Surface Oxidation Research Articles

Theoretical investigation of multipulse femtosecond laser processing on silicon carbide: ablation, shielding effect, and recast formation

In this study, we propose a transient multi-physics coupling model for ultrafast laser ablation based on the material point method (MPM). By employing the continuum assumption for material, heat transfer equation and particle phase change, as well as spatial discretization of the model, we achieve simulations of various coupled physical phenomena such as material temperature, phase change, stress, and recast layer formation. In terms of time, we simulate laser processing processes with up to 1000 pulses. The model is validated by comparing with experimental results on ablation morphology, recast layer formation from melted particles, and surface oxidation. The proposed model accurately captures the multi-physics aspects of ultrafast laser ablation processes in SiC ceramics. The experimental validation confirms the model’s reliability and offers valuable insights into the underlying physical phenomena.

Molecular imprinting sensor based on zeolitic imidazolate framework derived Co, N-doped carbon loaded on reduced graphene oxide toward the determination of dopamine.

Anovel voltammetric sensor designed for dopamine(DA) detectionis presented utilizing a combination of zeolitic imidazolate framework (ZIF-67) derived cobalt and nitrogen-doped carbon on reduced graphene oxide (Co-N-C/rGO). ZIF-67 cubic crystals were synthesized in situ and deposited onto the graphene oxide (GO) surface through room-temperature reactions. High-temperature calcination resulted in partially collapsed cubic and spherical carbon, while simultaneously reducing GO to rGO. A molecular imprinting resorcinol polymer (MIP) membrane was also in situ applied to the Co-N-C/rGO/glassy carbon electrode (GCE) via electropolymerization. Analyses using cyclic voltammetry, electrochemical impedance, and pulse voltammetry reveal that the modified MIP/Co-N-C/rGO/GCE electrodes show improved electroconductivity and notable electrochemical reactivity towards dopamine. After optimizing detection parameters, the sensor demonstrates a wide linear detection range of 0.01-0.5 and 0.5-100μmol/L, with a limit of detection (LOD) of 3.33nmol/L (S/N = 3). Additionally, the sensor displays strong robustness, including excellent selectivity, significant resistance to interference, and long-term stability. It also shows satisfactory recovery in detecting spiked real samples.

Assessing the sustainability and safety of polyethylene terephthalate (PET) liners for lead service lines (LSL) upgrades

Polyethylene Terephthalate (PET) liners have been proposed by industry as a more cost effective and less disruptive alternative to lead service lines (LSL) replacement. However, concerns have been raised about their aging under real-use conditions and their potential health and environmental impacts. In this study, two approaches were implemented. First, bench and pilot scale experiments were carried out to investigate the aging of a PET liner under conditions that simulate normal usage. Results show early surface oxidation and leaching of potentially hazardous metals (lead, zinc and titanium). No short-term fragmentation of the PET liner into microplastics was observed. Next, a life cycle assessment (LCA) compared the health and environmental impacts of three LSL upgrade alternatives: PET liners and full LSL replacement using either copper or PEX pipes. The installation phase was shown to be the main contributor to impact scores, while the benefits of PET liners are highly dependent on their lifespan. PEX pipes installed by torpedoing lower impacts as compared to PET liners and copper pipes for equal lifespan, while the use of PET liners remains less impactful regarding human health and ecosystem quality when a complete excavation is needed. LCA derived global human health effects due to ingestion of leached metals from PET liners, copper pipes and unreplaced LSL, and showed that PET liners and copper pipes significantly reduce health impacts by 14 and 80 DALY respectively compared to unreplaced LSL. Finally, the Integrated Exposure Uptake Biokinetic (IEUBK) model was used to assess the impact of lead exposure specifically for drinking water ingestion. Estimated Blood Lead Levels (BLL) in children and infants in households with long unreplaced LSL was up to 263.7% and 207.8% greater compared to either replacement with copper pipes or rehabilitation with PET liners, showing the clear benefits of corrective action. Combining experimental results, LCA and biokinetic modeling provides actionable information for utilities to select the best upgrade options, considering environmental, health and practical constraints, whilst identifying remaining data gaps. The relative benefits of PET liners should be carefully evaluated considering their lifespan under real-life conditions, the complete replacement costs after failure, and the growing evidence of micro- and nanoplastics (MNP) risks.

