Search Results (478)

Electrochemical reduction processes enable the CO to be converted into a useful chemical fuel. Our study employs density functional theory calculations to analyze the (110) facets of the transition metal carbide surfaces for CO capture, incorporating the Mars–van Krevelen (MvK) mechanism. All the possible adsorption sites on the surface, including carbon, metal, and bridge sites, were fully investigated. The findings indicate that the carbon site is more active relative to the other adsorption sites examined. The CO hydrogenation paths have been comprehensively investigated on all the surfaces, and the free energy diagrams have been constructed towards the product. The results conclude that the TiC is the most promising candidate for the formation of methane, exhibiting an onset potential of −0.44 V. The predicted onset potential for CrC, MoC, NbC, VC, WC, ZrC, and HfC are −0.86, −0.61, −0.61, −0.93, −0.87, −0.61, and −0.81 V, respectively. Our calculated results demonstrate that MvK is selectively relevant to methane synthesis. Additionally, we investigated the stability of these surfaces against decomposition and conversion to pure metals concerning thermodynamics and kinetics. It was found that these carbides could remain stable under ambient conditions. The exergonic adsorption of hydrogen on carbon sites, requiring smaller potential values for product formation, and stability against decomposition indicate that these surfaces are highly suitable for CO reduction reactions using the MvK mechanism. Full article

The transition to low-carbon energy systems requires efficient hydrogen production methods that minimise CO₂ emissions. This study presents a techno-economic assessment of hydrogen production via methane pyrolysis, utilising a novel liquid metal bubble column reactor (LMBCR) designed for CO₂-free hydrogen and solid carbon outputs. Operating at 20 bar and 1100 °C, the reactor employs a molten nickel-bismuth alloy as both catalyst and heat transfer medium, alongside a sodium bromide layer to enhance carbon purity and facilitate separation. Four operational scenarios were modelled, comparing various heating and recycling configurations to optimise hydrogen yield and process economics. Results indicate that the levelised cost of hydrogen (LCOH) is highly sensitive to methane and electricity prices, CO₂ taxation, and the value of carbon by-products. Two reactor configurations demonstrate competitive LCOHs of 1.29 $/kgH₂ and 1.53 $/kgH₂, highlighting methane pyrolysis as a viable low-carbon alternative to steam methane reforming (SMR) with carbon capture and storage (CCS). This analysis underscores the potential of methane pyrolysis for scalable, economically viable hydrogen production under specificmarket conditions. Full article

The effect of dislocation pile-ups responsible for the generation or annihilation of dislocations during friction of Ag and Ni was considered. The steady-state friction was accompanied by the formation of twin bundles, intersecting twins, dislocations, adiabatic elongated shear bands, and intense dynamic recrystallization. The mechanisms of microstructural stability and friction instability were analyzed. The theoretical models of dislocation generation and annihilation in nanocrystalline FCC metals in the context of plastic deformation and failure development under friction were proposed. The transition to unstable friction was estimated. The damage of Ag was exhibited in the formation of pores, reducing the contact area and significantly increasing the shear stress. The brittle fracture of Ni represents a catastrophic failure associated with the formation of super-hard nickel oxide. Deformation resistance of the dislocation structures in the mesoscale and macroscale was compared. The coefficient of similitude (K) has been introduced in this work to compare plastic deformation at different scales. The model of the strength–ductility trade-off and microstructural instability is considered. The interaction between the migration of dislocation pile-ups and the driving forces applied to the grain boundaries was estimated. Nanostructure stabilization through the addition of a polycrystalline element (solute) to the crystal interiors in order to reduce the free energy of grain boundary interfaces was investigated. The thermodynamic driving force and kinetic energy barrier involved in strengthening, brittleness, or annealing under plastic deformation and phase formation in alloys and composite materials were examined. Full article

Chronic injuries and diseases related to oxidative stress are major global concerns as they impose a great medical burden and lead to serious public health issues. Antioxidant peptides derived from pea protein can serve as potent antioxidants and food additives, contributing to address the challenges posed by oxidative stress. This review will focus on the antioxidant effects of pea peptides demonstrated in various in vitro chemical, cellular, and in vivo antioxidant models. Additionally, this review also summarizes the regulatory role of pea peptides on the Nrf2 (NF-E2-related factor 2)/Kelch-like ECH-associated protein 1 (Keap1) pathway, aiming to elucidate their antioxidant mechanisms. Our review found that pea peptides with smaller molecular weights (<1 kDa) obtained through enzymatic hydrolysis or fermentation and/or those containing amino acids such as Glu, Asp, Gly, Pro, and Leu tend to exhibit higher antioxidant activity. These pea peptides exert their antioxidant effects by scavenging free radicals, chelating pro-oxidative transition metals, reducing hydrogen peroxide, inactivating reactive oxygen species, enhancing the expression of antioxidant enzymes, and reducing the accumulation of lipid peroxides. Our study provides a theoretical foundation for the development of pea resources and the processing of pea-related functional foods. Full article

