Search Results (1,001)

Aluminum–hydrogen compounds have drawn considerable interest for applications in solid-state hydrogen storage. The structural, hydrogen storage, electronic, mechanical, phonon, and thermodynamic properties of XAl₂H₂ (X = Ca, Sr, Sc, Y) hydrides are investigated using density functional theory. These hydrides exhibit negative formation energies in the hexagonal phase, indicating their thermodynamic stability. The gravimetric hydrogen storage capacities of CaAl₂H₂, SrAl₂H₂, ScAl₂H₂, and YAl₂H₂ are calculated to be 1.41 wt%, 0.94 wt%, 1.34 wt%, and 0.93 wt%, respectively. Analysis of the electronic density of states reveals metallic characteristics. Furthermore, the calculated elastic constants satisfy the Born stability criteria, confirming their mechanical stability. Additionally, through phonon spectra analysis, dynamical stability is verified for CaAl₂H₂ and SrAl₂H₂ but not for ScAl₂H₂ and YAl₂H₂. Finally, we present temperature-dependent thermodynamic properties. This research reveals that XAl₂H₂ (X = Ca, Sr, Sc, Y) materials represent promising candidates for solid-state hydrogen storage, providing a theoretical foundation for further studies on XAl₂H₂ systems. Full article

Hybrid implants composed of magnesium and titanium are a promising direction in orthopaedics, as these implants combine the stability of titanium with the biological activity of magnesium. These partly soluble implants require careful investigation, as the degradation of magnesium releases hydrogen, which can enter the Ti matrix and thus alter the mechanical properties. To investigate this scenario and quantify the hydrogen uptake along with its structural impacts, we employed inert gas fusion, scanning electron microscopy, X-ray diffraction, and a combination of synchrotron absorption and X-ray diffraction tomography. These techniques enabled us to investigate the concentration and distribution of hydrogen and the formation of hydrides in the samples. Titanium hydride formation was observed in a region approximately 120 µm away from the titanium surface and correlates with the amount of absorbed hydrogen. We speculate that the degradation of magnesium at the magnesium/titanium implant interface leads to the penetration of hydrogen due to a combination of electrochemical and gaseous charging. Full article

TiVCr-based alloys are well-explored body-centered cubic (BCC) materials for hydrogen storage applications that can potentially store higher amounts of hydrogen at moderate temperatures. The challenge remains in optimizing the alloy-hydrogen stability, and several transition elements have been found to support the reduction in the hydride stability. In this study, Ni and Nb transition elements were incorporated into the TiVCr alloy system to thoroughly understand their influence on the (de)hydrogenation kinetics and thermodynamic properties. Three different compositions, (TiVCr)₉₅Ni₅, (TiVCr)₉₀ Ni₁₀, and (TiVCr)₉₅Ni₅Nb₅, were prepared via arc melting. The as-prepared samples showed the formation of a dual-phase BCC solid solution and secondary phase precipitates. The samples were characterized using hydrogen sorption studies. Among the studied compositions, (TiVCr)₉₀Ni₁₀ exhibited the highest hydrogen absorption capacity of 3 wt%, whereas both (TiVCr)₉₅Ni₅ and (TiVCr)₉₀Ni₅Nb₅ absorbed up to 2.5 wt% hydrogen. The kinetics of (de)hydrogenation were modeled using the JMAK and 3D Jander diffusion models. The kinetics results showed that the presence of Ni improved hydrogen adsorption at the interface level, whereas Nb substitution enhanced diffusion and hydrogen release at room temperature. Thus, the addition of Ni and Nb to Ti-V-Cr-based high-entropy alloys significantly improved the hydrogen absorption and desorption properties at room temperature for gas-phase hydrogen storage. Full article

