Iron Surface Research Articles

Deciphering the Catalytic Mechanism of Peroxidase-like Activity of Iron Sulfide Nanozymes.

Iron sulfide nanomaterials represented by FeS2 and Fe3S4 nanozymes have attracted increasing attention due to their biocompatibility and peroxidase-like (POD-like) catalytic activity in disease diagnosis and treatments. However, the mechanism responsible for their POD-like activities remains unclear. Herein, taking the oxidation of 3,3,5,5-tetramethylbenzidine (TMB) by H2O2 on FeS2(100) and Fe3S4(001) surfaces, the catalytic mechanism was investigated in detail using density functional theory (DFT) calculations and experimental characterizations. Our experimental results showed that the catalytic activity of FeS2 nanozymes was significantly higher than that of Fe3S4 nanozymes. Our DFT calculations indicated that the surface iron ions of iron sulfide nanozymes could effectively catalyze the production of HO• radicals via the interactions between Fe 3d electrons and the frontier orbitals of H2O2 in the range of -10 to 5 eV. However, FeS2 nanozymes exhibited higher POD-like activity due to the surface Fe(II) binding to H2O2, forming inner-orbital complexes, which results in a larger binding energy and a smaller energy barrier for the base-like decomposition of H2O2. In contrast, the surface iron ions of Fe3S4 nanozymes bind to H2O2, forming outer-orbital complexes, which results in a smaller binding energy and a larger energy barrier for the base-like decomposition of H2O2. The charge transfer analysis showed that FeS2 nanozymes transferred 0.12 e and Fe3S4 nanozymes transferred 0.05 e from their surface iron ions to H2O2, respectively. The simulations were consistent with the experimental observations that the FeS2 nanozymes had a greater affinity for H2O2 compared to that of Fe3S4 nanozymes. This work provides a theoretical foundation for the rational design and accurate preparation of iron sulfide functional nanozymes.

Understanding anti-corrosion mechanisms of the 2,6-dithiopurine (DTP) inhibitor molecule on iron surfaces

Purine derivatives present a high efficiency for anti-corrosion purposes while the nanoscale mechanisms are not yet fully understood. In this work, the inhibition mechanism of the 2,6-dithiopurine (DTP) molecule was investigated using advanced characterizations and atomic simulations. We revealed that the DTP molecule undergoes a multi-layer adsorption mode and is governed by both chemisorption and physisorption processes. An organometallic layer at a thickness of ∼3.8 nm was captured using TEM, comprised of Fe-N and Fe-S bonds strongly anchored to the iron interfaces, as confirmed by the XPS analysis. Our quantum chemical calculations showed that heteroatoms such as N or S in the DTP molecule offer reactive sites that facilitate its chemisorption onto iron surfaces, to form metal-organic bonds (specifically, Fe-N and Fe-S) at the DTP-iron interfaces. We further employed molecular dynamics simulations to investigate the interaction between DTP molecule and various substrates. Our findings suggest that the hydroxyl groups on the lepidocrocite surface can significantly promote bonding between DTP and iron surfaces. Based on large-scale molecular dynamics simulations, we discovered that DTP can exhibit a strong binding affinity for aggressive ions, leading to a considerable decrease in the self-diffusion coefficient of hydronium ions of up to 70 %. This work provides a new understanding of anti-corrosion mechanisms and offers opportunities to design new corrosion inhibitors possessing multiple reactive sites and strong bonding with the substrate.

Adsorption studies of isoxazole derivatives as corrosion inhibitors for mild steel in 1M HCl solution: DFT studies and molecular dynamics simulation.

