The study of self-assembled films of triazole on iron electrodes using electrochemical methods,XPS, SEM and molecular simulation

3-Alkyl-4-amino-5-mercapto-1,2,4-triazole (AAMT) has been evaluated as corrosion inhibition for iron in 0.1 M H₂SO₄ when the films of AAMT were self-assembled on the surface of iron. The films of AAMT inhibitor were characterized by electrochemical impedance spectroscopy, electrochemical polarization curves Results revealed that AAMT performed excellently as a corrosion inhibitor for iron in H₂SO₄ solution. Surface analysis was carried out using X-ray photoelectron spectroscopy and scanning electron microscope. The mechanism of adsorption was discussed using molecular simulation.     

Electrochemical Study of Schiff Bases by Means of Self‐Assembled Monolayers

In this paper, Schiffbases were investigated using cyclic voltammetry (CV) and impedance electrochemical spectroscopy (EIS) techniques by means of self‐assembled monolayers for the first time, where a 0.1 M KCl solution and the redox couple of Fe(CN)₆^3?/Fe(CN)₆^4?were used as the electrolyte and probing‐pin, respectively. The monolayers formed by the employed Schiff base were proved to be relatively stable, and its electrochemical response in the studied system with different pH values was also de scribed clearly with CV and EIS plots. The results show that the monolayer of Schiff bases could exist in the solution with pH value from 2 to 10. In the EIS measurement in the concentration range from 10^?5 M to 5× 10^?4 M, a nearly linear relation ship between the charge transfer resistance (R_ct) and the logarithm concentration of Cu²+was observed, suggesting that Cu²+ could be titrated with the EIS method quasi‐quantitatively. The phenomenon agreed with the former report very well. Using the self‐assembled monolayers to study Schiff bases with the electrochemical method is the major contribution of our work.     

Adsorption and inhibition properties of Tephrosia Purpurea as corrosion inhibitor for mild steel in sulphuric acid solution

Abstract

The present study investigated the adsorption and inhibition behavior of leaf extract of Tephrosia Purpurea (T. purpurea) on mild steel corrosion in 1?N H₂SO₄ solution using electrochemical and surface morphological methods. Techniques adopted for electrochemical studies were Potentiodynamic Polarization and Electrochemical Impedance Spectroscopy (EIS) technique; and surface morphological studies were carried out using Scanning Electron Microscopy (SEM), and Atomic Force Microscopy (AFM). The leaf extract of T. purpurea was characterized using UV-Visible spectroscopy (UV-Vis), Fourier-Transform Infrared Spectroscopy (FT-IR), Nuclear Magnetic Resonance Spectroscopy (NMR) and Gas Chromatography – Mass Spectrometry (GCMS). The results obtained from electrochemical studies exhibited the potential of T. purpurea as good corrosion inhibitor. And, it was found that, the inhibition efficiency (I.E in %) increases with increase in concentration of the inhibitor molecules, the optimum inhibitor concentration observed was 300?ppm and the inhibition efficiency of 93% was observed at this inhibitor concentration. Above 300?ppm, there was not much changes in inhibition efficiency. Polarization studies provided the information that the inhibition is of mixed type and EIS confirmed that the corrosion process is controlled by single charge transfer mechanism. And, it was obtained that, the adsorption of inhibitor molecules obeys Langmuir adsorption isotherm. The inhibition is mainly by the adsorption of inhibitor molecules on the mild steel electrode surface, which was confirmed by FT-IR, SEM and AFM studies. Through all the experimental results, it can be arrived that, the leaf extract of T. purpurea performed as a good corrosion inhibitor for mild steel in 1?N sulfuric acid medium.     

