Rosmarinus officinalis extract as eco-friendly corrosion inhibitor for copper in 1 M nitric acid solution: Experimental and theoretical studies

Badreah A. Al Jahdaly

doi:10.1016/j.arabjc.2022.104411

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Original article

01 2022

:16;

104411

doi:

10.1016/j.arabjc.2022.104411

Rosmarinus officinalis extract as eco-friendly corrosion inhibitor for copper in 1 M nitric acid solution: Experimental and theoretical studies

Badreah A. Al Jahdaly

Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia

Received: 2022-9-11, Accepted: 2022-11-7,

Disclaimer:
This article was originally published by Elsevier and was migrated to Scientific Scholar after the change of Publisher.

Peer review under responsibility of King Saud University.

Abstract

Rosmarinus officinalis extract (ROE) was studied chemically (mass loss, ML), electrochemically impedance spectrometry (EIS), and potentiodynamic polarization (PDP) as a corrosion inhibitor in 1 M nitric acid. According to ML, ROE is effective like a copper preservative in 1 M HNO₃ acid solution at R.T by improving inhibitor concentration up to 77 % at 300 ppm and 25 °C. A study was conducted regarding the effect of temperature on copper adsorption, as well as the calculation of adsorption coefficients. Results indicated that physisorption increases with temperature, indicating a decrease in inhibition efficiency (%IE). Langmuir's adsorption model was consistent with the adsorption mechanism. Using the PDP method, the inhibitor accumulated on the copper surface in mixed forms. Moreover, EIS revealed that the value of double-layer capacitance dropped with an increased dose of ROE, while the charge transfer resistance improved. A different approach was taken to the examination of surfaces. Both theoretical studies and practical results were calculated and compared to demonstrate that the results were valid.

Keywords

Rosmarinus officinalis

Electrochemical

Corrosion

Copper

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1 Introduction

Ancient civilizations used copper to create bronze mirrors, coinage, and copper seals (Hoffman, 2019). However, it is now directly tied to copper, whether it be the ongoing functioning of cars, the unavoidable comfortable ventilation, or the soaring missiles (Hussain, 2020; Marques et al., 2020; Scott and Schwab, 2019 ). Copper has always had strong links to social life and industrial endeavors because of its outstanding electrical and thermal conductivity. The pickling procedure is frequently used to guarantee the metal's quality (Galai et al., 2017). The corrosion of copper in acidic conditions is unsatisfactory (Zhang et al., 2020). Corrosion inhibitors are frequently employed in corrosion protection because of their low cost and excellent effectiveness (Palanisamy, 2019). Therefore, corrosion inhibitors can be added to pickling solutions to overcome this problem. Corrosion inhibitor application offers multiple benefits, including small volume, simple operation, low cost, wonderful effect, great compatibility, and more (Al Jahdaly et al., 2021; Agboola et al., 2022). Plant extracts are among the most popular green corrosion inhibitors because of how simple they are to prepare, the variety of materials they may be manufactured of, and how little harm they cause to people and the environment. In general, it is simple to access fresh plant tissues, and the extraction procedure is rapid, simple, and eco-friendly, all of which are helpful to further improve overall preparations (Zhang et al., 2022; Huang et al., 2022; Kumari et al., 2022 ). Because amino acids, polyphenols, and flavonoids provide a protective barrier on the metal's surface, these substances are found in the extracts as many functional groups, including (N—O—P—S) (Loto et al., 2022; Loto, 2020; Odunlami et al., 2021 ). There is a good number of antioxidants in ROE like such as methyl carnosate, rosmarinic acid, carnosic acid, rosmadial, rosmanol, and epirosmanol with phenolic diterpenoide. A phytochemical analysis of R. officinalis extracts has revealed that it contains rosmarinic acid, camphor, caffeic acid, ursolic acid, betulinic acid, carnosic acid, and carnosol (El Faydy et al., 2016). Consequently, R. Officinalis contains mostly phenolic compounds, diterpenes, and essential oils (Kadiri et al., 2018). R. officinalis L. leaves are commonly used as an analgesic, antibacterial, and carminative in traditional medicine (Miraj and Kiani, 2016; Kompelly et al., 2019). Besides treating minor wounds, rashes, headaches, dyspepsia, and circulatory issues, rosemary oil and extracts may also be used for expectorants, diuretics, and antispasmodics. It appears that Rosmarinus officinalis extract acts as an anticorrosion metal when used in acidic environments, as it protects XC48 steel from corrosion.The chemical composition of these compounds is outlined in Table 2. In this study, an eco-friendly, nontoxic substance namely a Rosmarinus officinalis extract (ROE) will be evaluated for its potency against the copper dissolution in an acidic medium (1.0 M nitric acid solution) by using chemical, electrochemical methods, Fourier transform infrared (FTIR), scanning electron microscopy (SEM) as well as characterization techniques from Monte Carlo simulation and density functional theory DFT to discover the adsorption type and corrosion mechanism on the metal surface.