The corrosion of mild steel is a significant issue in various industries, prompting the need for effective corrosion inhibitors. This study focuses on understanding the corrosion inhibition properties of organic compounds derived from isoxazole, namely series Iso(a), Iso(b), Iso(c), Iso(d), Iso(e), Iso(f), Iso(g), and Iso(h), which could have implications for materials science and industrial applications. By investigating the influence of different substitutions on these compounds, valuable insights can be gained into designing better corrosion inhibitors for practical use. Theoretical studies were conducted using density functional theory (DFT) with the B3LYP functional and the 6-31G (d,p) basis set. These calculations enabled the evaluation of various parameters including frontier orbital energies (EHOMO, ELUMO), energy gap (∆E), electronegativity (χ), absolute hardness (η), softness (σ), fraction of transferred electrons (∆N), as well as local properties such as natural atomic populations and Fukui indices. Additionally, molecular dynamics simulations were performed to study the adsorption behavior of the inhibitors on the surface of Fe (110). The simulations were conducted using Materials Studio version 8.0 software package using COMPASS force field to understand the impact of different functional groups on the inhibitors before and after adsorption on the iron surface.

Comparison of the Erosive Wear Resistance of Ductile Cast Iron Following Laser Surface Melting and Alloying

This article presents research results on the influence of the laser surface melting and alloying processes on the erosive wear resistance of ductile cast iron. For the research, an EN-GJS 350-22 ductile cast iron surface was laser-melted and laser-alloyed with titanium powder in an argon and nitrogen atmosphere. Solid-particle erosion tests were carried out on the laser-melted and -alloyed surface layers and the base material according to the ASTM G76-04 standard with 30° and 90° impingement angles. The erosive wear resistance results were correlated with Vickers hardness and microstructural test results with the use of SEM (scanning electron microscopy), TEM (transmission electron microscopy), EDS (energy dispersive spectroscopy), and XRD (X-ray diffraction). The mechanisms of erosive wear were also analyzed for the laser-treated surface layers and the base material. The research showed that the laser melting and alloying processes with titanium powder had a positive effect on the hardness and erosive wear resistance of the ductile cast iron surface due to microstructure modification. Moreover, despite the lower hardness of the laser-alloyed surface layers, their composite microstructure had a positive impact on the erosive wear resistance in comparison to the laser-melted surface layers.

Quinoline derivatives as corrosion inhibitors for mild steel in acid medium: Deeper insights from experimental, ab initio density functional theory modeling, and in silico ecotoxicity investigations

Two (E)-2-(((2-((7-chloroquinolin-4-yl)amino)ethyl)imino)methyl)-4-R-phenol Schiff bases derivatives CMN (R = NO2) and CMP (R = H) were successfully prepared. Then, CMN and CMP were evaluated as corrosion inhibitors for 1020 mild steel in 1.0 mol L–1 HCl using different methods. Gravimetric experiments have shown that CMN and CMP reach efficiencies of 80 and 91% at 1.45 mmol L–1. Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM) measurements have indicated the formation of a protective adsorbed film on the mild steel surface. Electrochemical Impedance Spectroscopy (EIS), Linear Polarization Resistance (LPR), Potentiodynamic Polarization (PP), and Electrochemical Frequency Modulation (EFM) have also shed some light on electrochemical behavior of compounds. These data have depicted better polarization resistance and lower corrosion current density in the presence of both organic molecules, also proving that the process is controlled by charge transfer and that CMN and CMP are mixed-type corrosion inhibitors. ab initio Density Functional Theory (DFT) investigated how two quinoline-based molecules (CMN and CMP) prevent corrosion on iron surfaces. Simulations revealed CMP bonds more strongly to iron than CMN, leading to better protection. Simulations also showed that these inhibitor molecules form a protective layer on the iron, slowing down the movement of corrosive substances. Environment risk assessment through QSAR-based models have indicated that the corrosion inhibitors do not have the potential to bioaccumulate in fish. Still, the acute and chronic toxicity values at the different trophic levels investigated call for attention for environmentally friendly structural optimization.

Microbial community response to hydrocarbon exposure in iron oxide mats: an environmental study.