Studies of Self-assembled Monolayers Formed by Imidazoline on Iron Surface by SEM and SECM

Self-assembled monolayers (SAMs) formed from organic substances can improve the inhibition of metal corrosion, because uniform and closely packed films formed on the metal surface providing an insulating layer1, 2. SAMs on the iron surface are studied so far because iron is one active metal which is easily corroded in the air. In this paper, SECM and SEM have successfully been applied in the study of SAMs inhibition corrosion for iron. SECM has been used to study the electrochemically a…     

Corrosion inhibition of iron in hydrochloric acid using pyrazole

The corrosion and corrosion inhibition of iron in HCl solutions in the absence and presence of pyrazole (PA) were investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Changes in impedance parameters (R_ct and C_dl) were indicative of the adsorption of PA on the iron surface. The adsorption of PA is found to obey Langmuir adsorption isotherm. The study suggests that this compound is an anodic inhibitor.     

Inhibitor effect of sodium benzoate on the corrosion behavior of nanocrystalline pure iron metal in near-neutral aqueous solutions

Nanocrystalline iron coating was produced on carbon steel surface by pulse electrodeposition using citric acid bath. The grain size of a nanocrystalline surface was analyzed by X-ray diffractometry and scanning electron microscopy. The electrochemical behavior of nanocrystalline iron coating in the presence of sodium benzoate was evaluated in 30 mg l^-1 NaCl + 70 mg l^-1 Na₂SO₄ aqueous solution using potentiodynamic polarization curves and electrochemical impedance spectroscopy. The results were compared with that of the coarse-grained iron surface. The thermodynamic properties of the inhibitor adsorption were also determined. The results indicated that corrosion inhibition of sodium benzoate in near-neutral aqueous solution was increased as the grain size of iron was decreased from micro- to nanocrystalline surface. This was reported in terms of excess free energy of nanocrystalline surface.     

Study on surface acid-base property of carboxylic acid-terminated self-assembled monolayers by cyclic voltammetry and electrochemical impedance spectroscopy

Cyclic voltammetry and electrochemical impedance spec-troscopy were used to study the surface acid-base property of carboxylic acid-terminated self-assembled monolayers(SAMs).A carboxylic acid-terminated thiol,such as thioctic acid(1,2-dithiolane-3-pentanoic acid),was self-assembled on gold electrodes.Electron transfer between the bulk solution and the SAM modified electrode was studied at different pH using Fe(CN)63-as a probe.The surface pka of thioctic acid was determined by cyclic voltammetry and electrochemical impedance spectroscopy to be 5.6 ±0.1 and 5.8±0.1,respectively.The method is compared with other methods of monolayer pKa measurement.     

Corrosion and corrosion inhibition characteristics of bulk nanocrystalline ingot iron in sulphuric acid

The corrosion and corrosion inhibition of bulk nanocrystalline ingot iron (BNII) fabricated from conventional polycrystalline ingot iron (CPII) by severe rolling was studied in 0.5 M H₂SO₄ solution using electrochemical impedance spectroscopy and potentiodynamic polarization techniques. The results indicate that BNII was more susceptible to corrosion in the acidic environment essentially because of an increase in the kinetics of the anodic reaction. An amino acid cysteine (cys) was employed as a corrosion inhibitor at concentrations of 0.001 and 0.005 M. Tests in inhibited solutions revealed that cys reduced the corrosion rates of both metal specimens by different mechanisms. For CPII cys inhibited the cathodic reaction but had a stimulating effect on the anodic process at low concentration and a trivial effect at higher concentration. For BNII, cys inhibited both the cathodic and the anodic reactions, although the former effect was more pronounced. Iodide ions improved the inhibitive effect of cys without altering the inhibition mechanism.     

Inhibition effect of hexadecyl pyridinium bromide on the corrosion behavior of some austenitic stainless steels in H2SO4 solutions

The inhibition effect of hexadecyl pyridinium bromide (HDPB) as a cationic surfactant on the corrosion behavior of some Egyptian austenitic stainless steel SS 304L, SS 316H and SS 304H in 0.5 M H₂SO₄ solutions was investigated by using potentiodynamic polarization technique and electrochemical impedance spectroscopy (EIS). The results indicate that HDPB is a good inhibitor for the samples under investigation in 0.5 M H₂SO₄ solutions. In addition, the inhibition efficiency η% increases with the inhibitor concentration while decreases with the increasing temperature referring to physical adsorption. The adsorption of the inhibitor obeys a Temkin adsorption isotherm. Polarization curves show that HDPB is a mixed inhibitor in H₂SO₄ solutions. The results obtained from polarization and impedance measurements are in good agreement. Activation-free energies, enthalpies, and entropies for the inhibition process of HDPB were determined.     

