​Statistical-based optimization and mechanism assessments of Arsenic (III)​ adsorption by ZnO-Halloysite nanocomposite​.

Arsenic contamination in aqueous media is a serious environmental problem, especially in developing countries. In this research, the Box-Behnken response surface methodology was used to optimize the most relevant variables affecting arsenic adsorption on the ZnO-halloysite surface, including temperature, adsorbent dosage, pH, contact time, and As (III) initial concentration. The regression analysis indicated that the experimental data were appropriately fitted to a quadratic model with the adjusted R-squared value (R2) of 0.982 for As(III) adsorption capacity and a linear model with R2 of 0.931 for As(III) removal. The p-values for both adsorption capacity and removal efficiency were below 0.05, with F-values of 116.91 and 115.58, respectively, supporting the model's validity. The optimum conditions for maximum removal of As(III) were determined through numerical and graphical optimization using the desirability function. It was found that the optimum conditions for adsorption were pH = 7.99, contact time of 3.99 h, As(III) initial concentration of 49.96 mg/L, and adsorbent dosage of 0.135 g/40 ml. The accuracy of the optimization procedure was confirmed by a confirmatory experiment, which showed a maximum arsenic removal of 91.31% and an adsorption capacity of 12.63 mg/g under optimized conditions. Moreover, XPS analysis was performed at different pH levels to investigate the As (III) adsorption mechanism. The results demonstrated that As(III) adsorption occurs at acidic and neutral pH levels. On the other hand, when pH is increased to 8, As (III) oxidizes to As (V), and then adsorption occurs.

Depth-Resolved X-Ray Photoelectron Spectroscopy Evidence of Intrinsic Polar States in HfO2-Based Ferroelectrics.

The discovery of ferroelectricity in nanoscale hafnia-based oxide films has spurred interest in understanding their emergent properties. Investigation focuses on the size-dependent polarization behavior, which is sensitive to content and movement of oxygen vacancies. Though polarization switching and electrochemical reactions is shown to co-occur, their relationship remains unclear. This study employs X-ray photoelectron spectroscopy with depth sensitivity to examine changes in electrochemical states occurring during polarization switching. Contrasting Hf0.5Zr0.5O2 (HZO) with Hf0.88La0.04Ta0.08O2 (HLTO), a composition with an equivalent structure and comparable average ionic radius, electrochemical states are directly observed for specific polarization directions. Lower-polarization films exhibit more significant electrochemical changes upon switching, suggesting an indirect relationship between polarization and electrochemical state. This research illuminates the complex interplay between polarization and electrochemical dynamics, providing evidence for intrinsic polar states in HfO2-based ferroelectrics.

A New Mechanism for the Inhibition of SA106 Gr.B Carbon Steel Corrosion by Nitrite in Alkaline Water.

The purpose of this study was to investigate the composition of oxide films formed on SA106 Gr.B carbon steel in nitrite solutions at 35 °C for 1000 h. The product of the reduction of nitrite during the corrosion inhibition process was also examined. The X-ray photoelectron spectroscopy results revealed that a thin Fe3O4 film was formed and ammonium ions were adsorbed on the outermost surface of the oxide film. The presence of ammonium ions was also demonstrated by ion chromatography. These results indicate that nitrites are reduced to ammonium ions, which in turn promotes the formation of the protective Fe3O4 film.

Probing Surface Dynamics of SiOx Thin-Film Electrodes during Cycling through X-Ray Photoemission Spectroscopy and Operando X-Ray Reflectivity.

SiOx electrodes are promising for high-energy-density lithium-ion batteries (LIBs) due to their ability to mitigate volume expansion-induced degradation. Here, we investigate the surface dynamics of SiOx thin-film electrodes cycled in different carbonate-based electrolytes using a combination of ex situ X-ray photoelectron spectroscopy (XPS) and operando synchrotron X-ray reflectivity analyses. The thin-film geometry allows us to probe the depth-dependent chemical composition and electron density from surface to current collector through the solid electrolyte interphase (SEI), the active material, and the thickness evolution during cycling. Results reveal that SiOx lithiation initiates below 0.4 V vs Li+/Li and indicate a close relationship between SEI formation and SiOx electrode lithiation, likely due to the high resistivity of SiOx. We find similar chemical compositions for the SEI in FEC-containing and FEC-free electrolytes but observe a reduced thickness in the former case. In both cases, the SEI thickness decreases during delithiation due to the removal or dissolution of some carbonate species. These findings give insights into the (de)lithiation of SiOx, in particular, during the formation stage, and the effect of the presence of FEC in the electrolyte on the evolution of the SEI during cycling.