Searching for new and efficient transfer hydrogenation catalysts, a series of new organometallic ruthenium(II)-arene complexes of the formulae [Ru(η⁶-p-cymene)(L)Cl][PF₆] (1–8) and [Ru(η⁶-p-cymene)(L)Cl][Ru(η⁶-p-cymene)Cl₃] (9–11) were synthesized and fully characterized. These were prepared from the reaction of pyridine–quinoline and biquinoline-based ligands (L) with [Ru(η⁶-p-cymene)(μ-Cl)Cl]₂, in 1:2 and 1:1, metal (M) to ligand (L) molar ratios. Characterization includes a combination of spectroscopic methods (FT-IR, UV-Vis, multi nuclear NMR), elemental analysis and single-crystal X-ray crystallography. The pyridine–quinoline organic entities encountered, were prepared in high yield either via the thermal decarboxylation of the carboxylic acid congeners, namely 2,2′-pyridyl-quinoline-4-carboxylic acid (pqca), 8-methyl-2,2′-pyridyl-quinoline-4-carboxylic acid (8-Mepqca), 6′-methyl-2,2′-pyridyl-quinoline-4-carboxylic acid (6′-Mepqca) and 8,6′-dimethyl-2,2′-pyridyl-quinoline-4-carboxylic acid (8,6′-Me₂pqca), affording the desired ligands pq, 8-Mepq, 6′-Mepq and 8,6′-Me₂pq, or by the classical Friedländer condensation, to yield 4,6′-dimethyl-2,2′-pyridyl-quinoline (4,6′-Me₂pq) and 4-methyl-2,2′-pyridyl-quinoline (4-Mepq), respectively. The solid-state structures of complexes 1–4, 6, 8 and 9 were determined showing a distorted octahedral coordination geometry. The unit cell of 3 contains two independent molecules (Ru-3), (Ru′-3) in a 1:1 ratio, due to a slight rotation of the arene ring. All complexes catalyze the transfer hydrogenation of acetophenone, using 2-propanol as a hydrogen donor in the presence of KOiPr. Among them, complexes 1 and 5 bearing methyl groups at the 8 and 4 position of the quinoline moiety, convert acetophenone to 1-phenylethanol quantitatively, within approximately 10 min with final TOFs of 1600 h⁻¹. The catalytic performance of complexes 1–11, towards the transfer hydrogenation of p-substituted acetophenone derivatives and benzophenone, ranges from moderate to excellent. An inner-sphere mechanism has been suggested based on the detection of ruthenium(II) hydride species. Full article

This study investigates the structure of a metal hydride (MH) cartridge as a hydrogen storage tank for small-scale fuel cells (FCs). This cartridge is designed to be stacked and used in layers, allowing flexible capacity adjustment according to demand. MH enables compact and safe hydrogen storage for small-scale fuel cell (FC) applications due to its high energy density and low-pressure operation. However, because hydrogen desorption from MH is an endothermic reaction, an external heat supply is required for stable performance. To enhance both the heat transfer efficiency and cartridge usability, we propose a heat supply method that utilizes waste heat from an air-cooled proton-exchange membrane fuel cell (PEMFC). The proposed cartridge incorporates four cylindrical MH tanks that require uniform heat transfer. Therefore, we proposed the tank arrangements within the cartridge to minimize the non-uniformity of heat transfer distribution on the surface. The flow of exhaust air from the PEMFC into the cartridge was analyzed using computational fluid dynamics (CFD) simulations. In addition, an empirical correlation for the Nusselt number was developed to estimate the heat transfer coefficient. As a result, it was concluded that the heat utilization rate of the exhaust heat flowing into the cartridge was 13.2%. Full article

This study focuses on the structural and electrochemical behavior of the compound ZnLaFeO₄ as a negative electrode material for nickel–metal hydride (Ni-MH) batteries. The material was synthesized by a sol–gel hydrothermal method to assess the influence of lanthanum doping on the ZnFe₂O₄ spinel structure. X-ray diffraction revealed the formation of a dominant LaFeO₃ perovskite phase, with ZnFe₂O₄ and La₂O₃ as secondary phases. SEM analysis showed agglomerated grains with an irregular morphology. Electrochemical characterization at room temperature and a discharge rate of C/10 (full charge in 10 h) revealed a maximum discharge capacity of 106 mAhg⁻¹. Although La³⁺ doping modified the microstructure and slowed the activation process, the electrode exhibited stable cycling with moderate polarization behavior. The decrease in capacity during cycling is due mainly to higher internal resistance. These results highlight the potential and limitations of La-doped spinel ferrites as alternative negative electrodes for Ni-MH systems. Full article

