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N2O and CO coexist in various industrial and mobile sources. The synergistic reaction of N2O and CO to generate N2 and CO2 has garnered significant research interest, but it remains extremely challenging. Herein, we constructed an atomically dispersed Rh-supported CeO2 catalyst with asymmetric Rh-O-Ce sites through gradient Rh 4d-O 2p-Ce 4f orbital coupling. This design effectively regulates the 4f electron states of Ce and promotes the electron filling of the O 3π* antibonding orbital to facilitate N-O bond cleavage. Near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) reveals that CO reacts with the surface-adsorbed O* generated by N2O decomposition through self-tandem catalysis, accelerating the rate-limiting step in N2O decomposition and activating the synergistic reaction of N2O and CO at temperatures as low as 115 °C. This work can guide the development of high-performance catalysts using the strategy of high-order orbital hybridization combined with the tandem concept to achieve versatile catalytic applications.

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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.

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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.

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Developing long-lasting humidity sensors is essential for sustainable advancements in nanotechnology. Prolonged exposure to high humidity can cause sensors to drift from their calibration points, leading to long-term accuracy issues. Our research aims to develop a fabrication method that produces stable sensors capable of withstanding the environmental challenges faced by humidity sensors. Traditional iron-based nanoparticles often require complex treatments, such as chemical modification or thermal annealing, to maintain their properties. This study introduces a novel, one-step synthesis method for iron-based thin films with exceptional stability. The synthesized films were thoroughly characterized using X-ray photoelectron spectroscopy (XPS) to evaluate their phase stability and nitride formation. The method proposed in this study employs an electrical sparking discharge process within a pure nitrogen atmosphere under a 0.2 T magnetic field, producing thin films composed of nanoparticles approximately 20 nm in size. The resulting films demonstrate superior performance in humidity sensing applications compared to conventional methods. This straightforward and efficient approach offers a promising path toward robust and sustainable humidity sensors.

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Thiol-functionalized mesoporous silica and materials potentially dedicated to diverse applications of composite materials, metal colloids, and metal catalysts, etc. Here, we developed a new synthesis route for 3-methacryloxypropyl trimethoxy silane (MPTMS) functionalized mesoporous silica (KIT-6), achieving a 71.5% enhancement in thiol functionalization on KIT-6 surfaces. Characterization using XRD, TEM, BET, FTIR, Raman, 29Si NMR, XPS, and ICP-OES revealed structural and morphological features. XRD, TEM, and BET confirmed the three-dimensional structural stabilization of mesoporous silica with ~4 nm pore diameter and a surface area of 1451 m2 g-1. FTIR, Raman, and 29Si NMR studies established the mechanism of thiol functionalization, the formation of a new wormhole chain structural framework (WCSF), and stabilization through hydrogen bonding within the mesopores. The 29Si NMR spectra showed characteristic peaks (T3, T2, Q4, Q3) indicating self-condensed functionalized thiols with siloxane networks. XPS analysis validated enhanced thiol functionalization, indicating a structurally homogeneous WCSF suitable for mercury adsorption. ICP-OES measured a mercury adsorption capacity of 3199.6 mg g-1 for KIT-6, with an Hg2+/S ratio of 1.8, corroborated by molecular structure and mechanism analysis. This innovative thiol functionalization approach enhances the efficacy of applications such as extracting Hg2+ from contaminated sources.

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In this study, biochars were produced from by-products of the herbal industry, specifically fennel seeds (Foeniculum vulgare), through direct activation by carbon dioxide at two different temperatures. The biochar samples were comprehensively analysed. Additionally, adsorption studies were conducted for methylene blue. The resulting adsorbents exhibited a specific surface area ranging from 2.29 to 14.60 m2/g. The resulting materials displayed a basic character on their surface. The constants for adsorption models were determined for each dye as well as thermodynamic parameters and the kinetics of the process. The sorption capacities of methylene blue for the samples exhibited a range of 22 to 43 mg/g. The adsorption kinetics of the dye on the biochar materials were found to follow a pseudo-second-order model, with the adsorption process best described by the Langmuir isotherm for the DA-800 sample and the Freundlich isotherm for the DA-750 sample. This indicates the development of a monolayer adsorbate on the biochar surfaces. The efficacy of the adsorption process in aqueous solutions of methylene blue was found to increase with rising temperature. Furthermore, based on thermodynamic studies, the adsorption process was found to be spontaneous and endothermic.