Nano-TiO2/TiN Systems for Electrocatalysis: Mapping the Changes in Energy Band Diagram across the Semiconductor|Current Collector Interface and the Study of Effects of TiO2 Electrochemical Reduction Using UV Photoelectron Spectroscopy.

TiO2 is the most widely used material in photoelectrocatalytic systems. A key parameter to understand its efficacy in such systems is the band bending in the semiconductor layer. In this regard, knowledge on the band energetics at the semiconductor/current collector interface, especially for a nanosemiconductor electrode, is extremely vital as it will directly impact any charge transfer processes at its interface with the electrolyte. Since direct investigation of interfacial electronic features without compromising its structure is difficult, only seldom are attempts made to study the semiconductor/current collector interface specifically. This work utilizes ultraviolet photoelectron spectroscopy (UPS) to determine the valence band maximum (EVBM) and Fermi level (EF) at different depths in a nano-TiO2/TiN thin-film system reached using an Ar gas-clustered ion beam (GCIB). By combining UPS with GCIB depth profiling, we report an innovative approach for truly mapping the energy band structure across a nanosemiconductor/current collector interface. By coupling it with X-ray photoelectron spectroscopy (XPS), correlations among chemistry, chemical bonding, and electronic properties for the nano-TiO2/TiN interface could also be studied. The effects of TiO2 in situ electrochemical reduction in aqueous electrolytes are also investigated where UPS confirmed a decrease in the semiconductor work function (WF) and an associated increase in n-type Ti3+ centers of nano-TiO2 electrodes post use in a 0.2 M potassium chloride solution. We report the use of UPS to precisely determine the energy band diagrams for a nano-TiO2/TiN thin-film interface and confirm the increase in TiO2 n-type dopant concentrations during electrocatalysis, promoting a much more comprehensive and intuitive understanding of the TiO2 activation mechanism by proton intercalation and therefore further optimizing the design process of efficient photocatalytic materials for solar conversion.

Preparation of a covalent organic framework-modified silica-gel composite for the effective adsorption of Pd(II), Zr(IV) and Mo(VI) from nitric acid solution.

In this study, a novel covalent organic framework-modified silica-gel composite (Si-COF) was synthesized for the adsorption of palladium [Pd(II)], zirconium [Zr(IV)], and molybdenum [Mo(VI)] from nitric acid solutions and its adsorption behaviors were systemically investigated under the effects of contact time, nitric acid concentration, solution temperature and others. The pseudo-second-order kinetic model governed the adsorption of these metal ions onto the Si-COF composite, and the Langmuir isotherm model well-matched with the experimental data, with maximum adsorption capacities of 0.588, 0.221, and 0.417 mmol/g for Pd(II), Zr(IV) and Mo(VI), respectively. The adsorption of these metal ions was clarified to originate from the interaction with the abundant nitrogenous groups on the Si-COF composite by the X-ray photoelectron spectroscopy (XPS) method.

Evaluation of Antibacterial Activity of Bismuth Ferrites Nanoparticles in the inhibition of E. coli and S. aureus bacteria.

In this work, bismuth ferrites (BFO) nanoparticles were produced in the form of using sol-gel technique, followed by annealing in a tube furnace in temperatures from 400 °C to 650 ºC. X-ray diffraction (XRD) results showed the formation of small sizes nanoparticles (NPs) with high purity. Structural analysis displayed that annealing at 600 ºC could make BFO NPs be fitted to rhombohedral space group (R3c), with small quantity of spurious phases. The sizes of the BFO nanoparticles determined by transmission electron microscopy (HRTEM) are between 50 to 100 nm. To evaluate the efficiency of BFO in antimicrobial susceptibility tests, the nanoparticles were dispersed through nanoemulsion and tested agar diffusion method and dilution in a 96 well plate using a Gram positive strains (Staphylococcus aureus) and Gram negative strain (Escherichia coli). The antibacterial activity of the BFO NPs was partially tested at concentrations of 2 mg/mL with MIC greater than 60 µg/mL for both bacteria.