Active and abandoned mining sites are significant sources of heavy metals and metalloid pollution, leading to serious environmental issues. This study assessed the environmental risks posed by potentially toxic elements (PTEs), specifically arsenic (As) and antimony (Sb), in the Technosols (mining residues) of the former Pejão coal mine complex in Northern Portugal, a site impacted by forest wildfires in October 2017 that triggered underground combustion within the waste heaps. Our methodology involved determining the “pseudo-total” concentrations of As and Sb in the collected heap samples using microwave digestion with aqua regia (ISO 12914), followed by analysis using hydride generation-atomic absorption spectroscopy (HG-AAS). The concentrations of As an Sb ranging from 31.0 to 68.6 mg kg⁻¹ and 4.8 to 8.3 mg kg⁻¹, respectively, were found to be above the European background values reported in project FOREGS (11.6 mg kg⁻¹ for As and 1.04 mg kg⁻¹ for Sb) and Portuguese Environment Agency (APA) reference values for agricultural soils (11 mg kg⁻¹ for As and 7.5 mg kg⁻¹ for Sb), indicating significant enrichment of these PTEs. Based on average I_geo values, As contamination overall was classified as “unpolluted to moderately polluted” while Sb contamination was classified as “moderately polluted” in the waste pile samples and “unpolluted to moderately polluted” in the downhill soil samples. However, total PTE content alone is insufficient for a comprehensive environmental risk assessment. Therefore, further studies on As and Sb fractionation and speciation were conducted using the Shiowatana sequential extraction procedure (SEP). The results showed that As and Sb levels in the more mobile fractions were not significant. This suggests that the enrichment in the burned (BCW) and unburned (UCW) coal waste areas of the mine is likely due to the stockpiling of lithic fragments, primarily coals hosting arsenian pyrites and stibnite which largely traps these elements within its crystalline structure. The observed enrichment in downhill soils (DS) is attributed to mechanical weathering, rock fragment erosion, and transport processes. Given the strong association of these elements with solid phases, the risk of leaching into surface waters and aquifers is considered low. This work underscores the importance of a holistic approach to environmental risk assessment at former mining sites, contributing to the development of sustainable remediation strategies for long-term environmental protection. Full article

A technique has been proposed and experimentally tested for measuring the hydrogen concentration in an inert atmosphere within a closed system. This method utilizes a metal-oxide-semiconductor field-effect capacity-type (MOSFEC) sensor under harsh conditions such as exposure to inert gases, pressure fluctuations, and varying temperatures. The measurement is performed during the thermal decomposition of metal hydrides in a liquid sodium environment. The developed measurement technique for determining hydrogen concentration released from metal hydride samples in a system with a closed gas path is cost-effective compared to standardized, resource-intensive open-volume flow measurement methods. The use of the developed MOSFEC sensor technique allows for rapid and efficient investigation of the in situ real-time dynamics of gas release from various metal hydride materials differing in their hydrogen content within a small closed volume. Additionally, this approach enables precise determination of the specific gas release temperatures. Full article

Lithium hydride (LiH) is one promising material for nuclear reactor shielding due to its high hydrogen content, but its poor mechanical strength and thermal conductivity pose challenges for fabricating large, crack-free ceramic components via conventional sintering. This study explores microwave sintering as a potential solution to enhance heating uniformity and reduce thermal stress during densification of bulk LiH ceramics. Using implicit function and level set methods, we numerically simulated the microwave field distribution and thermal response in both stationary and rotating samples. The results show that rotational heating improves temperature uniformity by up to 12.9% for specific samples, although uniform temperature control remains difficult through rotation alone. To mitigate stress accumulation from thermal gradients, we propose a cyclic sintering–resting strategy, which leverages LiH’s tensile strength–temperature envelope to guide safe and efficient processing. This strategy successfully reduced total sintering time from several days to 1.63 h without inducing cracks. Our findings offer practical insights into optimizing microwave sintering parameters for large-scale LiH ceramic production and contribute to enabling its application in advanced nuclear shielding systems. Full article