2 Experimental methods

2.1

2.1 Materials and solutions

Pieces of copper of certain chemical compositions were used as listed in Table 1. 2x2 cm² (height breadth) was the coupon's dimensions. Prior to beginning, the Cu surface was scraped with silicon carbide emery sheets varying in grade from 100 to 1500, and it was carefully scrubbed with D.W. Furthermore, samples were cleaned with acetone (Hamadi et al., 2018). Nitric acid was purchased from Sigma-Aldrich Chemicals Company with a concentration of 70 percent, and it was diluted to reach the desired concentration.

Table 1 Lists the mass percentages of the copper metal's chemical composition.

Element	As	Pb	Bi	Fe	Sn	Ag	Cu
mass percentages	0.0002	0.002	0.0005	0.01	0.001	0.001	The rest

2.2

2.2 Mass loss

For the measurements of mass loss, copper samples with a thickness of 2.0 * 2.0 * 0.2 cm were used, which were polished to different degrees of sandpaper, then washed with alcohol to remove impurities and dirt, distilled water, and then the process of good drying of the samples, followed by mass loss measurements by the usual methods at different temperatures which calculated according to the following equation (Xiao et al., 2022; Kadhim et al., 2021):

(1)

% I E = θ x 100 = 1 - \frac{W}{W_{O}} x 100

W and W^O are the mass loss of metal without and with investigated compounds, respectively.

2.3

2.3 Electrochemical measurements:

Electrochemical measurements were performed at a temperature of 25 °C with platinum electrodes, calomel electrodes, and copper electrodes. As part of this system, platinum electrodes were used as counters, calomel electrodes as references, and copper electrodes as working electrodes (Fergachi et al., 2019). A copper electrode dipped in an acidic medium at an open circuit voltage obtained a semi-stable state. An alternating current signal of 5 mv was used to determine inhibition efficiency by measuring impedance at various times and varying frequencies among 10^-2 and 10^-5 Hz and the IE% was calculated by using the following equation (Singh et al., 2019):

(2)

IE % = \frac{R_{c t} - R_{c t, 0}}{R_{c t}} \times 100

R_ct and R_ct,0 are charge-transfer resistances of inhibited and uninhibited copper, respectively.

An experiment was performed to determine the polarization value at 1 mV s-1 and in the −250 mV range. The following equation was used to calculate inhibitory efficiency values (Chen et al., 2020).

(3)

IE % = \frac{i_{c o r r, 0} - i_{c o r r}}{i_{c o r r, 0}} \times 100

i_corr,0, and i_corr mean current density values lack the existence of the protection of compounds. With a computer monitor attached to Potentiostat/Galvanostat/ZRA. A Gamry framework system based on the ESA 400 is included. EIS300 and DC105 polarization software are also included in Gamry applications.

2.4

2.4 Surface characterization:

The copper surface was screened in detail in both its inhibitor- and inhibitor-free states using the Scanning Electron Microscope (SEM - Quattro S) technique. Two copper pieces were submerged in nitric acid alone (Blank) and another in nitric acid with 300 ppm of ROE combinations for 48 h in this experiment (Onyeachu et al., 2022; Saleh et al., 2022).