Extending Copper Interconnects and Epoxy Dielectrics to Multi-GHz Frequencies.

Future multichip packages require Die-to-Die (D2D) interconnects operating at frequencies above 10 GHz; however, the extension of copper interconnects and epoxy dielectrics presents a trade-off between performance and reliability. This paper explores insertion losses and adhesion as a function of interface roughness at frequencies up to 18 GHz. We probe epoxy surface chemistry as a function of curing time and use wet etching to modulate surface roughness. The morphology is quantified by atomic force microscopy (AFM) and two-dimensional fast Fourier transform (2D FFT). Peel test and vector network analysis are used to examine the impacts of both type and level of roughness. The trade-offs between power efficiency and reliability are presented and discussed.

Ultraviolet Light-Induced Surface Changes of Tungsten Oxide in Air: Combined Scanning Transmission Electron Microscopy and X-ray Photoelectron Spectroscopy Analysis.

Scanning transmission electron microscopy (STEM) and X-ray photoelectron spectroscopy analyses were combined to clarify the ultraviolet light-induced surface changes of WO3 in air. Identical-location STEM (IL-STEM) analysis showed that the WO3 particle surface was covered with an amorphous thin film after ultraviolet irradiation in air. X-ray photoelectron spectroscopy analysis showed that hydrocarbon decomposition and the formation of carboxyl/hydroxyl species occurred. These results suggested that the amorphous thin films consisted of photocatalytic oxidative species of hydrocarbon. The IL-STEM analysis could detect small light-induced changes. This technique will be useful for the microscopic characterization of photocatalysis or photoinduced hydrophilic conversion.

Distinguishing Organomagnesium Species in the Grignard Addition to Ketones with X-ray Spectroscopy.

The addition of Grignard reagents to ketones is a well-established textbook reaction. However, a comprehensive understanding of its mechanism has only recently begun to emerge. X-ray spectroscopy, because of its high selectivity and sensitivity, is the ideal tool for distinguishing between an ensemble of competing pathways. With this aim in mind, we investigated the concerted mechanism of the addition of methylmagnesium chloride (CH$_3$MgCl) to acetone in tetrahydrofuran by simulating the X-ray spectra of different molecules in solution. We used electronic structure methods to calculate the X-ray absorption spectra at the Mg K- and L$_1$-edges and the X-ray photoelectron spectra at the Mg K-edge for different organomagnesium species, which coexist in solution due to the Schlenk equilibrium. The simulated spectra show that individual species can be distinguished throughout the different stages of the reaction.Each species has a distinct spectral feature which can be used as a fingerprint in solution. The absorption and photoelectron spectra consistently show a blue shift as the reaction progressed from reagents to products.

Phytomediated Copper Oxide Nanoparticles Derived from the Fronds of Adiantum venustum D.Don: Evaluation of their Biomedical Potential.

The green synthesis of copper oxide nanoparticles (CuO) mediated by crude ethanolic extract and the n-butanol fraction of Adiantum venustum represents a groundbreaking approach in nanotechnology, combining ecological sustainability with advanced functionality. This innovative method leverages the natural bioactive compounds present in A. venustum to produce CuO nanoparticles, which exhibit remarkable antioxidant, anti-inflammatory, antimicrobial, and anti-proliferative properties. The green synthesized nanoparticles were characterized using a variety of techniques, as XRD confirmed the crystalline nature of the CuO nanoparticles, with a crystallite size of 14.65 nm for CuO-C and 18.73 nm for CuO-B. The grain sizes of CuO-C (14.09 ± 0.17 nm) and CuO-B (67.88 ± 2.08 nm) were determined using transmission electron microscopy micrographs. Furthermore, the synthesized nanomaterial and the crude ethanolic extract, n-butanol fraction, were examined for their biological potentials namely antioxidant, anti-inflammatory, antimicrobial, and anti-proliferative activity against HeLa cancer cells. Among the synthesized nanomaterials, copper oxide nanoparticles synthesized by utilizing the n-butanol fraction have appeared as a potential biomedical agent. CuO-B has arisen as an antioxidant agent with IC50 values of 44.63 ± 0.49 µg/mL, 48.49 ± 0.17 µg/mL, and 35.39 ± 0.61 µg/mL for DPPH, FRAP, and reducing power assay, respectively. Furthermore, the significant antibacterial potential of CuO-B against gram-positive (S. aureus MIC 46.88 µg/mL) and gram-negative (K. pneumonia MIC 23.48 µg/mL) bacterial strains cannot be neglected either. Along with this, the IC50 value (138.07 µg/mL) of CuO-B against HeLa cells proved it to be a potential anticancerous agent. Hence, this novel approach emphasized that these synthesized nanoparticles have tremendous biological potential and can be applied to various fields of agriculture and biomedicine.

