6. The OCP curves and Tafel curves of copper in different concentrations of MLE H2SO4 solution at 298 K.

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Table 3 on the copper surface that impedes electron transfer, creating a barrier
The corrosion parameters of Cu in H2SO4 mediums with or without MLE. to charge transfer between the copper substrate and sulfuric acid [46].
T C Ecorr icorr(μA βc(mV βa(mV η(%) SD This observation is consistent with the results obtained from Bode and
(k) (mg/ (mV/ cm− 2) dec− 1) dec− 1) (%) Nyquist plots, providing further evidence for the formation of an MLE
L) SCE) film and its role in mitigating copper corrosion. The following formula is
298 Blank − 70 12.23 − 314.56 130.11 / / used to determine the η. [47–50]:
50 − 110 2.306 − 179.69 37.38 81.14 1.69
100 117 1.903 166.81 35.49 84.44 0.27 RP − RP,0
− − η(%) = × 100% (7)
200 − 117 1.373 − 157.79 29.02 88.77 0.09 RP
300 − 123 1.223 − 165.54 28.29 90 0.11
303 Blank − 64 16 − 527.43 51.15 / / At the temperature of 298 K and 300 mg/L, the value of η could reach
300 − 117 1.65 − 176.80 21.99 89.67 0.15 91.23%. With the increase of temperature, the η still reached about 90%.
308 Blank − 64 17.38 − 592.07 91.12 / /
300 − 118 1.84 − 170.10 20.28 89.44 0.94 3.3. OCP curves and PDP curves
SD, standard deviation of 3η.
The OCP curves and Tafel curves provide evidence of the corrosion
( )n− 1 inhibition effect of MLE on the Cu/H2SO4 system. Fig. 6 shows the tafel
C = Y0 (ω)n− 1
= Y0 2πf(Zim− Max) (6) curves and OCP curves measured in H2SO4 solution with MLE. The
values of OCP curves that fluctuate little in the last 400 s are considered
The note is that the values of Rf and Rct showed an increasing trend as
stable, suggesting equilibrium between precipitation and dissolution on
MLE concentration increased, whereas Cf, Cdl and Warburg impedance
the copper surface. MLE concentration increased from 0 mg/L to 300
values were decreasing. The decreasing Cf and Cdl processes represent
mg/L, and the values of the OCP curves show a decreasing trend, which
the process by which MLE displaces water molecules at the Cu/H2SO4
shows that the MLE can effectively slow down the rate of cathode re­
interface.
action. Moreover, the Ecorr values of the MLE-containing solution,
The note is that the values of Rf and Rct showed an increasing trend as
compared to the blank solution, show a deviation of less than 85 mV,
MLE concentration increased, whereas Cf, Cdl and Warburg impedance
indicating that MLE acts as a mixed-type corrosion inhibitor. The Table 3
values were decreasing. The decrease in Cf and Cdl values indicates the
showed the related electrochemical physical quantities: corrosion cur­
replacement of water molecules by MLE molecules through surface
rent density (icorr), the slope of cathodic corrosion potential (Ecorr), and
adsorption, forming an interfacial layer that hinders the solvation of
the slope of anode and cathode (βa, βc), and the efficiency of anti-
water molecules during the charge transfer process [44,45]. Simulta­
corrosion (η) [51]. The calculation formula of η is as follows (5) [52–55]:
neously, the increase in Rf and Rct values suggests the formation of a film

Fig. 7. The OCP curves and Tafel curves of copper in 0.5 M H2SO4 medium (with or without MLE) were measured at different temperatures.

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electron to become Cu+ is very fast and sticks to the surface of copper,
however, the process of Cu+ becoming Cu2+ is very slow, so the trans­
formation of Cu+ into Cu2+ is a decisive step, and the corrosion of copper
in H2SO4 medium comes down to the process of Cu2+ being transferred
to the solution [57]. MLE can provide a large number of lone pair
electrons to combine with Cu+ to form a protective film to prevent the
further dissolution of Cu+ and effectively prevent copper corrosion. The
reaction process is shown below:

Cu+ +
ads + nMLE→[Cu − MLEn ]ads (11)

