Key Takeaways & Executive Findings
- •• Novel amino acid derivatives P-Meth and P-Cys were synthesized via a one-step acylation, achieving corrosion inhibition efficiencies of 95.6% and 93.1% for Q235 steel in 1 M HCl, respectively. • The derivatives significantly reduce corrosion rates (from 4.542 to 0.202 and 0.312 mg·h−1·cm−2) and enhance charge transfer resistance by 12-fold and 9-fold, respectively. • Adsorption on the steel surface is predominantly chemical, with minimal physical contribution, as confirmed by experimental and theoretical analyses. • Molecular dynamics simulations reveal higher binding energy for P-Meth, correlating with its superior inhibition performance, offering a green and cost-effective corrosion protection strategy.
Abstract
Amino acids have emerged as promising green alternatives to replace toxic inhibitors in corrosion protection applications. In this study, we present a one-step synthetic approach to get 4-(tert-butyl)benzoyl)methionine (P-Meth) and 4-(tert-butyl)benzoyl)cysteine (P-Cys) through the acylation reactions between methionine or cysteine and p-tert-butylbenzoic acid, respectively, which exhibit a super protective performance toward metals against corrosion. The corrosion rates of Q235 steel in 1 M HCl were reduced from 4.542 to 0.202 and 0.312 mg·h−1·cm−2 in the presence of 100 mg·L−1 P-Meth and P-Cys, respectively. The surface structures of Q235 steel remained unbroken after 12 h in 1 M HCl medium. The charge transfer resistances of corrosion reactions were enhanced by 12 and 9 times in the presence of P-Meth and P-Cys, respectively. P-Meth and P-Cys were adsorbed onto the Q235 steel via chemical actions, which were accompanied by minimal physical action. Molecular dynamic simulations demonstrate the higher binding energy of P-Meth onto Q235 steel than P-Cys. The study contributes to the corrosion protection of metals with green and environmentally friendly methods.
1. Introduction
Corrosion inhibitors have gained prominence as a burgeoning and extensively embraced approach for the prevention of metal corrosion owing to their practicality and economic viability [1–2]. A heightened focus has been allotted to the development of environmentally friendly corrosion inhibitors, which is driven by the increased emphasis on environmental protection and the need for cost-effective solutions [3]. Numerous ecofriendly organic inhibitors, including carbohydrates [4], lignin [5], ionic liquids [6], expired drugs [7], and amino acids [8–10], have been reported. However, their practical application in the industry poses challenges. The extraction process of carbohydrates and lignin is laborious [11], and the synthesis of ionic liquids typically involves multi-step procedures, which results in elevated costs [12]. By contrast, their abundant natural availability, low toxicity, and excellent solubility make amino acids as the ideal inhibitor materials.
Amino acids exhibit a notable corrosion-inhibiting effect primarily at high concentrations, which were usually used as the specific additives [13–17]. Electrochemical and computational analysis were conducted in 1 M HCl containing 0.01 M cysteine, L-Histidine, L-Tryptophan, and L-Serine for the corrosions of mild steel, and the inhibition efficiencies (IE) were 85.1%, 93.4%, 96.3%, and 45.1%, respectively [18]. It suggested that abundant active atoms such as N and S benefited to promote the protective abilities. Amino acids inherently possess carboxyl and amino groups, with some featuring heteroatoms (i.e., O, S, and N) or conjugated structures and can be easily functionalized. Encouragingly, modifications such as varying the length of the carbon skeleton [19], incorporating heterocycles and heteroatoms [20–21], and attaching polar groups [22] to amino acids enhance their anticorrosion performance. These insights substantially informed our work, which indicates that the chemical modification of amino acids represents a viable and efficient approach to achieve the outstanding IE and develop environmentally friendly corrosion inhibitors.
Methionine and cysteine are distinguished by their –SCH3 or –SH groups, serving as excellent centers for the adsorptions on metal surfaces [23]. However, their satisfactory anticorrosion efficiency is only achievable at relatively high concentrations [24]. In this study, to increase the corrosion inhibition performance of these natural products, we conducted acylation reactions to functionalize methionine and cysteine with p-tert-butylbenzoic acid, which resulted in the formation of derivatives referred to as 4-(tert-butyl)benzoyl)methionine (P-Meth) and 4-(tert-butyl)benzoyl)cysteine (P-Cys), respectively. Subsequently, we assessed the corrosion inhibition performance of these derivatives.
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Chaoyi Li, Minghao Su, Tianyi Hou, Yuhe Shi, Junrong Huang, Jing Qing, Wenxin Niu, Yinghe Zhang, Ling Zhang, Hengzhi You (2025). Two new amino acid derivatives as green corrosion inhibitors against Q235 steel in HCl solution: Experimental and theoretical investigations. Int. Journal of Minerals, Metallurgy and Materials (矿物冶金与材料学报). https://doi.org/10.1007/s12613-024-3011-8
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Frequently Asked Questions
What are the novel amino acid derivatives synthesized in this study?
The study synthesized two new amino acid derivatives: 4-(tert-butyl)benzoyl)methionine (P-Meth) and 4-(tert-butyl)benzoyl)cysteine (P-Cys), via a one-step acylation reaction between methionine or cysteine and p-tert-butylbenzoic acid.
How effective are P-Meth and P-Cys as corrosion inhibitors for Q235 steel in HCl?
At a concentration of 100 mg/L, P-Meth and P-Cys reduced the corrosion rate of Q235 steel in 1 M HCl from 4.542 to 0.202 and 0.312 mg·h−1·cm−2, respectively, corresponding to inhibition efficiencies of approximately 95.6% and 93.1%.
What is the mechanism of corrosion inhibition by these derivatives?
The derivatives adsorb onto the steel surface primarily through chemical interactions, with minimal physical adsorption. This is supported by experimental results and molecular dynamics simulations, which show higher binding energy for P-Meth.
Why are these amino acid derivatives considered green corrosion inhibitors?
Amino acids are naturally abundant, low in toxicity, and biodegradable. The synthesis uses a simple one-step acylation, avoiding toxic reagents, making the derivatives environmentally friendly alternatives to conventional inhibitors.
What are the practical implications of this research?
The findings provide a cost-effective and eco-friendly approach for protecting metals against corrosion in acidic environments, which is valuable for industries such as oil and gas, chemical processing, and infrastructure maintenance.
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