Impedance spectroscopic study of corrosion inhibition of Al-Pure by organic Schiff base in hydrochloric acid

A new corrosion inhibitor namely o-Chloroaniline-N-benzylidene (o-CANB) has been synthesized and its inhibitive performance toward the corrosion of Al-Pure in 1.0 M hydrochloric acid has been investigated. Corrosion inhibition was studied by chemical method (weight loss) and electrochemical techniques including polarization method and electrochemical impedance spectroscopy (EIS). The present study has shown that this inhibitor is good in acidic media and the inhibition efficiency up to >99% in 1.0 M HCl. Polarization measurement revealed that the investigated inhibitor is a mixed type with a predominant action on cathode. Impedance measurement showed that the charge transfer resistance (R_ct) increased and double layer capacitance (C_dl) decreased with an increase in the inhibitor's concentration. Obtained results about inhibition efficiency from weight loss, polarization study and EIS are in good agreement with each other. The adsorption of the inhibitor on the metal surface in the acid solution was found to obey Langmuir's adsorption isotherm.     

The litchi (Litchi Chinensis) peels extract as a potential green inhibitor in prevention of corrosion of mild steel in 0.5 M H2SO4 solution

The corrosion inhibition of mild steel in 0.5 M H₂SO₄ solution by the extract of litchi peel (Litchi chinensis) was studied by weight loss method, potentiodynamics polarization and electrochemical impedance spectroscopy (EIS). The results show that the litchi peels extract acts as mixed-type inhibitor. The inhibition of corrosion is found to be due to adsorption of the extract on metal surface, which is in conformity with Langmuir’s adsorption isotherm. UV–Vis, Fourier transform infrared (FT-IR) spectroscopy and Scanning electron microscopy (SEM) studies confirm that the inhibition of corrosion of mild steel occurs through adsorption of the inhibitor molecules.     

Modification of Electrode Surfaces by Self‐Assembled Monolayers of Thiol‐Terminated Oligo(Phenyleneethynylene)s

The wire‐like properties of four S‐(4‐{2‐[4‐(2‐phenylethynyl)phenyl]ethynyl}phenyl) thioacetate derivatives, PhC≡CC₆H₄C≡CC₆H₄SAc ( 1 ), H₂NC₆H₄C≡CC₆H₄C≡CC₆H₄SAc ( 2 ), PhC≡CC₆H₂(OMe)₂C≡CC₆H₄SAc ( 3 ) and AcSC₆H₄C≡CC₆H₄C≡CC₆H₄SAc ( 4 ) (Figure 1 ), all of which possess a high degree of conjugation along the oligo(phenyleneethynylene) (OPE) backbone, were investigated as self‐assembled monolayers (SAMs) on gold and platinum electrodes by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The redox probe [Fe(CN)₆]₄^? was used in both the CV and impedance experiments. The results indicate that the thiolates derived from thioacetate‐protected precursor molecules 1 and 2 form well‐ordered monolayers on a gold electrode, whereas SAMs derived from 3 and 4 exhibit randomly distributed pinholes. The electron tunnelling resistance and fractional coverage of SAMs of all four compounds were examined using electron tunnelling theory. The analysis of the results reveal that the well‐ordered SAMs of 1 and 2 exhibit higher charge‐transfer resistance in comparison to the defect‐ridden SAMs of 3 and 4 . The additional steric bulk offered by the methoxy groups in 3 is likely to prevent efficient packing within the SAM, leading to a microelectrode behaviour, when assembled on a gold electrode surface. The protected dithiol derivative 4 probably binds to the surface through both terminal groups which prevents dense packing and leads to the formation of a monolayer with randomly distributed pinholes. Atomic force microscopy (AFM) was used to examine the morphology of the monolayers, and height images gave root‐mean‐square (RMS) roughness′s which are in agreement with the proposed SAM structures.     

