Search Results (165)

Metal hydride-based hydrogen storage reactors combine high volumetric hydrogen density with intrinsic safety, yet their performance is fundamentally limited by inefficient thermal management arising from the strong coupling among heat transfer, thermodynamics, and reaction kinetics. The highly exothermic and endothermic nature of hydrogen absorption and desorption requires rapid and spatially uniform heat removal or supply, which is difficult to achieve due to the low thermal conductivity and complex internal structure of hydride beds. This review presents a mechanistic and architectural overview of thermal management in metal hydride hydrogen storage reactors. Key heat transfer limitations within hydride beds are first analyzed, followed by a systematic classification and critical comparison of major thermal management architectures, including bed-level modifications, structural reactor designs, and heat-exchanger intensification strategies such as embedded tubes, fins, and phase-change materials. The advantages and limitations of these approaches are discussed in terms of heat transfer efficiency, hydrogen storage capacity, structural complexity, and scalability. Finally, the review highlights the central design trade-offs governing compactness, efficiency, and manufacturability, and outlines future directions toward application-oriented and scalable reactor design through integrated thermal and structural optimization. Full article

The use of metal-based species bearing existing pharmaceuticals as ligands—often resulting in enhanced bioactivity—represents an attractive strategy for the development of novel therapeutic formulations. In this context, five well-known non-steroidal anti-inflammatory drugs (NSAIDs) were employed to substitute both PPh₃ and hydride ligands in [Ru(H)₂(CO)(PPh₃)₃] (1), thereby selectively affording neutral κ²-(O,O)–chelate complexes in satisfactory yields via molecular hydrogen release. Among the obtained species, two complexes coordinating diclofenac (4) and aspirin (5) were further investigated by single-crystal X-ray diffraction (SCXRD). Preliminary biological studies were conducted on the ruthenium–salicylic acid species 2 and ibuprofen 6. The former showed promising antiproliferative activity against HeLa cancer cells, consistent with the well-established role of NSAID–ruthenium(II) complexes as a platform for the development of novel anticancer metallotherapeutics. Full article

The composite material MgH₂-EEWNi-Cr (20 wt. %) with a hydrogen content of 5.2 ± 0.1 wt.% is characterized by improved hydrogen interaction properties compared to the original MgH₂. The dissociation of the material occurs in three temperature ranges (86–117, 152–162, and 281–351 °C), associated with a complex of effects consisting of changes in the specific surface area of the material, alterations in the crystal lattice during ball milling, and changes in the electronic structure in the presence of a Ni–Cr catalyst, based on first-principles calculations. The decrease in desorption activation energy (E_d = 65–96 ± 1 kJ/mol, ΔE_d = 59–90 kJ/mol) is due to the catalytic effect of N–Cr, leading to a faster decomposition of the hydride phase. Based on the results of ab initio calculations, Ni–Cr on the MgH₂ surface leads to a significant decrease in hydrogen binding energy (ΔE_b = 60%) compared to pure magnesium hydride due to the formation of Ni–H and Cr–H covalent bonds, which reduces the degree of H–Mg ionic bonding. The results obtained allow us to expand our understanding of the mechanisms of hydrogen interaction with storage materials and the possibility of using these as mobile hydrogen storage and transportation materials. Full article

Although a large number of copper hydride complexes and clusters have been reported, phosphine-stabilized copper hydrides remain comparatively rare. This is particularly noteworthy given the continuing interest in Stryker’s reagent [HCu(PPh₃)]₆ due to its use as a hydrogenation reagent. In this work, we report on the synthesis and full characterization of a novel copper hydride cluster, [Cu₁₄H₁₂(P^tBu₃)₆Cl₂]. The structure of this copper hydride was determined via SC-XRD. In addition, the reactivity of the hydrides and their position were investigated via a convolutional neural network, quantum chemical calculations, and NMR, and they are compared to the well-known, smaller Stryker’s reagent. Full article

