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