Hydrocarbon pollution is a widespread issue in both groundwater and surface-water systems; however, research on remediation at the interface of these two systems is limited. This interface is the oxic-anoxic boundary, where hydrocarbon pollutant from contaminated groundwaters flows into surface waters and iron mats are formed by microaerophilic iron-oxidizing bacteria. Iron mats are highly chemically adsorptive and host a diverse community of microbes. To elucidate the effect of hydrocarbon exposure on iron mat geochemistry and microbial community structure and function, we sampled iron mats both upstream and downstream from a leaking underground storage tank. Hydrocarbon-exposed iron mats had significantly higher concentrations of oxidized iron and significantly lower dissolved organic carbon and total dissolved phosphate than unexposed iron mats. A strong negative correlation between dissolved phosphate and benzene was observed in the hydrocarbon-exposed iron mats and water samples. There were positive correlations between iron and other hydrocarbons with benzene in the hydrocarbon-exposed iron mats, which was unique from water samples. The hydrocarbon-exposed iron mats represented two types, flocculent and seep, which had significantly different concentrations of iron, hydrocarbons, and phosphate, indicating that iron mat is also an important context in studies of freshwater mats. Using constrained ordination, we found the best predictors for community structure to be dissolved oxygen, pH, and benzene. Alpha diversity and evenness were significantly lower in hydrocarbon-exposed iron mats than unexposed mats. Using 16S rDNA amplicon sequences, we found evidence of three putative nitrate-reducing iron-oxidizing taxa in microaerophile-dominated iron mats (Azospira, Paracoccus, and Thermomonas). 16S rDNA amplicons also indicated the presence of taxa that are associated with hydrocarbon degradation. Benzene remediation-associated genes were found using metagenomic analysis both in exposed and unexposed iron mats. Furthermore, the results indicated that season (summer vs. spring) exacerbates the negative effect of hydrocarbon exposure on community diversity and evenness and led to the increased abundance of numerous OTUs. This study represents the first of its kind to attempt to understand how contaminant exposure, specifically hydrocarbons, influences the geochemistry and microbial community of freshwater iron mats and further develops our understanding of hydrocarbon remediation at the land-water interface.

Coarse grained MD simulation of bulk and interfacial behavior of mixture of CTAB/SDS surfactants.

This study involves simulating the process of inhibiting corrosion through the formation of micelles by surfactants and their deposition on iron (Fe) surfaces. The primary focus is on examining CTAB/SDS mixtures in aqueous solutions with different concentrations. Micelle properties, including size, shape, aggregation number, cluster size, and surfactant diffusion, were calculated and validated with experimental data. The coarse-grained Fe surface was modeled and validated against experimental water contact-angle data. Subsequently, the deposition of CTAB/SDS mixtures on the Fe surface and air-water interface was studied systematically. We found that the relative ratio of CTAB/SDS in the solution directly influences surfactant deposition behavior, which might impact the corrosion inhibition efficiency. All the MD simulations were performed using the GROMACS software with MARTINI2 force field and Martini polar water. The molecules are packed using PACKMOL software. Both NVT and NPT simulations are caried out at temperature and pressure of 303 K and 1 bar respectively, with a nonbonded interaction cut-off (rcut) of 1.1 nm. The LJ potential was shifted from 0.9 nm to rcut, while the electrostatic potential was shifted from 0.0 nm to rcut. For electrostatics, reaction-field coulomb type is used, relative dielectric constant (epsilon-r) and the reaction field dielectric constant (epsilon-rf) are equal to 2.5 and infinity respectively. The dielectric constant below rcut is epsilon-r, and beyond the cut-off is epsilon-rf. Coulomb-modifier used as potential-shift which leads to shift in the coulomb potential by a constant such that it is zero at the rcut. This makes the potential of the integral of the force . The neighbor list was updated every 10 steps, employing a neighbor list cut-off equal to rcut. Using a polar water model, we used a constant time step of 0.02 ps throughout the simulation. The used epsilon-r = 2.5, is recommended for polar water.

Influence of Cations on Direct CO2 Capture and Mineral Film Formation: The Role of KCl and MgCl2 at the Air/Electrolyte/Iron Interface.