In this work, density functional theory (DFT)-based first-principles investigations are performed by Generalized Gradient Approximation (GGA) with the Perdew–Burke–Ernzerhof (PBE) functional in the CASTEP code. These simulations provide the insights of the structural, electronic, optical, thermodynamic, mechanical and hydrogen storage gravimetric ratios of lithium-based tetrahydrides (LiBH₄, LiAlH₄, and LiMnH₄) for hydrogen storage and photovoltaic (PV) applications. All these structures crystallize in orthorhombic Cmcm (No. 63) geometry with different lattice parameters and bonding strengths. Thermodynamic stabilities of hydrides are obtained by dispersion of phonons and phonon density of states. The measured band gaps of hydrides are 3.81 eV (LiBH₄), 4.60 eV (LiAlH₄), and 0.53 eV (LiMnH₄), which are calculated by GGA-PBE approach. Moreover, the optical characteristics with strong optical activity are observed from visible to ultraviolet (2 eV to 6 eV) regions. High dielectric response between 6 and 8 and absorption coefficient up to 10⁵ cm⁻¹ for hydrides are observed. Debye temperature has exceeded from 300 K to 600 K for all hydrides and saturation occurred closer to Dulong–Petit limit ~75 J mol⁻¹ K⁻¹. Mechanical stability in hydrides has been observed by Born-Hung mechanical stability criterion, demonstrating ductile nature. These natural hydrides have shown exceptional hydrogen storage capacities, as 18.5 wt% for LiBH₄, 10.6 wt% for LiAlH₄, and 6.1 wt% for LiMnH₄, are measured; these values have exceeded the U.S department of energy (DOE) targets (5.5 wt% H₂). These analyses prove that LiXH₄ (X = B, Al, Mn) hydrides are promising candidates for solid state hydrogen storage materials. Full article

Low-temperature superconductivity has been known since 1957 to be described by BCS theory for effective single-band metals controlled by the density of states at the Fermi level, very far from band edges, the electron–phonon coupling constant l, and the energy of the boson in the pairing interaction w₀, but BCS has failed to predict high-temperature superconductivity in different materials above about 23 K. High-temperature superconductivity above 35 K, since 1986, has been a matter of materials science, where manipulating the lattice complexity of high-temperature superconducting ceramic oxides (HTSCs) has driven materials scientists to grow new HTSC quantum materials up to 138 K in HgBa₂Ca₂Cu₃O₈ (Hg1223) at ambient pressure and near room temperature in pressurized hydrides. This perspective covers the major results of materials scientists over the last 39 years in terms of investigating the role of lattice inhomogeneity detected in these new quantum complex materials. We highlight the nanoscale heterogeneity in these complex materials and elucidate their special role played in the physics of HTSCs. Especially, it is highlighted that the geometry of lattice and charge complex heterogeneity at the nanoscale is essential and intrinsic in the mechanism of rising quantum coherence at high temperatures. Full article

A form of long-term hydrogen storage with high volume efficiency is hydrogen absorption into the host lattice of a metal or an alloy. Unlike high-pressure hydrogen storage, this form of storage is characterised by a low operating pressure. By employing metal hydride (MH) materials in a low-pressure refuelling station, it is possible to significantly increase the safety of hydrogen storage and, at the same time, to facilitate the refuelling of external devices that use MH storage tanks without the necessity of using a compressor. In this article, a methodology for the identification of the mathematical correlations among the hydrogen pressure in the storage tank, the hydrogen concentration in the alloy and the volumetric flow rate of hydrogen is described. This methodology may be used to identify the kinetics of the process and to create simplified simulations of the hydrogen release from an absorption-based storage tank by applying a finite difference method. The mathematical correlations are based on measurements of hydrogen desorption, during which hydrogen was released from the storage tank at stabilised pressure levels. The resulting mathematical description facilitates the identification of the approximate hydrogen pressure, depending on its flow rate, for a particular MH storage tank, while respecting the complexity of its internal structure, heat transfer and the hydrogen’s passage through a porous powder MH material. The identified mathematical dependence applies to the certified MNTZV-159 storage tank at pressures ranging from 7 to 29.82 bar, with hydrogen concentrations ranging from 0.223 to 1.342%, an input temperature of 59.5 °C and a cooling water flow rate of 4.36 L·min⁻¹. This methodology for the identification of a correlation between the flow rate, pressure and hydrogen concentration applies to this particular type of storage tank, and it depends not only on the alloy used and the quantity of this alloy but also on the internal structure of the heat exchanger. Full article