Band alignment and surface photo-voltage analysis of c-Si/SiOx/poly-silicon passivating-contact stacks through X-ray photoelectron spectroscopy.

Ultrathin SiOx layers and c-Si/SiOx interfaces find application in tunnel-oxide passivated contacts (TOPcon) for high-efficiency silicon solar cells. Here, we investigate their detailed microscopic properties, with specific attention for the case of c-Si(100) substrates, capped either by p-type or n-type poly-silicon layers [c-Si/SiOx/poly-Si (p+) or c-Si/SiOx/poly-Si (n+)]. Our focus is on the effects of the substrate preparation conditions (either by a dry-plasma or wet SiOx process) and the high-temperature annealing step (as required for the poly-Si crystallization) on the SiOx stoichiometry and its microscopic structure. Through advanced photoemission techniques, we find a clear decreased valence band offset between the c-Si and SiOx (from 4.5 eV to 4.15 eV) when comparing the dry SiOx with the wet SiOx process, independent of the SiOx film thickness, but correlating with the relative fraction of sub-stochiometric Si states. We lastly examine the magnitude of band-bending of the contact structure through controlled in-situ exposure to light of the surfaces and subsequent tracking of core and valence band levels via a surface photovoltage and a junction photo-voltage (JPV) effect. By analyzing this JPV effect qualitatively, we find it to be proportional to the expected quasi fermi level splitting within the c-Si wafer.

A versatile sample-delivery system for X-ray photoelectron spectroscopy of in-flight aerosols and free nanoparticles at MAX IV Laboratory.

Aerosol science is of utmost importance for both climate and public health research, and in recent years X-ray techniques have proven effective tools for aerosol-particle characterization. To date, such methods have often involved the study of particles collected onto a substrate, but a high photon flux may cause radiation damage to such deposited particles and volatile components can potentially react with the surrounding environment after sampling. These and many other factors make studies on collected aerosol particles challenging. Therefore, a new aerosol sample-delivery system dedicated to X-ray photoelectron spectroscopy studies of aerosol particles and gas molecules in-flight has been developed at the MAX IV Laboratory. The aerosol particles are brought from atmospheric pressure to vacuum in a continuous flow, ensuring that the sample is constantly renewed, thus avoiding radiation damage, and allowing measurements on the true unsupported aerosol. At the same time, available gas molecules can be used for energy calibration and to study gas-particle partitioning. The design features of the aerosol sample-delivery system and important information on the operation procedures are described in detail here. Furthermore, to demonstrate the experimental range of the aerosol sample-delivery system, results from aerosol particles of different shape, size and composition are presented, including inorganic atmospheric aerosols, secondary organic aerosols and engineered nanoparticles.

NiOx Passivation in Perovskite Solar Cells: From Surface Reactivity to Device Performance.

