Atomic-scale investigation onto the inhibition process of three 1,5-benzodiazepin-2-one derivatives against iron corrosion in acidic environment

doi:10.1016/j.colcom.2020.100279

Colloid and Interface Science Communications

Volume 37, July 2020, 100279

https://doi.org/10.1016/j.colcom.2020.100279 Get rights and content

Highlights

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In silico study was carried out on three 1,5-benzodiazepin-2-one derivatives used as corrosion inhibitors.
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The protonation process has affected the reactivity of investigated inhibitors set.
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A good correlation was obtained between the inhibition efficiency and the adsorption energy of studied inhibitors.
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The potential inhibition mechanism of the studied inhibitors set was proposed.
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Predicting study on no-tested metallic materials was carried out.

Abstract

In the aim to understand the inhibition action of three 1,5-benzodiazepin-2-one derivatives (i.e. DMBD: 4,7-dimethyl-1,5-benzodiazepin-2-one, PBD: 3-phenyl-1,5-benzodiazepin-2-one, MPBD: 4-methyl-7-phenyl-1,5-benzodiazepin-2-one) against the dissolution of iron in acidic medium, both DFT-based calculations and Monte Carlo-SAA simulations were carried out. As a result, the protonation process was unfavorably affected the reactivity of investigated inhibitors. Further, the solvation free energy (∆G_Solv) can be used as a parameter to inspect the inhibition performance of organic inhibitors. According to Monte Carlo-SAA simulations, the investigated inhibitors exhibited a great tendency to replace pre-adsorbed corrosive entities onto the iron surface and then forming a protective film via a parallel adsorption orientation. Finally, a predicting study pointed out that the MPBD compound is expected to act as a moderate inhibitor for aluminum and copper metals, while lower inhibition efficiency is anticipated in the case of tin in acidic environments.

Graphical abstract

Introduction

Iron is the most important used metallic material in the word, which has an extensive variety of applications [1]. This is due to its ductility, high tensile strength, and availability [2]. However, its contacts with acid environments, e.g. during acid cleaning and descaling treatments, involve its severe degradation [3]. In the aim to prevent iron corrosion, inhibitor compounds are added. Employing corrosion inhibitors is known as the most practical solution to prevent metals corrosion [4,5].

According to corrosion literature [[6], [7], [8]], numerous organic molecules containing heteroatoms (i.e. N, O, S) and/or p-electrons and conjugated double bonds were reported as efficient corrosion inhibitors for iron and its alloys. In this context, three new synthesized 1,5-benzodiazepin-2-one derivatives, namely 4,7-dimethyl-1,5-benzodiazepin-2-one (DMBD), 3-phenyl-1,5-benzodiazepin-2-one (PBD) and 4-methyl-7-phenyl-1,5-benzodiazepin-2-one (MPBD), have been reported as effective corrosion inhibitors for iron in molar hydrochloride solution [9]. Fig. 1 illustrates the molecular structure of reported compounds and experimentally obtained inhibition efficiencies (IE, %) at 0.01 M. As can be seen from this figure, MPBD derivative exhibited the highest prevention effectiveness in comparison with other evaluated derivatives. This shows the beneficial effect of methyl and phenyl substituents in improving the corrosion inhibition of 1,5-benzodiazepin-2-one compound.

In the last decade, the computational approach was widely used to study the corrosion inhibition process of several organic compounds under the atomic scale [[10], [11], [12], [13]]. Such interest is due to the development of calculation algorithms and the improvement of the hardware and software capabilities [14]. Among employed computational methods, DFT and molecular mechanics-based methods, like Monte Carlo simulations, have been frequently used [[15], [16], [17]]. Returning to 1,5-benzodiazepin-2-one derivatives, until now there is no report that treats their protection ability towards iron corrosion under an atomic scale using computational chemistry methods.

Given this, the current study aims to associate previously observed inhibition efficiencies with the structural properties of studied inhibitors (i.e. DMBD, PBD and MPBD), as well as understanding in depth their inhibition mechanism. Taking into account the effect of acidic medium on the protonation state of inhibitors, DFT-based calculations and Monte Carlo-SAA simulations were performed. Furthermore, this in silico investigation was extended to predict the potential inhibitive effect of MPBD derivative against the corrosion of non-tested metallic materials, namely aluminum, copper and tin.