Exploring the Molecular Structure of Imidazolium–Silica‐Based Nanoparticle Networks by Combining Solid‐State NMR Spectroscopy and First‐Principles Calculations

A DFT‐based molecular model for imidazolium–silica‐based nanoparticle networks (INNs) is presented. The INNs were synthesized and characterized by using small‐angle X‐ray scattering (SAXS), NMR spectroscopy, and theoretical ab initio calculations. ¹¹B and ³¹P HETCOR CP MAS experiments were recorded. Calculated ¹⁹F NMR spectroscopy results, combined with the calculated anion–imidazolium (IM) distances, predicted the IM chain density in the INN, which was also confirmed from thermogravimetric analysis/mass spectrometry results. The presence of water molecules trapped between the nanoparticles is also suggested. First considerations on possible π–π stacking between the IM rings are presented. The predicted electronic properties confirm the photoluminescence emissions in the correct spectral domain.     

Indole‐3‐acetic acid and N‐acetyltryptophan corrosion inhibition effects on mild steel in 1 M hydrochloric acid solution

Corrosion inhibition of indole‐3‐acetic acid and N‐acetyl tryptophan on carbon steel was investigated using polarization and electrochemical impedance spectroscopy (EIS). Polarization results revealed that corrosion inhibitors could reduce the rate of cathodic and anodic reactions on metal surface. EIS analysis showed inhibition efficiency of indoles increases by increasing the inhibitor concentration. The maximum inhibition efficiency was 97% and 80% in solutions containing 10 mM indole‐3‐acetic acid and 10 mM N‐acetyl tryptophan, respectively. The adsorption of inhibitors was found to follow Langmuir isotherm. Adsorption and film formation of inhibitors on the metal substrate were confirmed by calculating thermodynamic adsorption parameter (ΔG⁰_ads) and characterization of exposed metals' surface through contact angle measurements. Copyright © 2014 John Wiley & Sons, Ltd.     

Electrodes modified with iron porphyrin and carbon nanotubes: application to CO2 reduction and mechanism of synergistic electrocatalysis

Electrodes modified with iron porphyrin and carbon nanotubes (FeP–CNTs) were prepared and used for CO₂ electroreduction. The adsorption of iron porphyrin onto the multiwalled carbon nanotubes was characterized by scanning electron microscopy and ultraviolet and visible spectroscopy. The electrochemical properties of the modified electrodes for CO₂ reduction were investigated by cyclic voltammetry and CO₂ electrolysis. The FeP–CNT electrodes exhibited less negative cathode potential and higher reaction rate than the electrodes modified only with iron porphyrin or carbon nanotubes. A mechanism of the synergistic catalysis was proposed and studied by electrochemical impedance spectroscopy and electron paramagnetic resonance. The direct electron transfer between iron porphyrin and carbon nanotubes was examined. The current study shed light on the mechanism of synergistic catalysis between CNTs and metalloporphyrin, and the iron porphyrin–CNT-modified electrodes showed great potential in the efficient CO₂ electroreduction.     

An Electrochemical Impedance Immunosensor Based on Gold Nanoparticle‐Modified Electrodes for the Detection of HbA1c in Human Blood

A label‐free immunosensor for the detection of HbA1c was developed based on gold nanoparticle (AuNP)‐aryl diazonium salt modified glassy carbon (GC) electrode where transduction is achieved using electrochemical impedance spectroscopy (EIS). GC electrodes were first modified with 4‐aminophenyl (Ph‐NH₂) layers to which AuNPs were attached. Thereafter an oligo(ethylene glycol) (OEG‐COOH) species were covalently attached to the remaining free amine groups on the Ph‐NH₂ surface. The AuNP surfaces were further modified with Ph‐NH₂ followed by attachment of a glycosylated pentapeptide (GPP), an analogon to HbA1c. Exposure of this interface to anti‐HbA1c IgG resulted in a change in charge transfer resistance (R_ct) due to the anti‐HbA1c IgG selectively complexing to the surface bound GPP. To detect the amount of HbA1c, a competitive inhibition assay was employed where the surface bound GPP and HbA1c in solution compete for the anti‐HbA1c IgG antibodies. The higher the concentration of HbA1c, the less antibody binds to the sensing interface and the lower the change of R_ct. The response of the immunosensor is linear with the HbA1c% of total haemoglobin in the range of 0%–23.3%. This competitive inhibition assay can be used for the detection of HbA1c in human blood. The performance of the immunosensor for detection of HbA1c in human blood is comparable to the clinical laboratory method.     