Enhancing Titanium Osteoconductivity by Alkali-Hot Water Treatment.

Titanium and its alloys are essential in orthopedic and dental treatments owing to their high strength, corrosion resistance, and superior biocompatibility compared with those of other metals. However, titanium alloys are bioinert. Previous studies have indicated that alkali treatment (AT) is a straightforward method to create a surface oxidization layer on titanium, thereby improving its bioactivity. Herein, alkali-hot water pretreatment was used to enhance the osteoconductivity of titanium and to identify a simple and efficient means of enhancing the interaction between osteoblasts and implants for clinical applications. Commercial pure titanium plates were ground (CP Ti) and subjected to alkali solution and hot water treatments (AWT). Single-process CP Ti specimens were prepared via either AT or hot water treatment (WT). Network-like structural features were observed in the AT specimens and were further refined and densified in the AWT specimens. Water contact angle testing revealed that the hydrophilicity of the titanium specimen (80° for CP Ti) increased by 19° for the AT specimens but decreased by 59° for the AWT specimens. Mouse preosteoblasts (MC3T3-E1 cells) were used for in vitro evaluation. After 24 h of culturing, the number of attached MC3T3-E1 cells on the AWT specimens was 1.5 times larger than that on the CP Ti specimens, suggesting that the alkali-hot water treatment enhanced the initial cell attachment. Cell proliferation evaluation indicated that fewer cells were detected in the AT and AWT specimens compared with those in the CP Ti or WT specimens. However, osteogenic differentiation evaluation on day 10 revealed a 1.5-fold higher alkaline phosphatase expression in cells cultured on the AWT specimens than in cells cultured on the CP Ti specimens. These findings demonstrate the good cytocompatibility and osteoconductivity of AWT Ti, highlighting its benefits in orthopedics and dental treatments.

Investigation of the sorption activity of native coals to air oxygen

The influence of the gaseous medium during sample preparation, the granulometric composition, the duration of contact with air and the stage of metamorphism on the process of oxygen sorption from the air was established. It is shown that conducting sample preparation in an air atmosphere leads to primary oxidation of the outer surface of the coals, which introduces an error in determining the oxygen sorption rate constant. Fine coal fractions (0-0.2 mm) with a more developed outer surface have increased oxygen absorption activity. The rate of oxygen sorption is maximal at the initial moment of the interaction of active carbons with air and decreases with the duration of contact. The least metamorphosed hard coals of the D brand with a high content of reactive functional groups and a developed porous structure are characterized by the greatest chemisorption activity.

Exploring the mechanism of stress-induced passive layer degradation in additively manufactured Ni-Fe-Cr-based alloy 718

This study explores the formation and degradation mechanisms of the passive layer on laser powder bed fusion (L-PBF) processed Ni-Fe-Cr-based alloy 718 using high-resolution submicron analysis and microcapillary electrochemical techniques. The findings provide new insights into passive layer breakdown under tensile loading, revealing the influence of microstructural characteristics, dislocation distribution, and mechanical stresses. Tensile loading caused oxide layer cracking near cell boundaries with higher dislocation density. Detachment of the oxide layer from the matrix created voids, allowing aggressive ions to penetrate, promoting crevice corrosion. Cell boundaries remained mostly intact, as metallic particles within the surface oxide layer.