This work evaluates the effectiveness of in situ and ex situ passivation methods for mitigating the pyrophoricity of uranium–6 wt.% niobium spherical powders produced via the hydride–dehydride process coupled with plasma spheroidization. Oxide layer thickness was characterized using STEM/EDX, and pyrophoricity was assessed by a UN-recommended test method, which involves directly dropping the powders in the air. In situ passivation, performed by introducing flowing oxygen during spheroidization, produced oxide layers ranging from tens to hundreds of nanometers but resulted in inconsistent pyrophoricity mitigation at lower oxygen flow rates. Ex situ passivation, achieved by slow oxygen exposure over several months, formed uniform oxide layers of approximately 20 nm and consistently mitigated pyrophoricity. Despite requiring higher bulk oxygen content, in situ passivation enables faster processing and control of oxygen, while ex situ passivation achieves superior oxide uniformity with lower oxygen incorporation. These findings highlight the trade-offs between passivation methods and provide a foundation for improving the safety and scalability of reactive metal powder production. Full article

Hydrogen is critical for achieving carbon neutrality as a clean energy source. However, its low ambient energy density poses challenges for storage, making efficient and safe hydrogen storage a bottleneck. Metal hydride-based solid-state hydrogen storage has emerged as a promising solution due to its high energy density, low operating pressure, and safety. In this work, the thermodynamic and kinetic characteristics of the hydrogenation and dehydrogenation processes are investigated and analyzed in detail, and the effects of initial conditions on the thermochemical hydrogen storage reactor are discussed. Multiphysics field modeling of the magnesium-based hydrogen storage tank was conducted to analyze the reaction processes. Distributions of temperature and reaction rate in the reactor and temperature and pressure during the hydrogen loading process were discussed. Radially, wall-adjacent regions rapidly dissipate heat with short reaction times, while the central area warms into a thermal plateau. Inward cooling propagation shortens the plateau, homogenizing temperatures—reflecting inward-to-outward thermal diffusion and exothermic attenuation, alongside a reaction rate peak migrating from edge to center. Axially, initial uniformity transitions to bottom-up thermal expansion after 60 min, with sustained high top temperatures showing nonlinear decay under $∆$t = 20 min intervals, where cooling rates monotonically accelerate. The greater the hydrogen pressure, the shorter the period of the temperature rise and the steeper the curve, while lower initial temperatures preserve local maxima but shorten plateaus and cooling time via enhanced thermal gradients. Full article

Due to the depletion of hydrocarbon resources worldwide, intensive research is being conducted to identify alternative energy carriers. Hydrogen has emerged as a promising candidate due to its high energy density and environmentally friendly nature. However, large-scale implementation of hydrogen energy is hindered by the lack of safe, efficient, and cost-effective storage methods. Among the various materials studied for solid-state hydrogen storage, boron nitride (BN)-based compounds have attracted significant attention owing to their high thermal stability, tunable morphology, and potential for physisorption-based storage. This review focuses on recent advances in the synthesis, functionalization, and structural optimization of BN-based materials, including nanotubes, nanosheets, porous frameworks, and chemically modified BN. Although other boron-containing hydrides such as LiBH₄, Mg(BH₄)₂, and closo-borates are briefly mentioned for comparison, the primary emphasis is placed on BN-related systems. This paper discusses various modification strategies aimed at enhancing hydrogen uptake and reversibility, offering insights into the future potential of BN-based materials in hydrogen storage technologies. Full article