Fig. 8. Langmuir adsorption on copper surface of MLE at 298 K.
icorr,o − icorr
η(%) = × 100%
icorr
icorr,0 and icorr present the corrosion current density of copper in blank
solution of and MLE H2SO4 solutions, respectively. The decrease in
corrosion current density, as shown in Table 3 compared to the blank
solution, indicates that the addition of MLE slows down the rate of
corrosion reaction on the metal surface. This observation suggests that
MLE exhibits corrosion inhibition properties, effectively reducing the
interaction between the metal surface and the corrosive medium.
The kinetics of Cu/H2SO4 system can be reflected by polarization
curves. The equation of Copper in H2SO4 medium is as follows [56]:
1 regression coefficient is 0.99972 [60–62].
Cathode : O2 + 2H+ + 2e− →H2 O
2 1
Anode : Cu→Cu+ −
ads + e fast
Fig. 6b shows that the density of cathode and anode corrosion cur­
rent decreases as the concentration of MLE increases, and the corrosion
potential is negatively offset, MLE influences cathodic and anodic re­
action of Cu/H2SO4 system. The tafel curve cathode branches parallel to
each other (with or without MLE), suggesting that the addition of MLE
does not alter the mechanism of Cu surface cathode branch reaction. A
passivation platform appears in the anode branch, possibly due to MLE
adsorption on the copper surface [58].
Fig. 7 displays the OCP curves and Tafel curves of copper in a 0.5 M
H2SO4 medium, measured at various temperatures with and without
MLE as a corrosion inhibitor. The corresponding electrochemical pa­
rameters are presented in Table 3. Remarkably, at the same concentra­
tion, as the temperature increases, the corrosion current density rises,
(8) and the corrosion potential shifts towards the positive direction. This
finding suggests that elevated temperatures accelerate the oxidation and
corrosion processes of copper.
3.4. Adsorption model
To investigate the adsorption state of a corrosion inhibitor on a metal
surface, adsorption isotherms are frequently used. The value of EIS
spectroscopy were selected to analyze the adsorption type [59]. The
findings indicate that the most suitable model for MLE adsorption of Cu
in H2SO4 solution is Langmuir isothermal adsorption. The linear
(9) ( )
− ΔG0ads
Kads = exp (12)
C H2 0 RT

θ
Cu+ 2+
ads →Cuads+e− slow (10) = Kads C (13)
1− θ
As can be seen from the anode reaction, the process of Cu losing an

Fig. 9. SEM images of copper treated with H2SO4 medium (a-c) and MLE-H2SO4 medium (d-f) for 30 h.