Gas sensing properties of Ti0.2V1.8CTx/V2O5 nanocomposite

A method for the preparation of nanocomposite containing Ti0.2V1.8CTx MXene core and titanium-doped vanadium oxide surface layers as a result of relatively low-temperature partial oxidation of MXene multilayer - two-dimensional vanadium-titanium carbide has been developed. It is shown that during oxidation in air atmosphere of initial Ti0.2V1.8CTx at temperature 250°С, in general, the microstructure of accordion-like aggregates with some increase in porosity of their constituent layers and increase in their thickness due to the formation of V2O5 is preserved. At the same time, preservation of the MXene structure with a decrease in the interplanar spacing from 10.3 (initial powder Ti0.2V1.8CTx) to 7.3 Å was observed. Raman spectroscopy confirmed the formation of vanadium oxide. Kelvin-probe force microscopy data revealed that the formation of Ti0.2V1.8CTx/V2O5 nanocomposite results in a decrease in the work function from 4.88 (Ti0.2V1.8CTx) to 4.68 eV. The chemosensor properties towards a range of gaseous analytes (H2, CO, NH3, NO2, C6H6, C3H6O, CH4, C2H5OH and O2) have been comprehensively studied for Ti0.2V1.8CTx/V2O5 layers coated using the microplotter printing. At increased detection temperatures (125–200°С), high sensitivity to oxygen (10% O2) and NO2 (100 ppm) is observed; there are notable responses to humidity (50% RH) throughout the 25–200°С temperature range. At room temperature, good response to acetone, ethanol and ammonia is observed.

Exploring Mechanism of H2 Adsorption on Surfaces of Iron Oxides by Density Functional Theory Calculation

Exploring Mechanism of H2 Adsorption on Surfaces of Iron Oxides by Density Functional Theory Calculation

Tailoring electrochemical CO2 reduction selectivity over CuSn by modulating surface oxidation state with infrared laser treatment

Infrared laser treatment was used to precisely modify the surface structure of CuSn electrodes, effectively fine-tuning the selectivity of reduction products. With increasing laser power, the metallic Cu and Sn surfaces became more oxidized, and the Sn/Cu composition ratio varied with depth and further changed post-EC reaction. The diversity of reduction products, including C1 (CO, CH4, and formate), C2 (C2H4, ethanol, acetate, acetaldehyde, and glycolaldehyde), and C3 (propanol and isopropanol) compounds, shifted towards a more selective production of C1 (CO and formate) products. These tailored behaviors are attributed to variations in interfacial electronic structures, oxidation states, composition ratios, and the interaction between CO2 and the density of states (Cu, O, and Sn) near the Fermi level. The laser treatment method enables precise tuning of electrode surfaces, modulation of reduction products, and enhancement of selectivity. Moreover, this technique presents a novel approach for electrode design in the field of CO2 reduction, offering new avenues for optimizing catalytic performance.

In Situ STM Study of Roughening of Au(111) Single-Crystal Electrode in Sulfuric Acid Solution during Oxidation-Reduction Cycles.

Oxidation-reduction cycles (ORCs) on Au(111) in 0.1 M sulfuric acid solution change the electrode morphology due to the formation of many new nanosized islands. With increasing the cycle number, the roughness of the surface increases due to the formation of multiatomic-step adatom islands and pits. The final roughness value is a function of the applied potential window, number of ORCs, scan rate, electrolyte concentration, and any applied delay time. In a first experiment, the roughening was tracked by recording the STM images in 11 steps during 200 ORCs. The results show the formation of pyramidal islands and a linear correlation between the roughness amplitude and the cycle number. In a second experiment, the 200 cycles were studied in 38 steps, while after each step, two images were recorded with a 3 min delay by holding the potential in the double-layer window. This leads to a lower roughness increase due to the high surface mobility of the Au surface atoms, which smoothens the surface during the delay time. Finally, the oxidation-reduction charge density per cycle shows an inverse correlation with surface roughness due to the (111) terrace showing a higher surface oxidation charge than the other sites and facets. Each delay causes a strong increase in the oxidation charge which is a consequence of surface smoothening during the delays leading to an enhancement of the (111) related oxidation charge.

Nano‐Multiactive Sites Pd/PdO/CuO/PdCu3 Formed In Situ on the Surface Hetero‐Organometallic Pd(II)/Cu(II) Nanosheet: Investigation on the Formation of Active Sites, Synergistic, and Catalytic Activity