Motivated by two of the most unexpected discoveries in recent years—the detection of ArH⁺ and ${\mathrm{HeH}}^{+}$ noble gas molecules in the cold, low-pressure regions of the Universe—we investigate [He₂H]⁺ and [Ne₂H]⁺ as potentially detectable species in the interstellar medium, providing new insights into their energetic and spectral properties. These findings are crucial for advancing our understanding of noble gas chemistry in astrophysical environments. To achieve this, we employed a data-driven approach to construct a high-accuracy machine-learning potential energy surface using the reproducing kernel Hilbert space method. Training and testing datasets are generated via high-level CCSD(T)/CBS[56] quantum chemistry computations, followed by a rigorous validation protocol to ensure the reliability of the potential. The ML-PES is then used to compute vibrational states within the MCTDH framework, and assign spectral transitions for the most common isotopologues of these species in the interstellar medium. Our results are compared with previously recorded values, revealing that both cations exhibit a prominent proton-shuttle motion within the infrared spectral range, making them strong candidates for telescopic observation. This study provides a solid computational foundation, based on rigorous, fully quantum treatments, aiming to assist in the identification of these yet unobserved He/Ne hydride cations in astrophysical environments. Full article

Hydrogen possesses distinctive characteristics that position it as a potential energy carrier to substitute fossil fuels. Nonetheless, there is still an essential need to create secure and effective storage solutions prior to its broad application. The use of hydride-forming metals (HFMs) for hydrogen storage is a method that has been researched thoroughly over the past several decades. This study investigates the structural and chemical modifications in titanium (Ti) and zirconium (Zr) thin coatings over aluminum hydroxide (AlO₃) granules before and after hydrogenation. The materials were subjected to hydrogenation at 400 °C and 5 atm of hydrogen pressure for 2 h, with a hydrogen flow rate of 0.8 L/min. The SEM analysis revealed significant morphological changes, including surface roughening, a grain boundary separation, and microcrack formations, indicating the formation of metal hydrides. The EDS analysis showed a reduction in Ti and Zr contents post-hydrogenation, likely due to the formation of hydrides. The presence of hydride phases, with shifts in diffraction peaks indicating structural modifications due to hydrogen absorption, is confirmed by the XRD analysis. The FTIR analysis revealed dihydroxylation, with the removal of surface hydroxyl groups and the formation of new metal–hydride bonds, further corroborating the structural changes. The formation of metal hydrides was confirmed by the emergence of new peaks within the 1100–1200 cm⁻¹ range, suggesting the incorporation of hydrogen. Mathematical modeling based on the experimental parameters was conducted to assess the hydride formation and the rate of hydrogen penetration. The hydride conversion rate for Ti- and Zr-coated AlO₃ granules was determined to be 3.5% and 1.6%, respectively. While, the hydrogen penetration depth for Ti- and Zr-coated AlO₃ granules over a time of 2 h was found to be 1200 nm and 850 nm approximately. The findings had a good agreement with the experimental results. These results highlight the impact of hydrogenation on the microstructure and chemical composition of Ti- and Zr-coated AlO₃, shedding light on potential applications in hydrogen storage and related fields. Full article

As the presence of renewable energy production grows, so does the need to find alternative solutions for long–term energy storage. One solution may be hydrogen, and more generally, power-to-gas systems, which could allow energy storage for longer periods than batteries. However, the problem of hydrogen storage remains a limitation to the deployment of this technology. A possible solution for the hydrogen storage could be metal hydrides. In this work, a power-to-gas system based on a $2.5\mathrm{kW}$ commercial electrolyzer coupled to a pair of AB2-type metal hydride cylinders with a total volume of $4\mathrm{L}$ is studied. A special focus is placed on the electrolyzer power converter. In particular, the current ripple generated on the side connected to the stack and the efficiency of the converter are studied. A series of tests are carried out to verify the behavior of the system with varying types of thermal conditioning of the hydrides. The results show that the converter used is not optimized for the chosen application, and the thermal conditioning influences the hydrogen adsorption rate and thus the electrolyzer’s behavior. Finally, a technique to operate the system at maximum efficiency is proposed. Full article