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Z. Xu et al.
Fig. 10. AFM morphology of copper under different treatment methods for 30 h.
Where θ=η/100 represents surface coverage, Kads is equilibrium con­
stant, and C is the concentration of MLE, and CH2O is 1000 g/L. As shown
in Fig. 8, concentration (C) as horizontal coordinates, C/θ as vertical
coordinates for drawing. Generally, ΔG0ads of chemical adsorption less
than − 40 kJ/mol and that of physical adsorption is more than − 20 kJ/
mol, obtained in this experiment is − 28.66 kJ/mol, which is in the range
of − 40 and − 20 kJ/mol. Therefore, the MLE adsorbed on the copper
belongs to the mixed adsorption [63,64].
3.5. Morphology analysis
Fig. 9 depicts the topography of Cu after 30 h of immersion in H2SO4
medium (with or without MLE). Fig. 9 (a, b, c) displays the corrosion
morphology images of copper sheet in H2SO4 solution, from which it is
clear that they are all covered by particles in the shape of irregular hills,
with the increase of temperature, the morphology of granular hills be­
comes more irregular, obvious scratches disappear, and the corrosion
becomes more and more serious. Fig. 9 (d, e, f) shows the corrosion
morphology of copper treated with MLE H2SO4 medium at different
temperatures. It can be seen that the surface of copper becomes more
uniform, and some flaky substances are uniformly covered on the sur­
face. The surface of copper becomes more uniform, with the presence of
some flaky substances uniformly covering its surface. By adding MLE,
the interaction between the abundant heteroatom groups in MLE and the
Cu+ ions on the copper surface forms a protective film. It is effectively
isolates the copper substrate from the corrosive medium and results in a
reduction in the corrosion process. These findings are in line with the
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Journal of the Taiwan Institute of Chemical Engineers 150 (2023) 105044
electrochemical results, supporting the notion that MLE plays a crucial
role in mitigating copper corrosion. At 308 K, slight corrosion occurred
on the surface of Cu. This may be due to the increase in temperature,
which damaged the structure of surface materials, so that MLE could not
be uniformly covered on the copper surface, and H2SO4 medium eroded
the surface of copper.
AFM can observe the micromorphology of the metal surface at
atomic scale [65]. Fig. 10 respectively shows the 3D micromorphology
of the newly polished copper surface and copper after soaked in sulfuric
acid medium (with or without MLE) for 16 h. The 3D map of the freshly
polished copper surface is relatively flat, as can be seen, and the Ra value
is only 7.444 nm. However, Due to the erosion by the blank H2SO4
medium, the surface of copper forms uneven corrosion pits, resulting in
a significantly increased Ra value of 88.27 nm [66]. Although the copper
surface after immersed in the H2SO4 medium containing MLE is rougher
than that of the newly polished copper, the difference is not significant.
This could be attributed to the adsorption of MLE through physical and
chemical interactions, forming a protective layer on the copper surface
that isolates the copper substrate from the corrosive medium and slows
down the corrosion process [67]. Compared with copper after immersed
in blank H2SO4 solution, the surface difference is also very obvious, Ra
value is only 15.165 nm, the conclusion is consistent with SEM, indi­
cating that MLE can effectively protect copper surface.
3.6. XPS
The primary use of XPS is to identify the chemical characteristics and
Z. Xu et al.
Fig. 11. XPS spectra of copper after immersed with MLE-H2SO4 medium for 30 h (a) survey (b) C 1 s, (c) Cu 2p, (d) O 1 s, and (f) N 1 s.
content of the sample surface analysis by calculating the binding energy
of electrons. Fig. 11(e) shows the full XPS spectrum of copper after
immersed with MLE-H2SO4 solution, it is obvious that the peaks of C, N,
O and Cu appear on the full spectrum. Fig. 11(b) shows the XPS spec­
trum of Cu 2p. The peak at 932.69 eV and 952.49 eV are assigned to Cu
2P3/2 /Cu (I) and Cu 2P1/2/ Cu (I), at 935.1 eV and 954.6 eV, corre­
sponding to Cu (II) 2p3/2 and Cu (II) 2p1/2, respectively. Charge transfer
(CT), a recognized model to describe transition metal XPS, attributed to
the transition of copper ions to 2p53d9 > state during photoemission,
despite the presence of trace amounts of divalent copper ions in the XPS
spectrum, there is no denying the anticorrosion effect of MLE on Cu/
H2SO4. Fig. 11(c) shows the XPS spectrum of N 1 s, the binding energy
values of N-Cu, N-C and N=C are 401.52 eV,400.16 eV and 399.49 eV,
respectively, it is noteworthy that the N-Cu bond is formed, indicating
that the N in MLE has chemical adsorption with the Cu surface. It is
worth noting that the formation of N-Cu bond displays that coordination
9
Journal of the Taiwan Institute of Chemical Engineers 150 (2023) 105044
occurs surface N and Cu in MLE. Meanwhile, Fig. 11(d) is attributed to
Cu2O at 531.64 eV, which further proves that the N and O atoms in MLE
indicate reactions with Cu.
3.7. Quantum chemistry calculation
The ability of active molecules in MLE to protect Cu from sulfuric
acid was theoretically revealed by quantum chemistry calculation. The
frequency correction and structure optimization of Palmatine (PLT),
Jatrorrhizine (JTH) and Berberine (BBR) were performed by hybrid
density functional theory. Fig. 12 displays the calculated results,
including the optimized structure, HOMO and LUMO orbital electron
cloud density, and the EHOMO, ELUMO, ΔE, χ , η, σ and μ are shown in
Table 5 [68].
It is self-evident that QRT and FA’s HOMO and LUMO orbital elec­
tron clouds are all over the molecule, from this, it is not difficult to infer
Z. Xu et al. Journal of the Taiwan Institute of Chemical Engineers 150 (2023) 105044

Fig. 12. Different molecular structures and distribution of HOMO, LUMO orbital electrons.