Uncovering the mechanisms associated with CO2 capture through mineralization is vital for addressing rising CO2 levels. Iron in planetary soils, the mineral cycle, and atmospheric dust react with CO2 through complex surface chemistry. Here, the effect of cations on the growth of carbonate films on iron surfaces was investigated. In situ polarized modulated infrared reflection absorption spectroscopy was used to measure CO2 adsorption and oxidation of iron in MgCl2(aq) and KCl(aq), compared to FeCl2(aq) at the air/electrolyte/iron interface. The cation was found to influence the film composition and growth rates, as corroborated by infrared and photoelectron spectroscopy. In MgCl2(aq), a mixture of hydromagnesite, magnesite, and a Mg hydroxy carbonate film was grown on iron, while in KCl(aq), a potassium-rich bicarbonate film was grown. The cations were found to affect the rates of hydroxylation and carbonation, confirming a specific cation effect on carbonate film growth. In the submerged region, a heterogeneous mixture of lepidocrocite and iron hydroxy carbonate was produced, suggesting that Fe2+ dominates the surface products. Surface roughness measurements from in situ atomic force microscopy indicate iron initially corrodes faster in MgCl2(aq) than KCl(aq), due to the Cl- ions that initiate pitting and corrosion. In this region, cations were not found to affect the morphologies. This study shows surface corrosion is necessary to provide nucleation sites for film growth and that the cations influence the carbonate film, relevant for CO2 capture and planetary processes.

Experimental Investigation of the Effects of Grooves in Fe2O4/Water Nanofluid Pool Boiling

In this study, we systematically explored how changing groove surfaces of iron oxide/water nanofluid could affect the pool boiling heat transfer. We aimed to investigate the effect of three types of grooves, namely rectangular, circular, and triangular, on the boiling heat transfer. The goal was to improve heat transfer performance by consciously changing surface structure. Comparative analyses were conducted with deionized water to provide valuable insights. Notably, the heat transfer coefficient (HTC) exhibited a significant increase in the presence of grooves. For deionized water, the HTC rose by 91.7% and 48.7% on circular and rectangular grooved surfaces, respectively. Surprisingly, the triangular-grooved surface showed a decrease of 32.9% in HTC compared to the flat surface. On the other hand, the performance of the nanofluid displayed intriguing trends. The HTC for the nanofluid diminished by 89.2% and 22.3% on rectangular and triangular grooved surfaces, while the circular-grooved surface exhibited a notable 41.2% increase in HTC. These results underscore the complex interplay between groove geometry, fluid properties, and heat transfer enhancement in nanofluid-based boiling. Hence, we thoroughly examine the underlying mechanisms and elements influencing these observed patterns in this research. The results provide important insights for further developments in this area by shedding light on how surface changes and groove geometry may greatly affect heat transfer in nanofluid-based pool boiling systems.

Reproduction of fissure corrosion and mechanism for fissure formation on ductile cast iron

On some cast iron pipes corroded under tensile stress, corrosion with a characteristic surface appearance, known as “fissure corrosion,” was occasionally observed. Because fissure corrosion on ductile cast iron pipes has been rarely studied, the detailed conditions and mechanism for fissure formation are still elusive. In this study, the levels of tensile stress and anodic current density causing fissure corrosion on ductile cast iron were investigated through laboratory experiments to reproduce fissure corrosion and elucidate its mechanism. Fissure corrosion was reproduced at bending tensile stresses ≥200 MPa. The depth difference between the peak and valley of fissures increased with increasing anodic current density, and the fissure corrosion was attributed to the difference between the anodic current densities of the peak and valley due to plastic deformation by stress concentration. Fissure corrosion was likely to be suppressed by reducing the anodic current flowing out of ductile cast iron surface.

Microelectrode investigation of iron and copper surfaces aged in presence of monochloramine.

Ductile iron and copper coupons were aged 137-189 days and 2 days, respectively, with 2 mg Cl2 L-1 monochloramine under four water chemistries (pH 7 or 9 and 0 or 3 mg L-1 orthophosphate). Subsequently, microelectrode profiles of monochloramine concentration, oxygen concentration, and pH were measured from the bulk water to near the coupon reactive surface, allowing estimation of flux and apparent surface reaction rate constants for monochloramine and oxygen. Both metals showed similar trends with orthophosphate where orthophosphate decreased metal reactivity with monochloramine (pH 9) and oxygen (pH 7). Comparing iron and copper coupons, apparent surface reaction rate constants for monochloramine and oxygen were one and two orders of magnitude greater, respectively, for iron coupons under all conditions. Overall, this research provides the first insights into monochloramine concentration, oxygen concentration, and pH by direct measurement near ductile iron and copper reactive surfaces aged in the presence of monochloramine.