2.5

2.5 Theoretical calculation

Through Materials Studio's Dmol3 module, the quantum chemical properties of ROE are computed. Geometry optimization is the mathematical operation, GGA and PBE are the functional operators, DNP is levied as the basis set and a COMPASS was the force field (Chkirate et al., 2021; Shahmoradi et al., 2021; Pal and Das, 2022 ).

3 Results and Discussion

3.1

3.1 Extract characterization

Rosmarinus officinalis extract IR spectra were obtained using SPEACTUM-65 (PerkinElmer® FT-IR spectrometer) in the region of 4000 – 400 cm⁻¹. Fig. 1 shows the different infrared spectra of the various groups present in the extract. The presence of vibration at 3371 cm⁻¹ is related to the presence of a hydroxyl group (O—H) bond (Boukaoud et al., 2021). At 1684 cm⁻¹, a sharp peak is attributed to the carbon–oxygen or carbonyl group (C⚌O), and another vibration at 1016 cm⁻¹ is associated with the presence of a (C—O) single bond (Mintz et al., 2021). We note the occurrence of vibration between 1016 and 1455 cm⁻¹ associated with the presence of a Carboxylic acid's (O—H) bond (Karolina et al., 2022; Jiang et al., 2021). The most important compounds found in ROE are rosmarinic acid, carnosic acid, and carnasol, which are primarily responsible for the presence of antioxidants, inflammation, and anti-carcinogenic (Esmeeta et al., 2022; Erigoni, 2021).

IR spectrum of the different Rosmarinus officinalis extracts.

3.2

3.2 Mass loss method

Based on Table 3 and Fig. 2, we show the results of Cu mass loss in 1.00 M HCl in the absence or presence of amended inhibitor doses. According to Table 3, Cu corrosion rates in 1.0 M HCl were inhibited by all tested doses of the inhibitor. Inhibitor dose affects corrosion rate. It is evident that IE rises as inhibiting concentration increases (Alaoui et al., 2016).

Table 3 Different measurements of inhibition for the corrosive effects of 1 M HNO₃ on copper with different doses both with and without ROE at 25 °C.

[inh], ppm	θ	%IE
50	0.271	27.1
100	0.448	44.8
150	0.626	62.6
200	0.672	67.2
250	0.72	72.0
300	0.77	77.0

Effect of immersion times on mass loss of Cu in 1 M HNO3 with and without different doses of ROE at 25 °C.

3.3

3.3 Adsorption isotherm

The isotherm of adsorption is useful in determining the inhibition pathway. Also, isotherm diagrams can be used to visualize the inhibitor-metal interaction. It was tested if Langmuir, Freundlich, and Temkin diagrams were best suited for the task (Alaoui et al., 2016). Fig. 3 illustrates the approximate right correlation coefficient. A Langmuir adsorption isotherm can be observed in 1.0 M nitric acid solutions where ROE molecules adsorb with correlation coefficients and slopes close to 1. The K_ads The intersections of the lines could be used to calculate values. on the C/θ-axis and K_ads was connected to the standard adsorption-free energy ΔG^o_ads as follows:

(4)

\frac{C}{θ} = \frac{1}{K_{ads}} + C

Langmuir adsorption plot as C/θ vs C, M of ROE for corrosion of copper in 1 M HNO3 solution at 25 °C.

The value of the adsorption constant K_ads was calculated, and through it, the free energy ΔG^o_ads values were computed using the equation:

(5)

K = \frac{1}{55.5} \exp^{\frac{{- Δ G}_{ads}}{RT}}

Table 4 illustrates that the ROE molecules are thought to be electrostatically interconnected in an acidic solution when the ΔG°_ads value is around − 20 kJ mol⁻¹ or lower, while a value of − 40 kJ mol⁻¹ or higher indicates a charge exchange or transfer between the copper surface and the ROE molecules (Jafari et al., 2022). Using ΔG° _ads, it was confirmed that physical adsorption had taken place. The ΔG° _ads enthalpy values resulting from electrostatic interactions between charged molecules and charged metal (physisorption) range up to 41.9 kJ mol⁻¹, whereas those, resulting from chemisorption, range up to about 100 kJ mol⁻¹. Physisorption produces molecules with small absolute enthalpy values. When the examined chemicals are present, ΔS°_ads values were negative and large, indicating the increase in the ordering on the copper surface (Zhang et al., 2019).