Effect of hyamine on electrochemical behaviour of brass alloy in HNO3 solution

The electrochemical behaviours of a brass alloy in 0.1 M nitric acid, including the hyamine inhibitor with concentrations between 2.5 × 10^?4 M and 1.0 × 10^?5 M, were studied. For this purpose, potentiodynamic polarisation, electrochemical impedance spectroscopy (EIS), linear polarisation resistance (LPR) techniques, and flame atomic absorption spectroscopy (FAAS) were utilised. The inhibitor molecules adsorbed on the brass surface were calculated to be in good agreement with the Langmuir adsorption isotherm and the standard free enthalpy of adsorption (??G _ads ^° ). Hyamine effectively improved the corrosion inhibition of brass and acted as a mixed-type inhibitor on alloy surfaces. The surface morphology of the alloy was also clarified by optical microscopic and SEM techniques. A theoretical study of the corrosion inhibition efficiency of hyamine molecule was carried out using density functional theory (DFT) at the B3LYP/6-311G(d,p) basis set level.     

Iron(III) Oxide Graphite Composite Electrodes: Application to the Electroanalytical Detection of Hydrazine and Hydrogen Peroxide

Composite electrodes based on iron(III) oxide, Fe₂O₃, carbon powder and epoxy resin have been prepared and characterized using electrochemical methods and X‐ray photoelectron spectroscopy (XPS). Initially composite electrodes were made by mixing micron sized carbon powder surface with iron(III) oxide. However, the voltammetric responses were unsatisfactory. Therefore, a new type of composite electrodes was made using carbon powder modified with iron(III) oxide via a wet impregnation procedure. This technique involves saturation of the carbon powder with iron(III) nitrate followed by thermal treatment at ca. 623 K forming iron(III) oxide on the surface of the carbon powder.     

Application of the Synthesized Novel 3,6,9,12,15,18,21-heptaoxatricosane-1,23-diyl bis(4-((4-(dimethylamino)benzylidene)amino)benzoate) as a Corrosion Inhibitor for Carbon Steel in Acidic Media

A 3,6,9,12,15,18,21-heptaoxatricosane-1,23-diyl bis(4-((4-(dimethylamino)benzylidene)amino)benzoate) was synthesized and characterized by spectroscopy analysis. The corrosion inhibition effect of the synthesized compound on carbon steel in hydrochloric acid solution had been investigated using potentiodynamic polarization, electrochemical impedance spectroscopy, and weight loss measurements. Polarization studies indicated that the compound acted as a mixed-type inhibitor. Impedance measurement showed that the charge transfer resistance (R _ct) increased and double layer capacitance (C _dl) decreased with the increase in the inhibitor's concentration. Adsorption of the inhibitor on the metal surface was found to obey Langmuir isotherm. Quantum chemical parameters were also calculated to characterize adsorption mechanism. Acceptable correlations were obtained between inhibition efficiency and the calculated quantum chemical parameters.     

Electrochemical Characterization of Self‐Assembled Monolayer of a Novel Manganese Tetrabenzylthio‐Substituted Phthalocyanine and Its Use in Nitrite Oxidation

Manganese phthalocyanine MnPc(SPh)₄ has been synthesized and used to form self assembled monolayers on gold electrodes. The well packed SAM monolayer was characterized by analyzing the blocking of a number of Faradic processes by cyclic voltammetry, evaluating the electrical characteristics of the modified electrode by electrochemical impedance and imaging the modified surface by electrochemical scanning microscopy. Finally, MnPc(SPh)₄‐SAM modified electrode displayed an electrocatalytic behavior toward the oxidation of nitrite.