Density Functional Theory Studies on New Possible Biobased Gemini Corrosion Inhibitors Derived from Fatty Hydrazide Derivatives.

Several new possible biobased corrosion inhibitors derived from fatty hydrazide derivatives were analyzed using quantum chemical calculations via the density functional theory method to investigate the chemical reactivity and inhibition efficiencies against corrosion in metal steel. The study confirmed that the fatty hydrazides showed significant inhibitive performances based on their electronic properties, revealing band gap energies of 5.20 to 7.61 eV between the HOMO and LUMO. These energy differences decreased from 4.40 to 7.20 eV when combined with substituents of varying chemical compositions, structures, and functional groups, associated with higher inhibition efficiency. The most promising fatty hydrazide derivatives are terephthalic acid dihydrazide combined with a long-chain alkyl chain, which resulted in the lowest energy difference of 4.40 eV. Further inspection showed that the fatty hydrazide derivatives' inhibitive performances increased with increasing carbon chain length [from 4 (4-s-4) to 6 (6-s-6)], with a concomitant increase and decrease in hydroxyl and carbonyl groups, respectively. Fatty hydrazide derivatives containing aromatic rings also showed increased inhibition efficiencies following their contribution to improve the compounds' binding ability and adsorption on the metal surface. Overall, all data were consistent with previously reported findings, envisaging the potential of fatty hydrazide derivatives as effective corrosion inhibitors.

DFT Calculation and MD Simulation Studies on Gemini Surfactant Corrosion Inhibitor in Acetic Acid Media.

Gemini surfactant corrosion inhibitor (CI) is one type of CI mainly used in mitigating corrosion in the complex system of oil/gas production industries. Computer modeling methods such as density functional theory (DFT) calculation and molecular dynamic (MD) simulation are required to develop new CI molecules focusing on their application condition as a prediction or screening process before the physical empirical assessment. In this work, the adsorption inhibition efficiencies of two monomer surfactants (2B and H) and their respective Gemini structures with the addition of different spacers (alkyl, benzene, ester, ether, and ketone) are investigated using DFT calculation and MD simulation method in 3% sodium chloride (NaCl), and 1500 ppm acetic acid solutions. In DFT calculation, 2B-benzene molecules are assumed to have the most promising inhibition efficiency based on their high reactivity and electron-donating ability at their electron-rich benzene ring region based on the lowest bandgap energy (0.765 eV) and highest HOMO energy value (-2.879 eV), respectively. DFT calculation results correlate with the adsorption energy calculated from MD simulation, where 2B-benzene is also assumed to work better as a CI molecule with the most adsorption strength towards Fe (110) metal with the highest negative adsorption energy value (-1837.33 kJ/mol at temperature 323 K). Further, diffusion coefficient and molecular aggregation analysis in different CI concentrations through MD simulation reveals that only a small amount of Gemini surfactant CI is needed in the inhibition application compared to its respective monomer. Computer simulation methods successfully predict and screen the Gemini surfactant CI molecules that can work better as a corrosion inhibitor in acetic acid media. The amount of Gemini surfactant CI that needs to be used is also predicted. The future planning or way forward from this study will be the development of the most promising Gemini surfactant CI based on the results from DFT calculation and MD simulations.