Table 4 ROE adsorption data on a copper surface at various temperatures in 1 M HNO_3.

Temperature,^oC	K_ads × 10^-3 M⁻¹	-ΔG°_ads kJ/mol	ΔH°_ads kJ/mol	ΔS°_ads J mol⁻¹
25	8.8683	15.36	67.59	278.38
30	20.533	17.73		281.62
35	37.11952	19.54		282.92
40	45.599	20.39		281.13
45	51.177	21.0		278.69

3.4

3.4 Potentiodynamic polarization (PDP) measurements

As shown in Fig. 4, copper polarization in a 1 M HNO3 medium is characterized by typical curves. It is evident from the polarization curve that both current and voltage have increased in value until they have reached their highest peak without inhibition (Yang et al., 2019; Abd El Aziz et al., 2022). In response to the formation of Cu (NO3)2, the current value rapidly decreased after reaching its maximum value. The inhibitor significantly reduced cathodic and anodic current density. A change in the E_corr value is also noticed in the presence of (ROE). If the E_corr displacement is greater than 85 mV, an inhibitor may be classified as cathodic or anodic; otherwise, it may be classified as mixed. The current study indicates that the examined inhibitor is a mixed-type inhibitor because the maximum displacement in Ecorr is 85 mV (Yan et al., 2020). In Fig. 4, higher (ROE) concentrations inhibit Cu electrode anodic corrosion. Also, the cathodic reaction is suppressed to a lesser extent when (ROE) is present. As shown in Table 5, there is a reduction in anodic dissolution by ROE and a delay in hydrogen evolution reaction due to ROE, which results in values of βa that are higher than those obtained by a blank in the absence of ROE. Hence, the oxidation mechanism is suppressed by the (ROE), which controls the anodic reactions on the metal surface (Benarioua et al., 2019).

Potentiodynamic polarization curves for the dissolution of copper in 1 M HNO3 in the lack and existence of various doses of ROE at 25 °C.

Table 5 Corrosion potential (e_corr), corrosion current density (i_corr), Tafel slopes (β_a, β_c), degree of surface coverage(θ), and inhibition efficiency (%IE) of copper in 1 M HNO₃ at 25 °C for ROE.

Inhibitor	[inh] ppm	-E_corr Mv vs SCE	I_corrx10^-4 μA cm-2	βa, mV dec^-1	βc, mV dec^-1	C.R mpy	ϴ	%IE
Blank	0	16.20	512.0	318.7	–222.3	252.6	0.0	0.0
ROE	50	45.00	66.40	72.30	−207.3	32.75	0.870	87.0
	100	39.30	65.80	70.60	−188.8	32.47	0.871	87.1
	150	42.50	64.70	74.50	−198.4	31.92	0.874	87.4
	200	49.10	37.60	58.50	−203.1	18.56	0.926	92.6
	250	89.30	33.50	99.80	−227.9	16.53	0.935	93.5
	300	83.10	28.00	70.90	−216.7	13.83	0.945	94.5