Metal hydrides are emerging hydrogen-storage materials that have attracted much attention for their stability and practicality. The novel magnesium-based metal hydride Mg₂CsH₉ was investigated using the CALYPSO software (version 7.0). First-principles predictive methods were then employed to investigate the structural, mechanical, electronic, optical, and hydrogen-storage properties of Mg₂CsH₉ and its alkali metal substitution structure Mg₂RbH₉. The negative formation energy, compliance with the Born stability criterion, and absence of imaginary modes in the phonon spectrum collectively confirm the thermodynamic, mechanical, and dynamic stability of Mg₂XH₉ (X = Cs, Rb), fulfilling the basic criteria for practical hydrogen-storage applications. Mg₂RbH₉ is particularly outstanding in terms of its hydrogen-storage capacity, with a gravimetric capacity of 6.34 wt% and a volumetric capacity as high as 92.70 g H₂/L, surpassing many conventional materials. The pronounced anisotropic characteristics of both compounds further enhance their practicality and adaptability to complex working conditions. An analysis of Poisson’s ratio revealed that the chemical bonding in both compounds is predominantly ionic. The details of the band structures and density of states indicate that Mg₂CsH₉ and Mg₂RbH₉ are semiconductors. Their optical properties confirm them as being high-refractive-index materials. 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

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

The current world is increasingly focusing on renewable energy sources with strong emphasis on the economically viable use of renewable energy to reduce carbon emissions and safeguard human health. Solid-state hydrogen (H₂) storage materials offer a higher density compared to traditional gaseous and liquid storage methods. In this context, this review evaluates recent advancements in binary, ternary, and complex metal hydrides integrated with 2D Ti₃C₂ MXene for enhancing H₂ storage performance. This perspective highlights the progress made in H₂ storage through the development of active sites, created by interactions between multilayers, few-layers, and internal edge sites of Ti₃C₂ MXene with metal hydrides. Specifically, the selective incorporation of Ti₃C₂ MXene content has significantly contributed to improvements in the H₂ storage performance of various metal hydrides. Key benefits include low operating temperatures and enhanced H₂ storage capacity observed in Ti₃C₂ MXene/metal hydride composites. The versatility of titanium multiple valence states (Ti⁰, Ti²⁺, Ti³⁺, and Ti⁴⁺) and Ti-C bonding in Ti₃C₂ plays a crucial role in optimizing the H₂ absorption and desorption processes. Based on these promising developments, we emphasize the potential of solid-state Ti₃C₂ MXene interfaces with various metal hydrides for fuel cell applications. Overall, 2D Ti₃C₂ MXenes represent a significant advancement in realizing efficient H₂ storage. Finally, we discuss the challenges and future directions for advancing 2D Ti₃C₂ MXenes toward commercial-scale H₂ storage solutions. Full article

The utilisation of fossil fuels has resulted in the continuous increase in anthropogenic carbon dioxide (CO₂) emissions and has led to significant environmental impacts. To this end, the catalytic hydrogenation of captured CO₂ into value-added C1 chemicals has attracted great attention. In this case, significant research efforts have been directed towards the development of heterogeneous catalysts. Owing to the unique properties and functionalities of hydridic hydrogen (H⁻), metal hydrides have shown great promise in hydrogen-involved catalytic processes. This is attributed to their enhanced hydrogen (H₂) absorption-desorption reversibility and newly developed active sites. Nevertheless, their application in the activation and hydrogenation of CO₂ has been overlooked. In this review paper, we provide an overview of recent advances in catalytic CO₂ hydrogenation using metal hydride-based materials. Firstly, the reaction mechanisms of CO₂ hydrogenation toward different C1 products (CO, CH₄, CH₃OH and HCOOH) are introduced to better understand their application trend. Thereafter, we highlight the challenges of developing robust hydride catalysts with different components and structures that enable tuning of their catalytic activity and selectivity. A brief introduction of the CO₂ hydrogenation over typical homogeneous metal hydrides complexes is also presented. Lastly, conclusion, future outlook and perspectives are discussed. Full article