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Pure zinc tetraphenylporphyrin (ZnTPP) adsorbs on rutile TiO2(110) as flat-lying molecules, mostly interacting with the surface through weak van-der-Waals interactions. Pure monocarboxyphenyl triphenylporphyrin (2HMCTPP) forms a covalent bond to the rutile TiO2(110) surface through the carboxylic acid group, yielding densely-packed layers of upright-standing molecules. If given the chance, 2HMCTPP could therefore be expected to displace the weaker-bonding ZnTPP molecules. However, if 2HMCTPP is deposited on top of a ZnTPP layer, a coadsorption structure instead forms, with the carboxylic-acid groups of the 2HCMTPP molecules bonding to titanium atoms of the surface exposed by gaps between the molecules in the flat-lying ZnTPP adsorption structure.

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Since enormous amounts of antibiotics are consumed daily by millions of patients all over the world, tons of pharmaceutical residuals reach aquatic bodies. Accordingly, our study adopted the Fenton catalytic degradation approach to conquer such detrimental pollutants. (Ce0.33Fe) MIL-88A was fabricated by the hydrothermal method; then, it was supported on the surface of g-C3N4 sheets using the post-synthetic approach to yield a heterogeneous Fenton-like (Ce0.33Fe) MIL-88A/10%g-C3N4 catalyst for degrading the tetracycline hydrochloride drug. The physicochemical characteristics of the catalyst were analyzed using FT-IR, SEM-EDX, XRD, BET, SEM, and XPS. The pH level, the H2O2 concentration, the reaction temperature, the catalyst dose, and the initial TC concentration were all examined as influencing factors of TC degradation efficiency. Approximately 92.44% of the TC was degraded within 100 min under optimal conditions: pH = 7, catalyst dosage = 0.01 g, H2O2 concentration = 100 mg/L, temperature = 25 °C, and TC concentration = 50 mg/L. It is noteworthy that the practical outcomes revealed how the Fenton-like process and adsorption work together. The degradation data were well-inspected by first-order and second-order models to define the reaction rate. The synergistic interaction between the (Ce0.33Fe) MIL-88A/10%g-C3N4 components produces a continuous redox cycle of two active metal species and the electron-rich source of g-C3N4. The quenching test demonstrates that •OH is the primary active species for degrading TC in the H2O2-(Ce0.33Fe) MIL-88A/10%g-C3N4 system. The GC-MS spectrum elucidates the yielded intermediates from degrading the TC molecules.

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Optical paths in telescopes frequently incorporate silver mirrors for high sensitivity. Unfortunately, silver mirrors without protective coatings are susceptible to sulfurization and oxidation, compromising their quality. Even with protective layers, insufficient adhesion between the coating and the silver film can lead to peeling, exposing the silver to external environments and affecting its quality. This study aimed to identify dielectric materials with superior adhesion to silver, rendering them ideal choices for silver coating applications. By electron gun evaporation, different dielectric layers were deposited on the top and bottom of the silver film under a substrate temperature below 150 °C. These coatings were composed of materials with desired refractive indices, including aluminum oxide (Al2O3), aluminum-doped silicon, magnesium fluoride (MgF2), and other dielectrics. Following the deposition, a tape adhesion test was conducted to evaluate the bond strength of the samples. X-ray photoelectron spectroscopy (XPS) analysis was carried out to investigate the interaction between silver and its neighboring layers. The results revealed that Al2O3 and MgF2 exhibited exceptional adhesion to silver. Moreover, these multilayer coatings can effectively enhance the reflectance of silver in the visible (VIS) wavelength ranges.

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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.

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This study investigates the synthesis and characterization of KSrVO4 phosphors doped with Er3+ ions using combustion synthesis route by using urea as a fuel. X-ray diffraction analysis confirmed the orthorhombic phase and nano-scale crystallite size of around 21 nm, while transmission electron microscopy showed spherical and rod-shaped morphologies. The studies detected upconversion emission spectra at 526, 542 and 643 nm, representing green and red transitions under 980 nm excitation. Downshifting emissions under 350 nm excitation revealed peaks at 492, 544 and 680 nm. The critical quenching concentration was 2.5 mol%, resulting from dipole-quadrupole interactions among dopant ions. The direct and indirect optical band gaps were calculated as 3.61 and 3.41 eV, respectively. The calculated chromaticity coordinates and color correlated temperature values of the phosphor surpassed 5000 K, suggesting its viability for cool LED applications. These findings emphasize KSrVO4:Er3+ as a promising greenish component in white LEDs and a potent upconverting luminescence material for bio-imaging and photovoltaics.