3.5

3.5 Electrochemical impedance spectroscopy (EIS) measurements

We have also applied the EIS approach to investigate the corrosion behavior of copper in 1 M nitric acid solution, both in the lack and existence of various ROE concentrations (Dhouibi et al., 2021). Nyquist plots presented imperfect semicircles with a time constant due to the rough surface of the copper electrode. The diameter of the capacitive ring increases significantly when the inhibitor is added to the 1 M solutions of HNO₃, and this improvement becomes more pronounced as the doses of the inhibitor raise. These observations indicate the adsorption of inhibitory molecules on the copper surface and the creation of a protective film. This film reduces the active surface area of copper, improves its corrosion resistance, and greatly inhibits copper corrosion in the 1 M HNO₃ solution (Zhang et al., 2021). The impedance data in Table 6 indicate that the R_ct value increases as the inhibitor dose increases (Fouda et al., 2021), and this indicates that the inhibitory effect becomes stronger in acidic solutions and this was proved by calculating the chi-square (χ2) values shown in Table 7. Due to this, a protective layer is formed at the metal solution contact during copper dissolution, and a single semicircle was observed, suggesting that a single charge transfer mechanism took place and that this mechanism was unaffected by the bound molecule (Bedair et al., 2021). When the inhibitor dose increases, the capacitance of the double layer diminishes. There is a density difference between the electrical double layer and the insulating layer. A polarization and mass loss approach yield similar results in terms of percent IE acquisition.

Table 6 Copper electrochemistry kinetics in HNO3 with and without ROE concentrations.

Inhibitor	[inh] ppm	R_ct, Ω cm²	R_s x10^-3, Ω cm²	C_dl x10^-4, µFcm⁻²	ϴ	% IE
Blank	0	28.60	968.1	6.045	0.0	0.0
ROE	50	39.35	982.6	2.8	0.273	27.3
	100	63.98	910.5	5.83	0.553	55.3
	150	84.22	1778	4.45	0.660	66.0
	200	112.5	1463	3.83	0.746	74.6
	250	134.2	844.1	9.72	0.787	78.7
	300	231.3	827.4	2.41	0.876	87.6

Table 7 Chi Square (χ2) of R_ct.

Observed Value 1	Expected Value1	Chi Square 1 X 10^-4	Observed Value 2	Expected Value 2	Chi Square 2 X 10^-6	Observed Value 3	Expected Value 3	Chi Square 3 X 10^-4
28.512	28.612	4.400	28.661	28.656	111	28.908	28.729	10.203
39.352	39.285	1.071	39.352	39.349	0.0151	39.386	39.445	1.090
63.964	63.891	0.731	63.983	63.995	3.918	64.154	64.152	0.430
84.211	84.073	2.233	84.223	84.210	1.125	84.273	84.416	2.542
112.110	112.286	3.092	112.521	112.469	8.430	112.933	112.740	2.149
133.703	133.944	4.483	134.221	134.163	0.101	134.751	134.491	3.223
231.271	230.926	3.231	231.324	231.303	0.0487	231.643	231.861	3.144

All capacitance elements in Fig. 5 are replaced with constant phase elements (CPEs), namely CPE_f and CPE_dl. A solution resistance is represented by Rs, and a passive film's capacitance is represented by CPE_f. In passive films, R_f corresponds to the ionic resistance. Double layer corrosion area's capacitive behavior is described by CPE_dl, while charge transfer resistance is expressed as Rct (Zuñiga-Diaz et al., 2020). As shown in (Fig. 6a and Fig. 6b), Nyquist and Bode plots for Cu corrosion in 1 M HNO3 solution are plotted based on phase angle and frequency (Charoen-amornkitt et al., 2020). Calculate the double-layer capacitance, C_dl, for a circuit from the following equation:

(6)

C_{dl} = Y_{O} (ω_{\max}) n - 1

Equivalent circuit model used to fit experimental EIS.

Copper corrosion plots in 1 M HNO3 without and with ROE at 25 °C.

The Bode plots for the corrosion of copper in 1 M HNO3 in the lack and existence of various concentrations of ROE at 25 °C.

whereY₀ is the magnitude of the CPE, ω_max = 2πf_max, f_max is the frequency at which the imaginary component of the impedance is maximal and the factor n a lies between 0.50 and 1.0 (Laschuk et al., 2021). The similarity of the general shape of the curves (in the presence or absence of an inhibitor) shows that there is no change in the corrosion mechanism. As a further evidence, Bode plots inhibited by a phase angle increase were shown to have a greater degree of phase angle. The morphology of protected surfaces improved with an increase in phase angle values (Zhang et al., 2019). A concentration of ROE results in an enlargement in Nyquist curve diameters and phase angle values in Bode plots (Fig. 6b).