Nonstoichiometric nickel oxide (NiOx) is one of the very few metal oxides successfully used as hole extraction layer in p-i-n type perovskite solar cells (PSCs). Its favorable optoelectronic properties and facile large-scale preparation methods are potentially relevant for future commercialization of PSCs, though currently low operational stability of PSCs is reported when a NiOx hole extraction layer is used in direct contact with the perovskite absorber. Poorly understood degradation reactions at this interface are seen as cause for the inferior stability, and a variety of interface passivation approaches have been shown to be effective in improving the overall solar cell performance. To gain a better understanding of the processes happening at this interface, we systematically passivated specific defects on NiOx with three different categories of organic/inorganic compounds. The effects on NiOx and the perovskite (MAPbI3) deposited on top were investigated using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Here, we find that the perovskite's structural stability and film formation can be significantly affected by the passivation treatment of the NiOx surface. In combination with density functional theory (DFT) calculations, a likely origin of NiOx-perovskite degradation interactions is proposed. The surface passivated NiOx layers were incorporated into MAPbI3-based PSCs, and the influence on device performance and operational stability was investigated by current-voltage (J-V) characterization, impedance spectroscopy (IS), and open circuit voltage decay (OCVD) measurements. Interestingly, we find that a superior structural stability due to interface passivation must not relate to high operational stability. The discrepancy comes from the formation of excess ions at the interface, which negatively impacts all solar cell parameters.

Reversible oxidation of ethylene on ferroelectric BaTiO3(001): An X-ray photoelectron spectroscopy study.

Adsorption and desorption of ethylene on BaO-terminated (001) barium titanate are investigated by X-ray photoelectron spectroscopy. Carbon is found in an oxidized state, at a binding energy similar to that resulting from CO adsorption on BaTiO3(001). The amount of carbon adsorbed on the surface is also similar to the case of CO/BaTiO3(001). Upon heating the substrate up to the loss of its ferroelectric polarization, the C 1s signal from the oxidized spectral region vanishes. At the same time, there was no noticeable oxygen depletion of the surface after repeated C2H4 adsorption and desorption. The substrate remains stable after repeated oxidative adsorption and desorption of ethylene. Desorption occurs at different temperatures, depending on the adsorption temperature, which suggests different adsorption geometries: non-dissociated adsorption at high temperature with ethylene bond on two surface oxygen atoms, and locally dissociated adsorption at lower temperatures, in "formaldehyde-like" local configurations.

Preliminary Evaluation of Bioactive Collagen-Polyphenol Surface Nanolayers on Titanium Implants: An X-ray Photoelectron Spectroscopy and Bone Implant Study.

To endow an implant surface with enhanced properties to ensure an appropriate seal with the host tissue for inflammation/infection resistance, next-generation bone implant collagen-polyphenol nanolayers were built on conventional titanium surfaces through a multilayer approach. X-ray Photoelectron Spectroscopy (XPS) analysis was performed to investigate the chemical arrangement of molecules within the surface layer and to provide an estimate of their thickness. A short-term (2 and 4 weeks) in vivo test of bone implants in a healthy rabbit model was performed to check possible side effects of the soft surface layer on early phases of osteointegration, leading to secondary stability. Results show the building up of the different nanolayers on top of titanium, resulting in a final composite collagen-polyphenol surface and a layer thickness of about 10 nm. In vivo tests performed on machined and state-of-the-art microrough titanium implants do not show significant differences between coated and uncoated samples, as the surface microroughness remains the main driver of bone-to-implant contact. These results confirm that the surface nanolayer does not interfere with the onset and progression of implant osteointegration and prompt the green light for specific investigations of the potential merits of this bioactive coating as an enhancer of the device/tissue seal.

Enhanced Photoluminescence of Plasma-Treated Recycled Glass Particles.

Recycled soda-lime glass powder is a sustainable material that is also often considered a filler in cement-based composites. The changes in the surface properties of the glass particles due to the treatments were analyzed by X-ray photoelectron spectroscopy (XPS) and optical spectroscopy. We have found that there is a relatively high level of carbon contamination on the surface of the glass particles (around 30 at.%), so plasma technology and thermal annealing were tested for surface cleaning. Room temperature plasma treatment was not sufficient to remove the carbon contamination from the surface of the recycled glass particles. Instead, the room temperature plasma treatment of recycled soda-lime glass particles leads to a significant enhancement in their room temperature photoluminescence (PL) by increasing the intensity and accelerating the decay of the photoluminescence. The enhanced blue PL after room-temperature plasma treatment was attributed to the presence of carbon contamination on the glass surface and associated charge surface and interfacial defects and interfacial states. Therefore, we propose blue photoluminescence under UV LED as a fast and inexpensive method to indicate carbon contamination on the surface of glass particles.