Table 5
Quantum chemistry computational data.
Substance EHOMO(eV) ELUMO(eV) ΔE(eV) μ(Debye) χ σ η
Palmatine − 2.69 − 2.03 0.66 5.29 2.36 3.03 0.33
Jatrorrhizine − 2.23 − 1.64 0.59 1.93 1.93 3.37 0.29
Berberine − 2.53 − 1.93 0.60 6.01 2.23 3.33 0.30
Quercetin − 4.80 − 2.30 2.50 4.86 3.55 0.80 1.25
Fumaric acid − 5.56 − 3.03 2.53 1.88 4.29 0.79 1.26

that QRT and FA cover the Cu surface with parallel adsorption because
this maximizes contact with the copper surface for optimal protection.
However, PLT, JRH, and BBR’s orbital electron clouds are distributed on
one side of the molecule, and such a large distorted structure gives them
directional adsorption on the Cu surface. ELUMO and EHOMO represent
molecules’ ability to receive and deliver electrons. The smaller ELUMO is,
the stronger the ability to accept electrons [69]. Therefore, ΔE can
represent the adsorption capacity, the smaller ΔE is, the easier it is to be
absorbed on the surface of Cu, and the more obvious the corrosion in­
hibition effect will be, ΔE can be arranged in the order of
FA>QCT>PLT>BBR>JTH, so JTH and BBR contribute the most to the
corrosion inhibition effect of Cu. In addition, dipole moments (μ) are
also an indicator for evaluating corrosion inhibition [70]. The larger the
dipole moment, the more easily inhibitor molecules accumulate on the
Cu surface, altering the dielectric properties of the dielectric capacitance
of the dielectric layer to achieve better anti-corrosion performance.
Therefore, considering the dipole moment, BBR and PLA exhibit a
greater contribution to the corrosion inhibition mechanism. It is
important to note that the relationship between dipole moment and
corrosion inhibition is complex, as it is influenced by various factors
such as molecular structure, adsorption mechanisms, and environmental
conditions [71,72].
In the electrostatic potential map (ESP), the red regions indicate the
nucleophilic center and the blue regions represent the electrophilic
center. The red regions are mostly distributed in electronegative groups
with heteroatoms, which are easy to form covalent bonds with electro­
philic Cu+ ions. The electrophilic region in the molecule can effectively
prevent the corrosion of the copper surface. It is fully proven that MLE
can effectively prevent the corrosion of copper in the H2SO4 medium.
As is known to all, the electronegativity (χ) can measure the ability to
gain or lose electrons. The greater the χ value, the greater the likelihood
that it will attract electrons. Compared with FA and QCT, the JTH, PLT
and BBR have smaller values of χ, suggesting a higher inclination to
donate electrons and interact with the copper surface’s sub-copper ions,
thereby forming a protective layer. Consequently, they contribute
significantly to the protection of copper. In addition, the greater the
global hardness (η) of a molecule, the harder it is for the molecule to
transfer electrons. Consequently, molecules with lower η values are

10
Z. Xu et al. Journal of the Taiwan Institute of Chemical Engineers 150 (2023) 105044

Fig. 13. Adsorption configurations of FA, Molecular dynamics mimic related energy of FA, QCT, PLT, BBR and JTH on Cu (111) surface.

efficiency. Table 6 shows relevant energy (FA, QCT, PLT, BBR and JTH)
Table 6
calculation results [73]. The binding energy formula is as follows
Molecular dynamics mimic related energy of FA, QCT, PLT, BBR and JTH.
[74–77]:
Substance Etot(kcal/ Esub(kcal/ Einh(kcal/ Ebinding(kcal/
mol) mol) mol) mol) Einteract = Etot − (Esubs + Einh ) (14)
Palmatine − 3112.4 − 3504.8 218.7 126.3
Jatrorrhizine − 3426.6 − 3501.8 205.8 130.6
Ebinding = − Einteract (15)
Berberine 3451.5 3531.4 200.1 120.2
Etot represents total energy, Esubs refer to the energy of all water
− −
Quercetin − 3528.3 − 3394.6 − 14.1 119.6
Fumaric acid − 3716.4 − 3598.1 − 77.8 40.5 molecules and Cu, and inhibitor molecular energy is expressed in Eint
[78]. The strength of the binding energy represents, to some extent, the
interaction capability between the inhibitor molecules and the copper
more effective as corrosion inhibitors. In line with the previous findings, surface in corrosion inhibition [79]. The Ebinding of FA, QCT, PLT, BBR
JTH and BBH exhibit stronger corrosion inhibition capabilities. This and JTH were 40.5, 119.6, 126.3, 120.2 and 130.6 kcal/mol, respec­
correlation reinforces the overall consistency of the results obtained tively, so the inhibition ability is ranked as JTH> PLT>BBR>QCT>FA.
from the various parameters. It is noteworthy that the main constituents of MLE exhibit high binding
energies on the copper surface, implying that they can offer stable,
strong and spontaneous adsorption on the copper surface [80,81].
3.8. Molecular dynamics study
Although the binding energy of FA is lowest, it cannot be denied that it
also plays a role [82].
Fig. 13 depicts the MLE adsorbed on copper that was simulated by
Materials Studio (MS). It is beyond dispute that parallel adsorption can
reduce the area of Cu exposed to H2SO4 solution, thus protecting copper
from corrosion and greatly improving the corrosion inhibition