3.6

3.6 SEM examination

SEM experiments verify the adsorption of a layer of ROE on the copper surface. Fig. 7(a-c) show SEM micrographs of the surface of Cu alone and after 48 h of immersion in 1 M HNO₃ with adding 300 ppm of ROE. The metal surface appears clearly, while in the absence of ROE, we find clear damage to the copper surface due to the corrosion of HNO₃ (Fig. 7b). Nevertheless, the metal surface does not appear to corrode when compared to the examined compound (Fig. 7c). It was found that a thin layer of the extract formed on the surface of the copper, thus protecting the surface from corrosion.

SEM micrographs of the surface of Cu alone and after immersion in 1 MHNO3

3.7

3.7 Quantum chemical analysis

The stabilized molecular configuration of carnosic acid, rosmarinic acid, and carnosol is shown in Fig. 8, together with the associated border molecular orbital distribution graphs. The HOMO and LUMO orbitals represent the molecular structure's capacity to give and accept electrons, respectively (Choudhary et al., 2019). There are oxygen atoms, —OH, and C⚌O groups, and hydroxyl groups in all components of the extract, which act as electron donors (HOMO), and benzene rings that act as acceptors (LUMO). The energy gap (ΔE) can be calculated based on these two energies. The energy gap (ΔE) and dipole moment (μ) values of Carnosic acid, Rosmarinic acid, and Carnosol. As shown in 10(a), the ΔE values of Carnosic acid, Rosmarinic acid, and Carnosol are 4.620 eV, 3.093 eV, and 5.284 eV, respectively. Previous researchers have revealed a relationship between decreased energy gaps and higher inhibitor efficiencies (Chen et al., 2020; Errahmany et al., 2020). A molecular orbital surface with a low unoccupied molecular orbital surface (LUMO) appears along with its highest occupied molecular orbital surface (HOMO). Surfaces with HOMO or LUMO charge indicate which sites of the molecule might donate electrons to the metal, and surfaces with LUMO charge indicate which electrons would be regifted to the inhibitor (Sayed and El-Lateef, 2020; Hadisaputra et al., 2020). A HOMO is primarily defined by oxygen atoms and the π bond on the benzene ring that is responsible for resonance. At the same time, the LUMO is centered around carbon atoms. The ΔE value has the potential to estimate the inhibitor molecule's reactivity to the metal atom; lower ΔE values may indicate better inhibition efficiency (Obi-Egbedi et al., 2011; Niamien et al., 2012). From these DFT calculations and the trends described, it was defined that Rosmarinic acid (ΔE = 3.082) as shown in Table 8 behaved as a superior corrosion inhibitor relative due to its lower ΔE. On the other hand, the dipole moment (DM) does not play an essential role in determining the efficiency of inhibition (Rodríguez-Valdez et al., 2005).

Optimized structure, HOMO, and LUMO of ROE components.

Table 8 Quantum Chemical parameters.

Structure	E_HOMO	E_LUMO	ΔE = E_LUMO- E_HOMO	Dipole moment
Carnosic acid	−6.386	−1.766	4.620	3.2100
Rosmarinic acid	−5.299	−1.526	3.093	2.4760
Carnosol	−5.435	−0.151	5.284	4.3777

3.8

3.8 Molecular dynamics analysis

The adsorption structure of carnosic acid, rosmarinic acid, and carnosol at the Cu(1 1 1) surface is depicted in Fig. 9 in the gaseous state. At the Cu(1 1 1) interface, carnosic acid, rosmarinic acid, and carnosol are mostly adsorbed in addition to adsorption to achieve a high level of protection for the Cu substrate (Belakhdar et al., 2020). Following adsorption to the Cu (1 1 1) interface, their binding energy is determined by formulas (6) and (7):

(6)

E_{interact} = E_{tot} - (E_{sub} + E_{inh})

(7)

E_{Binding} = - E_{interact}

Top and Side View of adsorption of ROE components on Cu surface.