ABSTRACTExploring the relationship between the structure of active site and the activity in molecular level and investigating the reason for deactivation are extremely important in designing the highly active catalyst. In this paper, new self‐assembly Schiff‐base Pd/Cu nanosheets supported on the surface of graphene oxide (GO) (called as GO@Hpmaba‐Pd/Cu) were fabricated and characterized. Among them, GO@Hpmaba‐Pd0.2/Cu0.8 exhibited a high activity with a TOF value of up to 95,357 h−1 and substrate suitability in Suzuki cross‐coupling reaction. GO@Hpmaba‐Pd0.2/Cu0.8 could be reused at least 13 times. GO@Hpmaba‐Pd0.2/Cu0.8 was a heterogeneous catalyst and the catalysis occurred on the surface. The truly active sites included Pd/PdO/CuO/PdCu3 formed in situ on the surface of the hetero‐organometallic Pd/Cu nanosheet during catalysis. The synergistic effects among these active sites could be described as that the electrons transferred from GO to CuO (PdO) or to Pd via ligand (Hpmaba) and subsequently electrons transferred from CuO (PdO) to Pd. These made more electron negative palladium, enhancing the oxidation addition between palladium and aryl halide and prompting the activity. The deactivation of catalyst was mainly caused by some destroyed organometallic in the nanosheet, residues adsorbed on catalytic surface, loss of active Pd due to the leaching with increase of recycling, and the aggregation of active metals.

Adsorption grand potential of OH on metal oxide surfaces.

Describing chemical processes at solid-liquid interfaces as a function of a fixed electron chemical potential presents a challenge for electronic structure calculations and is essential for understanding electrochemical phenomena. Grand Canonical Density Functional Theory (GCDFT) allows treating solid-liquid interfaces in such a way that studying the influence of a fixed electron potential arises naturally. In this work, GCDFT is used to compute the adsorption grand potential (AGP), a key parameter for understanding and predicting the behavior of adsorbates on surfaces. We focused on the adsorption of an OH molecule on three metallic surfaces commonly used in electrochemical processes, such as the oxygen evolution reaction (OER). Our study aims to offer insights into how AGP can be used to compare adsorption strengths under different fixed electron chemical potentials, which is crucial for designing efficient electrode materials. By determining the average number of electrons self-consistently under varying chemical potentials, we showed how one can distinguish between electron acquisition and depletion during the adsorption process, offering a deeper understanding of the adsorbate-surface interactions. The approach used in this work employs the Kohn-Sham-Mermin formulation of the Grand Canonical Density Functional Theory. The computations were performed using the periodic open-source density functional theory software, JDFTx, with the Garrity-Bennett-Rabe-Vanderbilt library of ultrasoft pseudopotentials. Calculations were made using truncated Coulomb potentials and the auxiliary Hamiltonian method with the PBE exchange-correlation functional, along with DFT-D2 long-range dispersion corrections. The implicit solvation model CANDLE was used to describe the electrolyte with a 1M concentration.

Enhancing Stability of Surface Au under Oxidizing Conditions through Reduced Bulk Au Content.

Contrary to the common assumption that a higher bulk content of precious metals facilitates the preservation of more surface noble metal by serving as a reservoir for surface enrichment, we demonstrate that a lower bulk content of Au results in a more stable arrangement of Au atoms at the surface of Cu-Au nanoparticles when exposed to an O2 atmosphere. Using ambient pressure X-ray photoelectron spectroscopy, we investigate the surface segregation and oxidation behavior of Cu-Au nanoparticles across various compositions. Our results reveal that in Au-rich nanoparticles exposed to an H2 atmosphere, surface segregation prompts the formation of a continuous Au-enriched shell, which subsequently oxidizes into a complete CuOx shell upon transitioning to an O2 atmosphere. Conversely, in Au-poor nanoparticles during H2 treatment, segregation results in the emergence of Au clusters embedded within the surface layer, persisting upon exposure to O2. This unexpected phenomenon shows that reducing the bulk content of precious metals can enhance the surface stability of noble atoms under oxidizing conditions, as further demonstrated by comparing the catalytic performance of Cu-Au nanoparticles with varying Au bulk contents in CO oxidation.

