Unraveling Bonding Mechanisms and Electronic Structure of Pyridine Oximes on Fe(110) Surface: Deeper Insights from DFT, Molecular Dynamics and SCC-DFT Tight Binding Simulations.

The development of corrosion inhibitors with outstanding performance is a never-ending and complex process engaged in by researchers, engineers and practitioners. The computational assessment of organic corrosion inhibitors' performance is a crucial step towards the design of new task-specific materials. Herein, the electronic features, adsorption characteristics and bonding mechanisms of two pyridine oximes, namely 2-pyridylaldoxime (2POH) and 3-pyridylaldoxime (3POH), with the iron surface were investigated using molecular dynamics (MD), and self-consistent-charge density-functional tight-binding (SCC-DFTB) simulations. SCC-DFTB simulations revealed that the 3POH molecule can form covalent bonds with iron atoms in its neutral and protonated states, while the 2POH molecule can only bond with iron through its protonated form, resulting in interaction energies of -2.534, -2.007, -1.897, and -0.007 eV for 3POH, 3POH+, 2POH+, and 2POH, respectively. Projected density of states (PDOSs) analysis of pyridines-Fe(110) interactions indicated that pyridine molecules were chemically adsorbed on the iron surface. Quantum chemical calculations (QCCs) revealed that the energy gap and Hard and Soft Acids and Bases (HSAB) principles were efficient in predicting the bonding trend of the molecules investigated with an iron surface. 3POH had the lowest energy gap of 1.706 eV, followed by 3POH+ (2.806 eV), 2POH+ (3.121 eV), and 2POH (3.431 eV). In the presence of a simulated solution, MD simulation showed that the neutral and protonated forms of molecules exhibited a parallel adsorption mode on an iron surface. The excellent adsorption properties and corrosion inhibition performance of 3POH may be attributed to its low stability compared to 2POH molecules.

Cinnamaldehyde-modified chitosan as a bio-derived corrosion inhibitor for acid pickling of copper: Microwave synthesis, experimental and computational study.

Chitosan (CS) was cross-linked using cinnamaldehyde (Cinn) in a single step procedure following microwave irradiation to produce cinnamaldehyde-modified chitosan (Cinn-CS). The synthesized Cinn-CS was used as a novel corrosion inhibitor for copper in 1 M hydrochloric acid. A comprehensive electrochemical investigation using the impedance measurements, and potentiodynamic polarization was undertaken, supported with surface analysis and computational studies. The inhibitor Cinn-CS functioned by adsorption on the copper surface and showed an inhibition efficiency of >89% at a dose of 1000 mgL-1. The charge transfer resistance showed a rise with increase in inhibitor dosage to the corrosive medium, and the corrosion currents showed a significant decrease with the addition of the inhibitor. The Cinn-CS displayed a mixed type of inhibition performance with cathodic nature. The study of the copper surface using scanning electron microscopy depicted a considerably smooth morphology in the presence of the adsorbed Cinn-CS. The computational studies indicated that the Cinn-CS Schiff base shows better adsorption behavior compared to the parent molecules of chitosan and cinnamaldehyde and can show an inhibition performance in the neutral, and the protonated form.

Aminotriazolethiol-functionalized chitosan as a macromolecule-based bioinspired corrosion inhibitor for surface protection of stainless steel in 3.5% NaCl.

Chitosan was chemically functionalized using aminotriazolethiol in a facile single-step synthesis. The macromolecule was evaluated as an inhibitor for corrosion of stainless steel in 3.5% NaCl solution. A detailed electrochemical investigation employing electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PDP) was performed, which showed that the inhibitor acts by adsorption on the steel surface and shows a mixed type behavior with the prevalence of cathodic behavior. The new inhibitor aminotriazolethiol-modified chitosan (ATT-Cht) exhibited excellent water solubility and behaved as an efficient inhibitor against corrosion of stainless steel in 3.5% NaCl showing a corrosion inhibition efficiency of 97.8% at a concentration as low as 100 mg L-1. The results of surface studies using scanning electron microscopy along with energy dispersive X-ray spectroscopy supported the adsorption of the inhibitor on the steel surface.