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This study aims to establish and optimize a process for the fabrication of 3D microstructures of the biocompatible polymer Parylene C using hot embossing techniques. The different process parameters such as embossing temperature, embossing force, demolding temperature and speed, and the usage of a release agent were optimized, utilizing adhesive micropillars as a use case. To enhance compatibility with conventional semiconductor fabrication techniques, hot embossing of Parylene C was adapted from conventional stainless steel substrates to silicon chip platforms. Furthermore, this adaptation included an investigation of the effects of the hot embossing process on metal layers embedded in the Parylene C, ensuring compatibility with the ultra-thin Parylene printed circuit board (PCB) demonstrated previously. To evaluate the produced microstructures, a combination of characterization methods was employed, including light microscopy (LM) and scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared spectroscopy (FTIR). These methods provided comprehensive insights into the morphological, chemical, and structural properties of the embossed Parylene C. Considering the improved results compared to existing patterning techniques for Parylene C like plasma etching or laser ablation, the developed hot embossing approach yields a superior structural integrity, characterized by increased feature resolution and enhanced sidewall smoothness. These advancements render the method particularly suitable for diverse applications, including but not limited to, sensor optical components, adhesive interfaces for medical wearables, and microfluidic systems.

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Amorphous ZrO2 thin films with increasing Mg content were deposited on quartz substrates, by dip coating method. The films are transparent in the visible domain and absorbent in UV, with an optical band gap that decreases with the increase of Mg content, from 5.42 eV to 4.12 eV. The temperature dependent conductivity measurements showed typical semiconductor comportment. The decrease of the electrical conductivity by Mg doping was related to the increase of the OH groups (37% to 63%) as seen from X-ray Photoelectron Spectroscopy. It was found out that the electrical conductivity obeys the Meyer-Neldel rule. This rule, previously reported for different disordered material systems is obtained for ZrO2 for the first time in the literature. Exploring novel aspects of Mg-doped ZrO2, the present study underscores the origin of the Meyer-Neldel rule explained by the small-polaron hopping model in the non-adiabatic hopping regime. Determination of the presence of such a conduction mechanism in the samples hold promise for comprehending the important aspects, which might be a concern in developing various devices based on Mg-doped ZrO2.

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In spite of its superior chemical sensitivity, XPS depth profiling is rarely used because of the alteration introduced by the sputter removal process and the resulting inhomogeneous in-depth concentration distribution. Moreover, the application of XPS becomes increasingly challenging in the case of the analysis of thin layers, if the thickness is in the range of 2-3 inelastic mean free paths (IMFP) of the photoelectrons. In this paper we will show that even in these unfavorable cases the XPS depth profiling is applicable. Herein the XPS depth profiling of a model system tungsten-carbide-rich nano-layer of high hardness and corrosion resistance is presented. We will show that the problems arising because of the relatively high IMFP can be corrected by introducing a layer model for the calculation of the observed XPS intensities, while the alteration, e.g. ion mixing, compound formation and similar artefact, introduced by the sputter removal process can be handled by TRIDYN simulation. The method presented here overcomes the limitation of XPS depth profiling.

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A simple, selective, and affordable dual fluorescence-colorimetric indicator for hydrogen sulfide was developed based on a complex of copper nanoparticles and N-doped carbon quantum dots (CuNPs/NCQDs). Real-time and visual freshness tracking of fish was done using a colorimetric indicator by incorporating CuNPs/NCQDs into agar hydrogel (AH-CuNPs/NCQDs). The fluorescence response of the CuNPs/NCQDs solution is quenched upon exposure to H2S. The field-emission scanning electron microscopy image of the AH-CuNPs/NCQDs film revealed a unified structure. The prepared indicator exhibited a good and irreversible response to H2S, with a LOD of 91.36 and a LOQ of 276.86 µM, based on the localized surface plasmon resonance (LSPR) mechanism. The X-ray photoelectron spectrometer and Fourier transform infrared spectrometer results confirmed the formation of a CuS bond in the colorimetric indicator exposed to fish spoilage. The prepared indicator demonstrated good stability and remained unaffected by pH or other volatile compounds. Notably, there was a strong correlation between ΔΕ and fish freshness parameters (pH, TV-BN, and TVC). Light green, pale yellow, and dark yellow colors, respectively, indicated freshness, semi-freshness, and spoilage of fish during storage in the refrigerator. Overall, the prepared indicator can be effectively used for detecting spoilage in meat products as a highly sensitive freshness indicator.

Asunto(s)

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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.