Study on the coating-formation process of micro arc oxidation coating on AZ31B magnesium alloy with Sc(NO3)3 addition

To investigate the effect of the addition of Sc(NO3)3 on the coating-formation process of AZ31B magnesium alloy MAO coating, microarc oxidation was conducted in a silicate-phosphate electrolyte containing 0.5 g/L Sc(NO3)3 for 15 s, 30 s, 60 s, 120 s, 240 s, and 1800 s. The oxidation voltage, surface morphology, and phase composition of the coatings were characterized using SEM, XRD, and XPS. The results indicated that Sc(NO3)3 hydrolytic complexation forms Sc(OH)2+ which leads to more uniform discharge micropores on the MAO coating surface, increasing the oxidation voltage. Compared to the MAO sample without Sc(NO3)3, the coating surface becomes denser and smoother. The MAO coating phase composition is MgO and Mg2SiO4, with Sc present as Sc2O3 in the coating.

A Procedure for Solid-Phase Extractions Using Metal-Oxide-Coated Silica Column in Lipidomics.

Lipid enrichment is indispensable for enhancing the coverage of targeted molecules in mass spectrometry (MS)-based lipidomics studies. In this study, we developed a simple stepwise fractionation method using a titanium- and zirconium-dioxide-coated solid-phase extraction (SPE) silica column that separates neutral lipids, phospholipids, and other lipids, including fatty acids (FAs) and glycolipids. Chloroform was used to dissolve the lipids, and neutral lipids, including steryl esters, diacylglycerols, and triacylglycerols, were collected in the loading fraction. Second, methanol with formic acid (99:1, v/v) was used to retrieve FAs, ceramides, and glycolipids, including glycosylated ceramides and glycosylated diacylglycerols, by competing for affinity with the Lewis acid sites on the metal oxide surface. Finally, phospholipids strongly retained via chemoaffinity interactions were eluted using a solution containing 5% ammonia and high water content (45:50 v/v, 2-propanol:water), which canceled the electrostatic and chelating interactions with the SPE column. High average reproducibility of <10% and coverage of ∼100% compared to those of the non-SPE samples were demonstrated by untargeted lipidomics of human plasma and mouse brain, testis, and feces. The advantage of our procedure was showcased by characterizing minor lipid subclasses, including dihexosylceramides containing very long-chain polyunsaturated FA in the testis, monogalactosyl and digalactosyl monoacylglycerols in feces, and acetylated and glycolylated derivatives of gangliosides in the brain that were not detected using conventional solvent extraction methods. Likewise, the value of our method in biology is maximized during glycolipidome profiling in the absence of neutral lipids and phospholipids that cover more than 80% of the chromatographic peaks.

Effect of chemical bond polarity on wafer and cleavage surface oxidation for GaAs, GaSb, InAs and InSb single crystals

Rapid development of III–V semiconductor device technologies and broadening of device applications are hindered by the high density of surface states produced in those materials by intrinsic complex oxides and surface contaminations. Surface oxides acting as non-radiating recombination centers produce a number of surface levels in the band gap. Oxidation mechanisms depend on the chemical composition of a specific III–V semiconductor compound because surface reactivities differ between materials. The effect of chemical bond polarity on surface oxidation processes in single crystal III–V semiconductor wafers is currently an important research topic. In this work, surface-sensitive XPS method has been used for studying oxidation regularities in GaAs, InAs, GaSb and InSb single crystals undergoing natural atmospheric oxidation and subjected chemical-mechanical polishing. A method of assessing oxidation levels based on chemical shifts of XPS spectral features has been developed. Oxidation level has been shown to depend on chemical bond ionicity degree, the latter being evaluated using the Sanderson and Phillips models. A decrease in surface oxidation level with an increase in bond ionicity degree has been observed for (110) single crystal wafer cleavage surfaces and for (100) single crystal wafer surfaces after single crystal slicing and chemical-mechanical polishing. We show that surface oxidation level increases in the InAs–GaAs–InSb–GaSb sequence, from arsenides to antimonides.

Unconventional structural evolution of an oxide surface in water unveiled by in situ sum-frequency spectroscopy.