Numerical Optimization and Performance Study of Ni-Based Coatings on Gray Cast Iron Surface by High-Speed Laser Cladding Based on Orthogonal Test

Numerical Optimization and Performance Study of Ni-Based Coatings on Gray Cast Iron Surface by High-Speed Laser Cladding Based on Orthogonal Test

Investigation of Corrosion Inhibition Efficiency of Pyridine-Quinoline Compounds through Machine Learning

Corrosion in materials is a significant concern for the industrial and academic fields because corrosion causes enormous losses in various fields such as the economy, environment, society, industry, security, safety, and others. Currently, material damage control using organic compounds has become a popular field of study. Pyridine and quinoline stand out as corrosion inhibitors among a myriad of organic compounds because they are non-toxic, inexpensive, and effective in a variety of corrosive environments. Experimental investigations in developing various candidate potential inhibitor compounds are time and resource-intensive. In this work, we use a quantitative structure-property relationship (QSPR)-based machine learning (ML) approach to investigate support vector machine (SVR), random forest (RF), and k-nearest neighbors (KNN) algorithms as predictive models of inhibition performance. (Inhibition efficiency) corrosion of pyridine-quinoline derivative compounds as corrosion inhibitors on iron. We found that the RF model showed the best predictive ability based on the coefficient of determination (R2) and root mean squared error (RMSE) metrics. Overall, our study provides new insights regarding the ML model in predicting corrosion inhibition on iron surfaces.

A Machine Learning Model for Evaluation of the Corrosion Inhibition Capacity of Quinoxaline Compounds

Investigating potential corrosion inhibitors via empirical research is a labor- and resource-intensive process. In this work, we evaluated various linear and non-linear algorithms as predictive models for corrosion inhibition efficiency (CIE) values using a machine learning (ML) paradigm based on the quantitative structure-property relationship (QSPR) model. In the quinoxaline compound dataset, our analysis showed that the XGBoost model performed the best predictor of other ensemble-based models. The coefficient of determination (R2), mean absolute percentage error (MAPE), and root mean squared error (RMSE) metrics were used to objectively assess this superiority. To sum up, our study offers a fresh viewpoint on the effectiveness of machine learning algorithms in determining the ability of organic compounds like quinoxaline to suppress corrosion on iron surfaces.

Characteristics of zero-valent iron surface oxide films under the catalytic interface reactions by assisting ligands in nitrate-contaminated groundwater

The surface passivation layer coating on zero-valent iron (ZVI) particles impedes the electron transfer from ZVI to nitrate. To enhance the efficiency of nitrate reduction by Fe(0), we tested the chemical process and the thickness of the iron oxide film on the surface of Fe(0) particles, utilizing Fe2+aq in aqueous solution and wheat straw as ligands. A novel principal surface catalyzing reaction was formulated as follows: NO3−+0.67Fe2++2.2Fe0+2.33H2O→NH4++1.18Fe3O4+0.64OH−. When Fe2+aq concentration increased from 0 - 200 mg·L−1, the NO3- removal rate increased from 6.95% to 82.6% respectively during 12 h and it was 48%, 72%, 79% and 94% respectively in Fe0/WS ratio of 0, 0.25, 0.5 and 1 system. Uniform surface iron oxide films formed around the Fe(0) particles within 12 h after the adding Fe2+aq or wheat straw to the Fe(0) system. The composition and thickness of these films were dependent on the quantity of added materials. X-ray diffraction (XRD) analysis revealed that surface oxide iron mainly consisted of Fe2+ or Fe3+ oxides, with Fe3O4 being predominant. The X-ray photoelectron spectroscopy (XPS) etching indicated that the addition of Fe(0)/straw at mass ratios of 1 or system with 20 mg·L−1 Fe2+aq resulted in the thinnest surface iron oxide layer. The study demonstrated that reducing the oxide layer’s thickness was achieved through partial catalysis and enhanced complexation capacity. This reduction was facilitated by the introduction of Fe2+aq or wheat straw into the Fe(0) system, potentially improving proton dissociation and promoting the ligand-assisted dissolution of Fe3+ oxides.