In response to the demand for advanced materials in extreme environments, researchers have developed a variety of bulk and thin-film materials. One of the best-known processes for altering the mechanical and tribological properties of materials is surface engineering techniques. These involve various approaches to synthesize thin-film coatings, along with post-deposition treatments. The need for self-lubricating materials in extreme situations such as high-temperature applications, cryogenic temperatures, and vacuum systems has attracted the attention of researchers. They have fabricated several types of thin films using CVD and PVD techniques to meet this demand. Among the various techniques used for fabricating self-lubricating coatings, sputtering stands out as a special one. It contributes to developing smooth, homogeneous, and crack-free dense microstructures, which further enhance the coatings’ properties. This review explains the need for self-lubricating materials and the different techniques used to synthesize them. It discusses and summarizes the concept of synthesizing various types of self-lubricating films. It shows the different types of self-lubricating material systems, like transition metal-based nitrides and carbides, diamond-like carbon-based materials, and so on. This work also reflects the governing factors like the deposition temperature, doping elements, thickness of the film, deposition pressure, gas flow rate, etc., that influence the deposition results and, consequently, the properties of the film, as well as their advanced applications in different areas. This work reflects the self-lubricating properties of different kinds of films exposed to various environments in terms of their coefficient of friction and wear rate, emphasizing how the friction coefficient affects the wear rate. Full article

Fast, spark-free detection of hydrogen leaks is indispensable for large-scale hydrogen deployment, yet electronic sensors remain power-intensive and prone to cross-talk. Optical schemes based on surface plasmons enable remote read-out, but single-metal devices offer either weak H2 affinity or poor plasmonic quality. Here we employ full-wave finite-difference time-domain (FDTD) simulations to map the hydrogen response of nanohole arrays (NAs) that can be mass-produced by colloidal lithography. Square lattices of 200 nm holes etched into 100 nm films of Pd, Mg, Ti, V, or Zr expose an intrinsic trade-off: Pd maintains sharp extraordinary optical transmission modes but shifts by only 28 nm upon hydriding, whereas Mg undergoes a large dielectric transition that extinguishes its resonance. Vertical pairing of a hydride-forming layer with a noble metal plasmonic cap overcomes this limitation. A Mg/Pd bilayer preserves all modes and red-shifts by 94 nm, while the predicted optimum Ag (60 nm)/Mg (40 nm) stack delivers a 163 nm shift with an 83 nm linewidth, yielding a figure of merit of 1.96—surpassing the best plasmonic hydrogen sensors reported to date. Continuous-film geometry suppresses mechanical degradation, and the design rules—noble-metal plasmon generator, buried hydride layer, and thickness tuning—are general. This study charts a scalable route to remote, sub-ppm, optical hydrogen sensors compatible with a carbon-neutral energy infrastructure. Full article

High-Temperature Proton-Exchange Membrane Fuel Cells (HT-PEMFCs) represent a promising clean energy technology and are valued for their fuel flexibility and simplified balance of plant. Their commercialization, however, is critically hindered by the prohibitive cost and resource scarcity of platinum-group metal (PGM) catalysts. The challenge is amplified in the phosphoric acid (PA) electrolyte of HT-PEMFCs, where the severe anion poisoning of PGM active sites necessitates impractically high catalyst loadings. This review addresses the urgent need for cost-effective alternatives by providing a comprehensive assessment of recent advancements in non-precious metal (NPM) catalysts for the oxygen reduction reaction (ORR) in HT-PEMFCs. It systematically explores synthesis strategies and structure–performance relationships for emerging catalyst classes, including transition metal compounds, metal–nitrogen–carbon (M-N-C) materials, and metal-free heteroatom-doped carbons. A significant focus is placed on M-N-C catalysts, particularly those with atomically dispersed Fe-Nx active sites, which have emerged as the most viable replacements for platinum due to their high intrinsic activity and notable tolerance to phosphate poisoning. This review critically analyzes key challenges that impede practical application, such as the trade-off between catalyst activity and stability, mass transport limitations in thick electrodes, and long-term degradation in the harsh PA environment. Finally, it outlines future research directions, emphasizing the need for a synergistic approach that integrates computational modeling with advanced operando characterization to guide the rational design of durable, high-performance catalysts and electrode architectures, thereby accelerating the path to commercial viability for HT-PEMFC technology. Full article