Oxide-water interfaces host a wide range of important reactions in nature and modern industrial applications; however, accurate knowledge about these interfaces is still lacking at the molecular level owing to difficulties in accessing buried oxide surfaces. Here we report an experimental scheme enabling in situ sum-frequency vibrational spectroscopy of oxide surfaces in liquid water. Application to the silica-water interface revealed the emergence of unexpected surface reaction pathways with water. With ab initio molecular dynamics and metadynamics simulations, we uncovered a surface reconstruction, triggered by deprotonation of surface hydroxylated groups, that led to unconventional five-coordinated silicon species. The results help demystify the multimodal chemistry of aqueous silica discovered decades ago, bringing in fresh information that modifies the current understanding. Our study will provide new opportunities for future in-depth physical and chemical characterizations of other oxide-water interfaces.

Studying the optical properties of assembled silver and gold nanoparticles for the purpose of creating SERS sensors

The optical properties of silver and gold sols with different sizes of nanoparticles and the method of their chemical deposition on the surface of silicon, silicon oxide, glass and aluminum foil were studied in order to obtain SERS substrates – promising platforms for the development of aptamer sensors and immunochemical analysis of various pathogens. It has been established that for operation on lasers with exciting radiation wavelengths of 532, 638 and 785 nm, it is possible to create universal SERS substrates based on colloidal solutions obtained by the liquid-phase chemical method with an average silver particle size of 40 nm and by the Leopold-Lendl method with an average size of 20 nm.

Implementation of frozen density embedding in CP2K and OpenMolcas: CASSCF wavefunctions embedded in a Gaussian and plane wave DFT environment.

Most chemical processes happen at a local scale where only a subset of molecular orbitals is directly involved and only a subset of covalent bonds may be rearranged. To model such reactions, Density Functional Theory (DFT) is often inadequate, and the use of computationally more expensive correlated wavefunction (WF) methods is required for accurate results. Mixed-resolution approaches backed by quantum embedding theory have been used extensively to approach this imbalance. Based on the frozen density embedding freeze-and-thaw algorithm, we describe an approach to embed complete active space self-consistent field simulations run in the OpenMolcas code in a DFT environment calculated in CP2K without requiring any external tools. This makes it possible to study a local, active part of a chemical system in a larger and relatively static environment with a computational cost balanced between the accuracy of a WF method and the efficiency of DFT, which we test on environment-subsystem pairs. Finally, we apply the implementation to an oxygen molecule leaving an aluminum (111) surface and a ruthenium(IV) oxide (110) surface.

Enhanced photoelectrochemical CO2 reduction activity towards selective generation of alcohols over CuxO/SrTiO3 heterojunction photocathodes

Photoelectrochemical reduction (PECR) of CO2 to value-added chemicals and fuels will reduce the dependency on fossil fuels, also it will solve environmental issues that arise due to greenhouse gases. A heterojunction of CuxO/SrTiO3 with varying post-annealing temperature ranges from 300 to 600 °C (CS300-600) was synthesized by overlying the spin-coated SrTiO3 on electrodeposited Cu2O over the FTO glass substrate. The synthesized photoelectrode's crystallinity and phase formation significantly varied by varying the post-annealing temperature, which was characterized via XRD and Raman spectroscopy. Optical, morphological, type of heterojunction formation and elemental surface oxidation states of photoelectrodes were studied through UV–visible DRS spectrum, FE-SEM, and XPS analysis respectively. Electrocatalytic analysis such as Linear Sweep Voltammetry (LSV), and Electrochemical Impedance Spectrometry (EIS) was employed, thus it conforms to the highest photocurrent density (−1.38 mA/cm2 at −0.6V vs. Ag/AgCl), and low charge transfer resistance (RCT=0.412 kΩ) at the electrode-electrolyte interfaces for CS500 photoelectrode as compared to others photoelectrodes. PECR of CO2 to liquid product formation was evaluated by applying different potential ranges (0 to −0.6 V vs. Ag/AgCl). Highest methanol formation of 48.69 μmol.cm−2hr−1, which is approximately 9 times enhanced as compared to the pure Cu2O (5.62 μmol.cm−2hr−1) photoelectrode at 0 V vs Ag/AgCl for CS500 heterojunction. Optimization of overlaying SrTiO3 synthesis temperature for crystallization formation on Cu2O and applied photoelectrode potential findings could pave the way for designing other new heterojunction types for selective liquid alcohol production.