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Modification of CeO2 (ceria) with 3d transition metals, particularly iron, has been proven to significantly enhance its catalytic efficiency in oxidation or combustion reactions. Although this phenomenon is widely reported, the nature of the iron-ceria interaction responsible for this improvement remains debated. To address this issue, we prepared well-defined model FeOx/CeO2(111) catalytic systems and studied their structure and interfacial electronic properties using photoelectron spectroscopy, scanning tunneling microscopy, and low-energy electron diffraction, coupled with density functional theory (DFT) calculations. Our results show that under ultrahigh vacuum conditions, Fe deposition leads to the formation of small FeOx clusters on the ceria surface. Subsequent annealing results in the growth of large amorphous FeOx particles and a 2D FeOx layer. Annealing in an oxygen-rich atmosphere further oxidizes iron up to the Fe3+ state and improves the crystallinity of both the 2D layer and the 3D particles. Our DFT calculations indicate that the 2D FeOx layer interacts strongly with the ceria surface, exhibiting structural corrugations and transferred electrons between Fe2+/Fe3+ and Ce4+/Ce3+ redox pairs. The novel 2D FeOx/CeO2(111) phase may explain the enhancement of the catalytic properties of CeO2 by iron. Moreover, the corrugated 2D FeOx layer can serve as a template for the ordered nucleation of other catalytically active metals, in which the redox properties of the 2D FeOx/CeO2(111) system are exploited to modulate the charge of the supported metals.

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An X-ray analysis of exfoliated MoS2, produced by means of microwave-assisted liquid-phase exfoliation (LPE) from bulk powder in 1-methyl-2-pyrrolidone (NMP) or acetonitrile (ACN) + 1-methyl-2-pyrrolidone (NMP) solvents, has revealed distinct structural differences between the bulk powder and the microwave-exfoliated samples. Specifically, we performed X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements to identify the elements of our exfoliated sample deposited on a Si substrate by drop-casting, as well as their chemical state and its structural crystalline phase. In the exfoliated sample, the peaks pattern only partially resemble the theoretical Miller indices for MoS2. In contrast, the bulk powder's spectrum shows the characteristic peaks of the 2H polytype of MoS2, but with some broadening. Notable is the retention of partial crystallinity in the post-exfoliation phases, specifically in the normal-to-plane orientation, thus demonstrating the effectiveness of microwave-assisted techniques in producing 2D MoS2 and attaining desirable properties for the material. XPS measurements confirm the success of the exfoliation procedure and that the exfoliated sample retains its original structure. The exfoliation process has been optimized to maintain the structural integrity of MoS2 while enhancing its surface area and electrochemical performance, thereby making it a promising material for advanced electronic and optoelectronic applications ranging from energy storage to sensing devices under ambient conditions.

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This work covers the formation of a passive state for two different alloys used in the aeronautical industry. The aim of this study is to investigate the effectiveness of passivation treatments on 17-7PH and 410 SS (stainless steel) samples, specifically when performed with citric and nitric acid solutions at 49 °C using an immersion time of 90 min and subsequent exposure in 3.5 wt.% NaCl solution. Employing the cyclic potentiodynamic polarization (CPP) technique, the corrosion properties of the passivated material were evaluated according to the ASTM G65-11 standard. A microstructural analysis was performed using scanning electron microscopy (SEM). The passivated layer was characterized via X-ray photoelectron spectroscopy. In the results, the CPP curves showed positive hysteresis, indicating pitting localized corrosion, and 17-7PH steel passivated at 49 °C for 90 min in citric acid exhibited lower corrosion rate values equivalent to ×10-3 mm/year.

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In this work, Ni3V2O8 (NVO) and Ni3V2O8-reduced graphene oxide (NVO-rGO) are synthesized hydrothermally, and their extensive structural, morphological, and electrochemical characterizations follow subsequently. The synthetic materials' crystalline structure was confirmed by X-ray diffraction (XRD), and its unique marigold-like morphology was observed by field emission scanning electron microscopy (FESEM). The chemical states of the elements were investigated via X-ray photoelectron spectroscopy (XPS). Electrochemical impedance spectroscopy (EIS), Galvanostatic charge-discharge (GCD), and cyclic voltammetry (CV) were used to assess the electrochemical performance. A specific capacitance of 132 F/g, an energy density of 5.04 Wh/kg, and a power density of 187 W/kg were demonstrated by Ni3V2O8-rGO. Key electrochemical characteristics were b = 0.67; a transfer coefficient of 0.52; a standard rate constant of 6.07 × 10-5 cm/S; a diffusion coefficient of 5.27 × 10-8 cm2/S; and a series resistance of 1.65 Ω. By employing Ni3V2O8-rGO and activated carbon, an asymmetric supercapacitor with a specific capacitance of 7.85 F/g, an energy density of 3.52 Wh/kg, and a power density of 225 W/kg was achieved. The series resistance increased from 4.27 Ω to 6.63 Ω during cyclic stability tests, which showed 99% columbic efficiency and 87% energy retention. The potential of Ni3V2O8-rGO as a high-performance electrode material for supercapacitors is highlighted by these findings.