A list of the binding energies of carnosic acid, rosmarinic acid, and carnosol is presented in Table 9. The E_Binding of Rosmarinic acid on the Cu (1 1 1) interface is signally greater than that of Carnosic acid and Carnosol. Therefore, Rosmarinic acid plays a vital effect in the adsorption of ROE onto the copper interface. It is evident from E_ads negative results that the copper substrate was strongly adsorption with carnosic acid, rosmarinic acid, and carnosol (Galai et al., 2020). Compared to Carnosic acid, and Carnosol, Rosmarinic acid exhibits greater adsorption energy, indicating it performs better as an inhibitor for copper protection in 1.0 M nitric acid. All available data is accurate and supported by this theoretical analysis. Lastly, (ROE) inhibitors offer great protection against corrosion.

Table 9 Estimated energies from adsorption of ROE on Cu surface.

Structures	Total energy	Binding energy	Rigid adsorption energy	Deformation energy
Carnosic acid	−64.8866	−87.2233	−91.5315	4.3082
Rosmarinic acid	−177.2225	−104.4682	−105.0472	0.5790
Carnosol	−151.6792	−97.5361	−99.1319	1.5957

3.9

3.9 Mechanism of corrosion inhibition

By adsorption at the interface between the Cu and solution, the (ROE) compound inhibited corrosion of Cu in 1 M HNO3 using electrochemical tests and mass loss experiments. During the mechanism of action of an (ROE) inhibitor, the inhibitor adsorption at the surface of the metal interface is regarded as the initial stage. There are four ways that organic substances can adsorb on a metal surface, namely:

Charged molecules interact electrostatically with charged metals.
Molecular electrons interact with metals through their lone pairs.
Interaction of π electrons with metal.
A combination of the above (Chaouiki et al., 2022). Complete adsorption (a combination of all adsorption types mentioned above) was found for inhibitors adsorbing on the surface of Cu, based on adsorption parameters calculated.

It is possible to form coordinated bonds with the inhibitory molecules by electrons transferring from the adsorbed species to the metal surface. Taking a look at the constitution of the examined compound, it was noted that in all compounds there are pairs of unshared electrons in oxygen atoms creating a σ-bond with copper. In addition, the double bonds in the substance aid d electrons of metal to be donated back to the π* orbital (Cao et al., 2019; Cao et al., 2020). Inhibitors' efficiency on copper surfaces and effectiveness are all affected by all of this, which depends largely on their type and quantity (Abdel Hameed et al., 2020; Omran and Abdel-Salam, 2020).