Integrating two-dimensional transition-metal dichalcogenides with graphene is attractive for low-power memory and neuromorphic hardware, yet sequential wet transfer leaves polymer residues and high contact resistance. We demonstrate a complementary metal–oxide–semiconductor (CMOS)-compatible, transfer-free route in which an atomically thin amorphous MoS₂ precursor is RF-sputtered directly onto chemical vapor-deposited few-layer graphene and crystallized by confined-space sulfurization at 800 °C. Grazing-incidence X-ray reflectivity, Raman spectroscopy, and X-ray photoelectron spectroscopy confirm the formation of residue-free, three-to-four-layer 2H-MoS₂ (roughness: 0.8–0.9 nm) over 1.5 cm × 2 cm coupons. Lateral MoS₂/graphene devices exhibit reproducible non-volatile resistive switching with a set transition (SET) near +6 V and an analogue ON/OFF ≈2.1, attributable to vacancy-induced Schottky-barrier modulation. The single-furnace magnetron sputtering + sulfurization sequence avoids toxic H₂S, polymer transfer steps, and high-resistance contacts, offering a cost-effective pathway toward wafer-scale 2D memristors compatible with back-end CMOS temperatures. Full article

Easily accessible and inexpensive potassium carbonate (K₂CO₃) has been applied as the base-catalyst for the synthesis of novel classes of functionalized nanomaterials. This eco-friendly approach has been proven to be effective for a wide range of substrates, leading to nine isocyanate derivatives of silsesquioxanes (SQs) with yields exceeding 90% in mild and transition metal-free conditions. The application potential of chosen products was assessed on the basis of thermogravimetric analyses and photochemical measurements. Full article

The transition to high-energy-density lithium metal batteries (LMBs) is essential for advancing electric vehicle (EV) technologies beyond the limitations of conventional lithium-ion batteries. A key challenge in scaling LMB production is the precise, contamination-free separation of lithium metal (LiM) anodes, hindered by lithium’s strong adhesion to mechanical cutting tools. This study investigates high-speed, contactless laser cutting as a scalable alternative for shaping double-coated LiM anodes. The effects of pulse duration, pulse energy, repetition frequency, and scanning speed were systematically evaluated using a nanosecond pulsed laser system on 30 µm LiM foils laminated on both sides of an 8 µm copper current collector. A maximum single-pass cutting speed of 3.0 m/s was achieved at a line energy of 0.06667 J/mm, with successful kerf formation requiring both a minimum pulse energy (>0.4 mJ) and peak power (>2.4 kW). Cut edge analysis showed that shorter pulse durations (72 ns) significantly reduced kerf width, the heat-affected zone (HAZ), and bulge height, indicating a shift to vapor-dominated ablation, though with increased spatter due to recoil pressure. Optimal edge quality was achieved with moderate pulse durations (261–508 ns), balancing energy delivery and thermal control. These findings define critical laser parameter thresholds and process windows for the high-speed, high-fidelity cutting of double-coated LiM battery anodes, supporting the industrial adoption of nanosecond laser systems in scalable LMB electrode manufacturing. Full article

Biothiols, including cysteine (Cys), homocysteine (Hcy), and glutathione (GSH), are crucial for physiological regulation and their imbalance poses severe health risks. Herein, we developed a pH-responsive liquid crystal (LC)-based sensing platform for detection of biothiols by doping 4-n-pentylbiphenyl-4-carboxylic acid (PBA) into 4-n-pentyl-4-cyanobiphenyl (5CB). Urease catalyzed urea hydrolysis to produce OH⁻, triggering the deprotonation of PBA, thereby inducing a vertical alignment of LC molecules at the interface corresponding to dark optical appearances. Heavy metal ions (e.g., Hg²⁺) could inhibit urease activity, under which condition LC presents bright optical images and LC molecules maintain a state of tilted arrangement. However, biothiols competitively bind to Hg²⁺, the activity of urease is maintained which enables the occurrence of urea hydrolysis. This case triggers LC molecules to align in a vertical orientation, resulting in bright optical images. This pH-driven reorientation of LCs provides a visual readout (bright-to-dark transition) correlated with biothiol concentration. The detection limits of Cys/Hcy and GSH for the PBA-doped LC platform are 0.1 μM and 0.5 μM, respectively. Overall, this study provides a simple, label-free and low-cost strategy that has a broad application prospect for the detection of biothiols. Full article