Effects of –NH2 and –COO− functional groups on the steel passivation in concrete pore solution: Passivation performance and interfacial adsorption mechanism

The use of organic corrosion inhibitors is a common method for enhancing the corrosion resistance of steel in concrete. Whereas, the effects of common functional groups (–NH2 and –COO−) on the steel passivation are still unclear. Herein, propylamine (C3H7NH2) and calcium butyrate ((C3H7COO)2Ca) were selected as representative inhibitors containing –NH2 and –COO− groups, respectively. The passivation performance of steel affected by C3H7NH2 or (C3H7COO)2Ca in simulated concrete pore solution was explored by electrochemical method, XPS tests, and DFT simulation. Experimental results show that the (C3H7COO)2Ca has little effect on passivation performance, while the C3H7NH2 exhibits an inhibition effect. The XPS data shows that the (C3H7COO)2Ca decreases the Fe/Fen+ ratio on the steel surface, thereby enhancing the physical protectiveness of passive film. Although the C3H7NH2 causes an increase in the chemical protectiveness of passive film (Fe2+/Fe3+ ratio increase), it induces a more pronounced decrease in physical protectiveness, resulting in the poor passivation performance of steel. DFT results indicate that the C4H7O2− adsorption increases the activity of iron surface, thereby promoting the adsorption of passivation substances (OH–/CaOH+). Moreover, insoluble C4H7O2-Ca-Fe compounds form due to the electron transfer between –COO− and CaOH+. Besides, the C3H7NH2 inhibits the adsorption of OH–/CaOH+ on steel surface.

Coupling Process between Droplet and Iron Investigated by Reactive Molecular Dynamics Simulations.

The droplet-to-iron electrochemical reaction is common in nature and industrial production, and it causes damage to the economy, safety, and the environment. The electrochemical reaction of droplet-to-iron is a coupling process of wetting and corrosion. Presently, investigations into electrochemical reactions mainly focus on the corrosions caused by a solution, and wetting is rarely considered. However, for the droplet-to-iron electrochemical reaction, the mechanism of charge transfer in the process is still unclear. In this paper, a reactive molecular dynamics simulation model for the droplet-to-iron electrochemical reaction is developed for the first time. The electrochemical reaction of droplet-to-iron is studied, and the interaction between droplet wetting and corrosion on iron is investigated. The effects of temperature, electric field strength, and salt concentration on the electrochemical reaction are explored. Results show that droplet wetting on the iron surface and the formation of a single-molecular-layer ordered structure are prerequisites for corrosion. The hydroxyl radicals that penetrate the ordered structure acquire electrons from iron atoms on the substrate surface under the action of Coulomb forces and form iron-containing oxides with these iron atoms. The corrosion products and craters lead to a reduced droplet height, which promotes droplet wetting on iron and further intensifies the droplet-to-iron electrochemical reaction.

Investigation of the accuracy of a portable 109Cd XRF system for the measurement of iron in skin