4 Conclusions

In experiments, it was proven that (ROE) works as a mixed-type inhibitor to inhibit copper corrosion in 1.0 M HNO₃ solution. This compound exhibited Langmuir adsorption isotherms upon adsorption on copper surfaces, which corresponds to inhibition. The spontaneity of the reaction was inferred due to the presence of the negative value of ΔG⁰_ads. Using DFT, it was found that the compound has a greater inhibition strength (ROE) because it can transfer electrons from the highest occupied orbital to the lowest unoccupied orbital (LUMO). During corrosion, metal receives electrons from compounds depending on their relative electron donation abilities. A comparison between the results and the measurements was found to be successful.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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[11] Cao S., Liu D., Ding H., Wang J., Lu H., Gui J., . Corrosion inhibition effects of a novel ionic liquid with and without potassium iodide for carbon steel in 0.5 M HCl solution: an experimental study and theoretical calculation. J. Mol. Liq.. 2019;275:729-740.
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[12] Cao S., Liu D., Ding H., Lu H., Gui J., . Towards understanding corrosion inhibition of sulfonate/carboxylate functionalized ionic liquids: an experimental and theoretical study. J. Colloid Interface Sci.. 2020;579:315-329.
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[13] Chaouiki A., Chafiq M., Al-Moubaraki A.H., Bakhouch M., El Yazidi M., Ko Y.G., . Electrochemical behavior and interfacial bonding mechanism of new synthesized carbocyclic inhibitor for exceptional corrosion resistance of steel alloy: DFTB, MD and experimental approaches. Arabian J. Chem.. 2022;104323
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[15] Chen S., Chen S., Zhu B., Huang C., Li W., . Magnolia grandiflora leaves extract as a novel environmentally friendly inhibitor for Q235 steel corrosion in 1 M HCl: combining experimental and theoretical researches. J. Mol. Liq.. 2020;311:113312
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[16] Chen S., Zhu B., Liang X., . Corrosion inhibition performance of coconut leaf extract as a green corrosion inhibitor for X65 steel in hydrochloric acid solution. Int. J. Electrochem. Sci. 2020;15(1):1.
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[17] Chkirate K., Azgaou K., Elmsellem H., El Ibrahimi B., Sebbar N.K., Benmessaoud M., El Hajjaji S., Essassi E.M., . Corrosion inhibition potential of 2-[(5-methylpyrazol-3-yl) methyl] benzimidazole against carbon steel corrosion in 1 M HCl solution: combining experimental and theoretical studies. J. Mol. Liq.. 2021;321:114750
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[19] Dhouibi I., Masmoudi F., Bouaziz M., Masmoudi M., . A study of the anti-corrosive effects of essential oils of rosemary and myrtle for copper corrosion in chloride media. Arabian J. Chem.. 2021;14(2):102961
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[20] El Faydy M., Galai M., Touir R., El Assyry A., Ebn Touhami M., Benali B., . Experimental and theoretical studies for steel XC38 corrosion inhibition in 1 M HCl by N-(8-hydroxyquinolin-5-yl)-methyl)-N-phenylacetamide. J. Mater. Environ. Sci.. 2016;7(4):1406-1416.
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[29] Hamadi L., Mansouri S., Oulmi K., Kareche A., . The use of amino acids as corrosion inhibitors for metals: a review. Egyptian J. Petroleum. 2018;27(4):1157-1165.
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[31] Huang L., Chen W.-Q., Wang S.-S., Zhao Q., Li H.-J., Wu Y.-C., . Starch, cellulose and plant extracts as green inhibitors of metal corrosion: a review. Environ. Chem. Lett. 2022:1-30.
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[35] Kadhim A., Al-Amiery A., Alazawi R., Al-Ghezi M., Abass R., . Corrosion inhibitors. A review. Int. J. Corrosion Scale Inhibition. 2021;10(1):54-67.
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[36] Kadiri L., Galai M., Ouakki M., Essaadaoui Y., Ouass A., Cherkaoui M., Rifi E.-H., Lebkiri A., . Coriandrum Sativum. L seeds extract as a novel green corrosion inhibitor for mild steel in 1.0 M hydrochloric and 0.5 M sulfuric solutions. Anal. Bioanal. Electrochem.. 2018;10:249-268.
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[37] Karolina D., Maja M.-S., Magdalena D.-S., Grażyna Ż., . Identification of treated Baltic amber by FTIR and FT-Raman–a feasibility study. Spectrochimica Acta Part A: Mol. Biomol. Spectrosc. 2022:121404.
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[38] Kompelly A., Kompelly S., Vasudha B., Narender B., . Rosmarinus officinalis L.: an update review of its phytochemistry and biological activity. J. Drug Delivery Therapeutics. 2019;9(1):323-330.
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[39] Kumari V., Singh P.P., Kaushal S., . Synthesis and applications of metal-organic frameworks and graphene-based composites: a review. Polyhedron. 2022;115645
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[44] Mintz K.J., Bartoli M., Rovere M., Zhou Y., Hettiarachchi S.D., Paudyal S., Chen J., Domena J.B., Liyanage P.Y., Sampson R., . A deep investigation into the structure of carbon dots. Carbon. 2021;173:433-447.
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[46] Niamien P., Essy F., Trokourey A., Yapi A., Aka H., Diabate D., . Correlation between the molecular structure and the inhibiting effect of some benzimidazole derivatives. Mater. Chem. Phys.. 2012;136(1):59-65.
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