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Amin, Hatem
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article
Experimental and DFT Atomistic Insights into the Mechanism of Corrosion Protection of Low-Carbon Steel in an Acidic Medium by Polymethoxyflavones from Citrus Peel Waste
Abstract
<jats:p>Developing green anticorrosive films is gaining great attention in science and engineering. Citrus fruit peels are mainly discarded as waste, although they can be an excellent repository of phytochemicals, that can be exploited as mitigating agents for corrosion. Herein, we report the high anticorrosion activity of a citrus extract for low-carbon steel in 1 M HCl solution at different temperatures. The main extract constituents were identified by MS and NMR. Two polymethoxyflavones (PMFs), namely nobiletin and heptamethoxyflavone, were identified as major constituents of the extract and the crude PMFs-based extract was investigated for corrosion protection. Using potentiodynamic polarization, weight loss and electrochemical impedance spectroscopy (EIS) methods, this extract revealed improved inhibition efficiency of 94%. The inhibition mechanism was elucidated by considering electrochemical kinetics and adsorption thermodynamics. SEM and UV–vis supported the electrochemical results. PMFs-based extract acted as a mixed-type inhibitor with a Langmuir model of adsorption. Importantly, DFT simulations provided atomic-level insights into the inhibition mechanism and unraveled donor-acceptor interactions between the methoxy groups of PMFs and iron atoms, facilitating the formation of a stable inhibition adsorption layer, and thus supporting the experimental findings. In addition to the physical barrier effect of PMF inhibitor, <jats:italic>π</jats:italic>-back bonding effect between PMF and steel was suggested.</jats:p><jats:p><jats:inline-formula><jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="jesacfa69-ga.jpg" xlink:type="simple" /></jats:inline-formula></jats:p>