We have previously reported the design of a portable 109Cd x-ray fluorescence (XRF) system to measure iron levels in the skin of patients with either iron overload disease, such as thalassemia, or iron deficiency disease, such as anemia. In phantom studies, the system was found to have a detection limit of 1.35 μg Fe per g of tissue for a dose of 1.1 mSv. However, the system must provide accurate as well as precise measurements of iron levels in the skin in order to be suitable for human studies. The accuracy of the system has been explored using several methods. First, the iron concentrations of ten pigskin samples were assessed using both the portable XRF system and ICP-MS, and the results were compared. Overall, it was found that XRF and ICP-MS reported average values for iron in skin that were comparable to within uncertainties. The mean difference between the two methodologies was not significant, 2.5 ± 4.6 μg Fe per g. On this basis, the system could be considered accurate. However, ICP-MS measurements reported a wider range of values than XRF, with two individual samples having ICP-MS results that were significantly elevated (p < 0.05) compared to XRF. Synchrotron μXRF maps of iron levels in pigskin were acquired on the BioXAS beam line of the Canadian Light Source. The μXRF maps indicated two important features in the distribution of iron in pigskin. First, there were small areas of high iron concentration in the pigskin samples, that were predominantly located in the dermis and hypodermis at depths greater than 0.5 mm. Monte Carlo modelling using the EGS 5 code determined that if these iron ‘hot spots’ were located towards the back of the skin at depths greater than 0.5 mm, they would not be observed by XRF, but would be measured by ICP-MS. These results support a hypothesis that iron levels in the two samples that reported significantly elevated ICP-MS results compared to XRF may have had small blood vessels at the back of the skin. Second, the synchrotron μXRF maps also showed a narrow (approximately 100μm thick) layer of elevated iron at the surface of the skin. Monte Carlo models determined that, as expected, the XRF system was most sensitive to these skin layers. However, the simulations found that the XRF system, when calibrated against homogenous water-based phantoms, was found to accurately measure average iron levels in the skin of normal pigs despite the greater sensitivity to the surface layer. The Monte Carlo results further indicated that with highly elevated skin surface iron levels, the XRF system would not provide a good estimate of average skin iron levels. The XRF estimate could, with correction factors, provide a good estimate of the iron levels in the surface layers of skin. There is limited data on iron distribution in skin, especially under conditions of disease. If iron levels are elevated at the skin surface by diseases including thalassemia and hemochromatosis, this XRF device may prove to be an accurate clinical tool. However, further data are required on skin iron distributions in healthy and iron overload disease before this system can be verified to provide accurate measurements.

Unraveling the Evolution of Dynamic Active Sites of LaNixFe1-xO3 Catalysts During OER.

Perovskites have attracted tremendous attention as potential catalysts for the oxygen evolution reaction (OER). It is well-known that the introduction of Fe into rare earth perovskites such as LaNiO3 enhances the intrinsic OER activity. Despite numerous studies on structure-property relationships, the origin of the activity and the nature of the active species are still elusive and unclear. In this work, we study a series of LaNixFe1-xO3 perovskites using in situ electrochemical surface-enhanced Raman spectroscopy and electron energy loss spectroscopy to decipher the surface evolution and formation of active species during OER. While the origin of the activity arises from NiOOH species formed from the active Ni centers in LaNiO3, our work shows that Fe serves as the active center in LaNi0.5Fe0.5O3 and forms Fe-O-Ni and FeOOH species during OER. The OER activity of LaFeO3 originates from FeOOH species, which interact with the soluble Ni species in the electrolyte forming an active electrode-electrolyte interface with high-valent stable surface iron species (Fe4+) and thereby improving the performance. Our work provides deeper insights into the synergistic effects of Ni and Fe on the catalytic activity, which in turn provides new design principles for perovskite catalysts for the OER.

The influence of cyclodextrin on hydrophobicity of pipeline and asphalt distribution: A green and efficient corrosion inhibitor

Corrosion inhibitors face significant limitations due to their non-degradability and poor applicability to asphalt systems. The molecular simulation studies show that cyclodextrin (CD) and asphalt can form supramolecular corrosion inhibitors with pipeline hydrophobic modification and corrosion inhibition effects. In particular, the rich hydroxyl structure of CD enables it to stably bind to the pipeline by forming coordination bonds and feedback bonds. When 2 CD molecules are added, the initial wetting time of the emulsion is delayed by 257.81 % compared to Span 80 with the same mass fraction. When 4 CD molecules are added, the emulsion cannot wet the iron surface within the simulation time. Furthermore, the combination of CD and asphalt allows more than 90 % of the asphalt to emulsify and prevent the emulsion from spreading on the pipeline. This results in a synergistic corrosion inhibition effect. These findings suggest that CD-based supramolecular corrosion inhibitors have the potential to be effective and environmentally friendly alternatives to traditional inhibitors in asphalt systems.