Over the past two decades, the high hydrogen content and favorable dehydrogenation conditions of multi-metallic amidoboranes have gained significant attention for their potential in hydrogen storage. Among them, Al-based complex hydrides have shown promise because of their high polarizing power, light weight, and abundant natural presence. In this work, we successfully synthesized two novel tetrahedrally coordinated Al-based amidoboranes, namely, Li[Al(BH₃NHCH₂CH₂NHBH₃)₂] and Na(THF)[Al(BH₃NHCH₂CH₂NHBH₃)₂], using BH₃NH₂CH₂CH₂NH₂BH₃ (EDAB) as a precursor. The structure of Na(THF)[Al(BH₃NHCH₂CH₂NHBH₃)₂] was determined through modeling based on synchrotron powder X-ray diffraction. Additionally, the formation of the Al-N bond in Li[Al(BH₃NHCH₂CH₂NHBH₃)₂] and Na(THF)[Al(BH₃NHCH₂CH₂NHBH₃)₂] was confirmed with IR spectra. Na(THF)[Al(BH₃NHCH₂CH₂NHBH₃)₂] is more stable in air than Li[Al(BH₃NHCH₂CH₂NHBH₃)₂]. Importantly, thermal gravimetric analysis and mass spectroscopic characterization confirmed that both compounds release hydrogen without the presence of ammonia, diborane, or ethylenediamine. Our work represents the first example of Al-based amidoboranes with chelation coordination geometry, which provides an essential foundation for understanding the relationship of complex multi-metallic amidoboranes in terms of synthesis, structure, and properties. Full article

We report the synthesis, characterisation and reactivity of the stable imidazol-2-ylidene ^EtIDip (^EtIPr), {EtCN(Dip)}₂C:, Dip = 2,6-iPr₂C₆H₃, as a chemically robust alternative to IDip (IPr), {HCN(Dip)}₂C:. The N-heterocyclic carbene ^EtIDip could be further converted to the oxidised species [^EtIDipCl]Cl, ^EtIDipF₂, ^EtIDipO, and ^EtIDipSe, and the group 13 element complexes ^EtIDipEX₃, with E = B, X = Br; E = Al, X = I; E = Ga, X = I; E = Al, X = H. The properties of the ^EtIDip and IDip ligands are compared and the molecular structures of (DipNCEt)₂, [^EtIDipH]Cl, [^EtIDipH]I, ^EtIDip, [^EtIDipCl]Cl, ^EtIDipF₂, ^EtIDipO, ^EtIDipBBr₃, ^EtIDipAlI₃, ^EtIDipGaI₃, and ^EtIDipAlH₃ have been determined. Full article

The Zr-2.5%Nb alloy used to manufacture the pressure tubes for the CANDU 600 power plant experiences continual corrosion when the reactor’s fuel channels are functioning normally. Analysis of the hydrogen accumulation circumstances, the creation of zirconium hydride platelets, evaluation of the platelets’ reorientation in the thermo–mechanical field at volumetric flaws, and determination of the hydrogen morphology are therefore significant goals of the worldwide research being conducted in this field. In this paper, pressure tube alloy samples with artificial V flaws were hydrided by the technique of electrolytic deposition of a hydrogen film layer, followed by a specific thermal treatment. Micrographs of the Zr-2.5%Nb alloy samples in the radial cross-section were taken to examine the hydride reorientation phenomenon that occurred when the samples were heated under mechanical stress. The complex stress field around a tip flaw promoted the formation of some circles from hydride filaments. To characterize the zirconium hydride morphology in the reorientation zone at the volumetric flaw tip, image analysis and processing techniques were applied. To better characterize the reorientation zone from the point of view of embrittlement and mechanical behavior, this paper proposes a novel metric for the morphology of hydrides located in the reorientation zone. This work’s findings are beneficial for the investigation of CANDU fuel channels’ structural integrity. Full article