In this study, we present a comprehensive theoretical analysis of modifications in the physical and chemical properties of MoSe₂ upon the introduction of substitutional transition metal impurities, specifically, Ti, V, Cr, Fe, Co, Ni, Cu, W, Pd, and Pt. Wet systematically calculated the adsorption enthalpies for various representative analytes, including O₂, H₂, CO, CO₂, H₂O, NO₂, formaldehyde, and ethanol, and further evaluated their free energies across a range of temperatures. By employing the formula for probabilities, we accounted for the competition among molecules for active adsorption sites during simultaneous adsorption events. Our findings underscore the importance of integrating temperature effects and competitive adsorption dynamics to predict the performance of highly selective sensors accurately. Additionally, we investigated the influence of temperature and analyte concentration on sensor performance by analyzing the saturation of active sites for specific scenarios using Langmuir sorption theory. Building on our calculated adsorption energies, we screened the catalytic potential of doped MoSe₂ for CO₂-to-methanol conversion reactions. This paper also examines the correlations between the electronic structure of active sites and their associated sensing and catalytic capabilities, offering insights that can inform the design of advanced materials for sensors and catalytic applications. Full article

This study presents the synthesis and physicochemical characterization of coordination compounds formed between chrysin, a natural flavonoid, and transition metal ions: Mn(II), Co(II), and Zn(II). The complexes were obtained under mildly basic conditions and analyzed using elemental analysis, thermogravimetric analysis (TGA), silver-assisted laser desorption/ionization mass spectrometry (SALDI-MS), FT-IR spectroscopy, and ¹H NMR. The spectroscopic data confirm that chrysin coordinates as a bidentate ligand through the 5-hydroxyl and 4-carbonyl groups, with structural differences depending on the metal ion involved. The mass spectrometry results revealed distinct stoichiometries: 1:2 metal-to-ligand ratios for Mn(II) and Co(II), and 1:1 for Zn(II), with additional hydroxide coordination. Biological assays demonstrated that Co(II) and Mn(II) complexes exhibit enhanced antibacterial and anti-biofilm activity compared to free chrysin, particularly against drug-resistant Staphylococcus epidermidis, whereas the Zn(II) complex showed negligible biological activity. Full article

In this article, an efficient and straightforward protocol for the construction of complex dispirocyclic skeletons via regioselective intramolecular Michael addition is presented. Diverse dispirocyclic compounds were synthesized under mild and transition-metal-free conditions with good to excellent yields. Most stereoisomers were conveniently separated by column chromatography, and their relative configurations were identified by single-crystal X-Ray diffraction of representative compounds. A scale-up experiment validated the practicality of this method. In an in vitro assay, some dispirocyclic compounds exhibited potent cytotoxicity with an IC₅₀ value of 10⁻⁶ mol/L. Full article

Tuberaria lignosa (Sweet) Samp. (Cistaceae) is a herbaceous species native to southwestern Europe, traditionally used to treat wounds, ulcers, and inflammatory or infectious skin conditions. This study aimed to characterize the phytochemical profile of its aqueous leaf extract and evaluate its skin-related in vitro biological activities. The phenolic composition was determined using UHPLC-HRMS/MS, HPLC-DAD, and quantitative colorimetric assays. Antioxidant activity was assessed against synthetic free radicals, reactive oxygen and nitrogen species, transition metals, and pro-oxidant enzymes. Enzymatic inhibition of tyrosinase, hyaluronidase, collagenase, and elastase were evaluated using in vitro assays. Cytocompatibility was tested on human keratinocytes and NIH/3T3 fibroblasts using MTT and resazurin assays, respectively, while wound healing was evaluated on NIH/3T3 fibroblasts using the scratch assay. Antifungal activity was investigated against several Candida and dermatophyte species, while antibiofilm activity was tested against Epidermophyton floccosum. The extract was found to be rich in phenolic compounds, accounting for nearly 45% of its dry weight. These included flavonoids, phenolic acids, and proanthocyanidins, with ellagitannins (punicalagin) being the predominant group. The extract demonstrated potent antioxidant, anti-tyrosinase, anti-collagenase, anti-elastase, and antidermatophytic activities, including fungistatic, fungicidal, and antibiofilm effects. These findings highlight the potential of T. lignosa as a valuable and underexplored source of bioactive phenolic compounds with strong potential for the development of innovative approaches for skin care and therapy. Full article