Section snippets

DFT calculations

DFT calculations were carried out using B3LYP functional with 6–311++g(d,p) basis set in aqueous phase [[18], [19], [20]]. The solvation effects were considered by employing integral equation formalism polarizable continuum model (IEFPCM) setting water as a solvent [21]. In addition to neutral inhibitor forms, the protonated forms (see Fig. 1) were also taking into consideration during the calculations process; this is due to the high acidity of used medium (i.e. 1 M HCl) [10], which can

Global reactivity

Nowadays, DFT-based methods have begun as effective calculation tools for studying inhibitor/metal systems. For this purpose, DFT/B3LYP/6–311++g(d,p) theoretical level was used to perform this study under the solvation condition. Fig. 4 displays, in part, the optimized molecular structures of studied inhibitors in neutral and protonated forms.

In order to mimic the real inhibition systems, in which hydrochloric acid was used, DFT calculations were carried out both for neutral and protonated

Conclusion

In summary, DFT-based calculations and Monte Carlo-SAA simulations were carried out to understand the corrosion inhibition efficiencies of three 1,5-benzodiazepin-2-one derivatives (i.e. DMBD, PBD, and MPBD) against iron corrosion in molar hydrochloride solution. The main conclusions of the current work are:

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The protonation process of studied inhibitors in the used medium was considered and confirmed by obtained protonation affinity values. Such a process was unfavorably affected the reactivity

Author contribution

B.E.I. planned and designed the whole study, did the theoretical calculations, write the manuscript and finalized the manuscript.

References (53)

R. Kumar et al.
Experimental and theoretical investigations of a newly synthesized azomethine compound as inhibitor for mild steel corrosion in aggressive media: a comprehensive study
J. Mol. Liq.
(2018)
P. Dohare
Pyranpyrazole derivatives as novel corrosion inhibitors for mild steel useful for industrial pickling rocess: experimental and quantum chemical study
J. Ind. Eng. Chem.
(2017)
B. El Ibrahimi
Amino acids and their derivatives as corrosion inhibitors for metals and alloys
Arab. J. Chem.
(2020)
C. Verma
Adsorption characteristics of green 5-arylaminomethylene pyrimidine-2,4,6-triones on mild steel surface in acidic medium: experimental and computational approach
Results Phys.
(2018)
S. John
Corrosion inhibition properties of 1,2,4-Hetrocyclic systems: electrochemical, theoretical and Monte Carlo simulation studies
Egypt. J. Pet.
(2017)
B. El Ibrahimi
Computational study of some triazole derivatives (un- and protonated forms) and their copper complexes in corrosion inhibition process
J. Mol. Struct.
(2016)
M.K. Awad et al.
Computational simulation of the molecular structure of some triazoles as inhibitors for the corrosion of metal surface
J. Mol. Struct. : THEOCHEM
(2010)
A. Aouniti et al.
Correlation between inhibition efficiency and chemical structure of some amino acids on the corrosion of Armco Iron in molar HCl
Int. J. Electrochem. Sci.
(2013)
G. Gece
The use of quantum chemical methods in corrosion inhibitor studies
Corros. Sci.
(2008)
B. El Ibrahimi
Understanding the influence of solution's pH on the corrosion of tin in saline solution containing functional amino acids using electrochemical techniques and molecular modeling
Surf. Interfaces
(2019)

S. Erdogan

A computational study on corrosion inhibition performances of novel quinoline derivatives against the corrosion of iron

J. Mol. Struct.

(2017)

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Atomic-scale investigation onto the inhibition process of three 1,5-benzodiazepin-2-one derivatives against iron corrosion in acidic environment

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

DFT calculations

Global reactivity

Conclusion

Author contribution

J. Mol. Liq.

J. Ind. Eng. Chem.

Arab. J. Chem.

Results Phys.

Egypt. J. Pet.

J. Mol. Struct.

J. Mol. Struct. : THEOCHEM

Int. J. Electrochem. Sci.

Corros. Sci.

Surf. Interfaces

J. Mol. Struct.

J. King Saud Univ. Sci.

Electrochim. Acta

Corros. Sci.

J. Colloid Interface Sci.

Corros. Sci.

J. Taiwan Inst. Chem. Eng.

Carbohydr. Res.

J. Saudi Chem. Soc.

Appl. Surf. Sci.

Process Saf. Environ.

Chem. Phys. Lett.

Corros. Sci.

Corros. Sci.

J. Mol. Struct.

J. Mol. Struct.