The role of pH in corrosion inhibition of tin using the proline amino acid: theoretical and experimental investigations.

Herein, the effect of a mediums' pH on the interfacial interactions between proline (Pro) amino acid and tin metal was studied. In this work, acidic and near-neutral pH values were considered. DFT-based calculations and Monte Carlo simulations were carried out in the aqueous phase to understand the role of pH in Pro/tin interactions. To confirm this role in terms of inhibition efficiency, the CC and AC electrochemical techniques were used. Based on the calculated parameters, it was outlined that the partially protonated Pro form exhibits significant affinity to interact with tin metal in near-neutral media. However, in acidic media, its affinity is decreased, whereas the full protonated form was found to be solvated in the solution and its interaction with the tin surface was not favorable. These findings indicated that the inhibition capability of Pro for tin could be better in near-neutral media than in acidic media. This expected behavior was confirmed experimentally, wherein an inhibition effectiveness of around 65% was obtained for Pro at pH 5, and 16% was observed at pH 2. Additionally, the results highlight the capability of employing computational studies to predict the prevention efficiency of anti-corrosion compounds by varying the solution pH.

Chitosan polymer as a green corrosion inhibitor for copper in sulfide-containing synthetic seawater.

The influence of chitosan on the copper corrosion in sulfide polluted synthetic seawater (SSW) containing 20 ppm of sulfide has been investigated for the first time. Potentiodynamic polarization measurements, electrochemical impedance spectroscopy at the open circuit potential and weight loss measurements were employed to assess the corrosion inhibition ability of chitosan. The impedance studies revealed that in the presence of chitosan at various concentrations, the charge transfer resistance increases. At a concentration of 800 ppm, chitosan exhibited a corrosion inhibition efficiency of 89% following physical adsorption. The influence of temperature and immersion time was studied in sulfide-contaminated synthetic seawater and significant inhibition was observed even after 90 days. SEM-EDS studies confirm the absence of the deterioration products on copper surface.

A comparative study of electrochemical oxidation of methidation organophosphorous pesticide on SnO2 and boron-doped diamond anodes.

BACKGROUND: Electrochemical oxidation considered to be among the best methods in waste water desalination and removing toxic metals and organic pesticides from wastewater like Methidathion. The objective of this work is to study the electrochemical oxidation of aqueous wastes containing Methidathion using boron doped diamond thin-film electrodes and SnO2, and to determine the calculated partial charge and frontier electron density parameters. RESULTS: Electrolysis parameters such as current density, temperature, supporting electrolyte (NaCl) have been optimized. The influences of the electrode materials on methidathion degradation show that BDD is the best electrode material to oxidize this pesticide organophosphorous. Energetic cost has been determinate for all experiments. The results provide that 2 % of NaCl, 60 mA cm(-2) and 25 ºC like the optimized values to carry out the treatment. For BDD the achieved Chemical Oxidation Demand reduction was about 85 %, while for SnO2 it was about 73 %. The BDD anode appears to be the more promising one for the effective electrochemical treatment of methidathion. Finally the theoretical calculation was done by using the calculation program Gaussian 03W, they are a permit to identify the phenomena engaged near the electrode and to completely determine the structures of the products of electrochemical oxidation formed during the degradation and which they are not quantifiable in experiments because of their high reactivity. CONCLUSIONS: The comparison of the results relating to the two electrodes indicates that these materials have a power to reduce the quantity of the organic matter in the electrolyzed solution. But the speed of oxidation of these compounds is different according to the materials of the electrodes used. Graphical abstract:Structural of methidathion [O,O-dimethyl-S-(5-methoxy-1,3,4-thiadiazolinyl-3-methyl) dithiophosphate] used for study the electrochemical oxidation.