Directional Electron Transfer in CuInS2/Mo2S3 S-Scheme Heterojunctions for Efficient Photocatalytic Hydrogen Production.

The photocatalytic conversion of solar energy to hydrogen is a promising pathway toward clean fuel production, yet it requires advancement to meet industrial-scale demands. This study demonstrates that the interface engineering of heterojunctions is a viable strategy to enhance the photocatalytic performance of CuInS2/Mo2S3. Specifically, CuInS2 nanoparticles are incorporated into Mo2S3 nanospheres via a wet impregnation technique to form an S-scheme heterojunction. This configuration facilitates directional electron transfer, optimizing electron utilization and fostering efficient photocatalytic processes. The presence of an S-scheme heterojunction in CuInS2/Mo2S3 is corroborated by in situ irradiation X-ray photoelectron spectroscopy and density functional theory analyses, which confirm the directional movement of electrons at the interface of heterojunction. Comprehensive characterization of the heterojunction photocatalyst, including phase, structural, and photoelectric property assessments, reveals a significant specific surface area and light absorption capability. These attributes augment the number of active sites available in CuInS2/Mo2S3 for proton reduction reactions. This study offers a pragmatic approach for designing metal sulfide-based photocatalysts via strategic interface engineering, potentially advancing the field toward sustainable hydrogen production.

Study of CO2 Adsorption Properties on the SrTiO3(001) Surface with Ambient Pressure XPS.

The adsorption properties of CO2 on the SrTiO3(001) surface were investigated using ambient pressure X-ray photoelectron spectroscopy under elevated pressure and temperature conditions. On the Nb-doped TiO2-enriched (1 × 1) SrTiO3 surface, CO2 adsorption, i.e., the formation of CO3 surface species, occurs first at the oxygen lattice site under 10-6 mbar CO2 at room temperature. The interaction of CO2 molecules with oxygen vacancies begins when the CO2 pressure increases to 0.25 mbar. The adsorbed CO3 species on the Nb-doped SrTiO3 surface increases continuously as the pressure increases but starts to leave the surface as the surface temperature increases, which occurs at approximately 373 K on the defect-free surface. On the undoped TiO2-enriched (1 × 1) SrTiO3 surface, CO2 adsorption also occurs first at the lattice oxygen sites. Both the doped and undoped SrTiO3 surfaces exhibit an enhancement of the CO3 species with the presence of oxygen vacancies, thus indicating the important role of oxygen vacancies in CO2 dissociation. When OH species are removed from the undoped SrTiO3 surface, the CO3 species begin to form under 10-6 mbar at 573 K, thus indicating the critical role of OH in preventing CO2 adsorption. The observed CO2 adsorption properties of the various SrTiO3 surfaces provide valuable information for designing SrTiO3-based CO2 catalysts.

The surface chemistry of the atomic layer deposition of metal thin films.

In this perspective we discuss the progress made in the mechanistic studies of the surface chemistry associated with the atomic layer deposition (ALD) of metal films and the usefulness of that knowledge for the optimization of existing film growth processes and for the design of new ones. Our focus is on the deposition of late transition metals. We start by introducing some of the main surface-sensitive techniques and approaches used in this research. We comment on the general nature of the metallorganic complexes used as precursors for these depositions, and the uniqueness that solid surfaces and the absence of liquid solvents bring to the ALD chemistry and differentiate it from what is known from metalorganic chemistry in solution. We then delve into the adsorption and thermal chemistry of those precursors, highlighting the complex and stepwise nature of the decomposition of the organic ligands that usually ensued upon their thermal activation. We discuss the criteria relevant for the selection of co-reactants to be used on the second half of the ALD cycle, with emphasis on the redox chemistry often associated with the growth of metallic films starting from complexes with metal cations. Additional considerations include the nature of the substrate and the final structural and chemical properties of the growing films, which we indicate rarely retain the homogeneous 2D structure often aimed for. We end with some general conclusions and personal thoughts about the future of this field.