11
Z. Xu et al. Journal of the Taiwan Institute of Chemical Engineers 150 (2023) 105044

Fig. 14. Anti-corrosion mechanism of MLE in Cu/H2SO4 system.

(2) MLE has a good anti-corrosion nature on Cu from the microscopic

Table 4
morphology, and XPS and infrared spectra prove that the het­
The information of XPS spectrum.
eroatom in MLE and a large number of lone pair electrons carried
Level Chemical States Binding Energies (eV) by aromatic ring structure have a non-negligible role in protect­
N 1s N=C 399.49 ing Cu.
N-C 400.16 (3) The adsorption of MLE on the copper surface follows the Lang­
N-Cu 401.52 muir isotherm model, indicating that the adsorption process in­
O 1s Cu2O 531.64
C-O-C 532.04
volves both physical adsorption (such as van der Waals forces)
Cu 2p Cu 2p3/2/Cu (I) 932.69 and chemical adsorption (formation of chemical bonds).
Cu 2p1/2/Cu (I) 952.49 (4) Theoretical calculation and molecular dynamics showed that
Cu (II) 935.1 MLE adsorbs on the copper surface in a parallel orientation,
CuO 954.7
maximizing its corrosion inhibition effectiveness.

3.9. Anti-corrosion mechanism

Declaration of Competing Interest
The mechanism of MLE protecting Cu from corrosion in H2SO4 so­
The authors declare that they have no known competing financial
lution is shown in Fig. 14. According to the results of electrochemical
interests or personal relationships that could have appeared to influence
measurement, the addition of MLE inhibited the anodic reaction of Cu+
the work reported in this paper.
to Cu2+ in H2SO4 solutions, this point can be verified by XPS, the Cu+ is
detected on the Cu surface, so MLE can coordinate with Cu+, thus pre­
Acknowledgements
venting the corrosion of Cu. The value of ΔG0ads calculated by the
isothermal adsorption curve, the adsorption of MLE on copper surface
The authors extend their appreciation to the Researchers Supporting
belongs to mixed adsorption. The reactive center composed of hetero­
Project number (RSP2023R396), King Saud University, Riyadh, Saudi
atoms and aromatic can not only react with Cu+, but also provide a
Arabia., Municipal Natural Science Foundation of Chongqing (No.
negative electric center to generate electrostatic adsorption (Table 4).
CSTB2022NSCQ-MSX1189 and CSTB2022NSCQ-MSX1369), Young
Elite Scientists Sponsorship Program by CAST (2022QNRC001), Open­
4. Conclusion
ing Project of Material Corrosion and Protection Key Laboratory of
Sichuan Province (No. 2021CL30), Research Foundation of Chongqing
In this study, the mechanism of MLE protecting Cu from corrosion in
University of Science and Technology (No. ckrc2021052), Opening
H2SO4 solution is studied. The following conclusions are obtained:
Project of Material Corrosion and Protection Key Laboratory of Sichuan
Province (2022CL18).
(1) Electrochemical experiments demonstrate that the anti-corrosion
efficiency does not change greatly within a certain temperature
range, the η can reach 91% when the MLE concentration is 300 References
mg/L at 298 K. Comparing with the reported literature, for
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