Mechanism of Alkaline Earth Metal Amide Catalyzed Hydrogenation of Challenging Alkenes and Arenes.

Recently, bulky alkaline earth (Ae=Mg, Ca, Sr, Ba) metal amide complexes AeN"2 (N"=N[Si(iPr)3]2) are shown to be active for catalyzing the hydrogenation of unactivated alkenes and arenes, presumably via the monomer N"AeH as catalyst. In sharp contrast, our extensive DFT calculations disclose that the double Ae-H-Ae bridged dimer (N"AeH)2 is kinetically more favorable in catalytic hydrogenation with H2, although rate-limited by the initial hydrogenolysis of AeN"2 to form the monomer N"AeH.

Zirconium-Modified Medium-Entropy Alloy (TiVNb)85Cr15 for Hydrogen Storage.

In this study, we investigate the effect of small amounts of zirconium alloying the medium-entropy alloy (TiVNb)85Cr15, a promising material for hydrogen storage. Alloys with 1, 4, and 7 at.% of Zr were prepared by arc melting and found to be multiphase, comprising at least three phases, indicating that Zr addition does not stabilize a single-phase solid solution. The dominant BCC phase (HEA1) is the primary hydrogen absorber, while the minor phases HEA2 and HEA3 play a crucial role in hydrogen absorption/desorption. Among the studied alloys, Zr4 (TiVNb)81Cr15Zr4 shows the highest hydrogen storage capacity, ease of activation, and reversibly retrievable hydrogen. This alloy can absorb hydrogen at room temperature without additional processing, with a reversible capacity of up to 0.74 wt.%, corresponding to hydrogen-to-metal ratio H/M = 0.46. The study emphasizes the significant role of minor elemental additions in alloy properties, stressing the importance of tailored compositions for hydrogen storage applications. It suggests a direction for further research in metal hydride alloys for effective and safe hydrogen storage.

Planar Tetranuclear Uranium Hydride Cluster Supported by ansa-Bis(cyclopentadienyl) Ligands.

Polynuclear metal hydride clusters play important roles in various catalytic processes, with most of the reported polynuclear metal hydride clusters adopting a polyhedral three-dimensional structure. Herein, we report the first example of a planar tetranuclear uranium hydride cluster [(CpCMe2CMe2Cp)U]4(µ2-H)4(µ3-H)4 (U4H8). It was synthesized by reacting an ansa-bis(cyclopentadienyl) ligand-supported uranium chloride precursor [(CpCMe2CMe2Cp)U]3(µ2-Cl)3(µ3-Cl)2 with NaHBEt3. The presence of hydrides in U4H8 was confirmed by NMR spectroscopy and its reactivity with phenol and carbon tetrachloride. DFT calculations also facilitated the determination of the hydrides' positions in U4H8, featuring four bridging µ2-H ligands and four face-capping µ3-H ligands, with the four U centers arranged in a rhombic geometry. The U4H8 represents not only the first example of planar polynuclear actinide metal hydride cluster but also the uranium hydride cluster with the highest nuclearity reported to date.

Recent Advances in Metal-Hydride-Based Disease Treatment.

In comparison to traditional antioxidant treatment methods, the use of hydrogen to eliminate reactive oxygen species from the body has the advantages of high biological safety, strong selectivity, and high clearance rate. As an energy storage material, metal hydrides have been extensively studied and used in transporting hydrogen as clean energy, which can achieve a high hydrogen load and controlled hydrogen release. Considering the antioxidant properties of hydrogen and the delivery ability of metal hydrides, metal-hydride-based disease treatment strategies have attracted widespread attention. Up to now, metal hydrides have been reported for the treatment of tumors and a range of inflammation-related diseases. However, limited by the insufficient investment, the use of metal hydrides in disease treatment still has many shortcomings, such as low targeting efficiency, limited therapeutic activity, and complex material preparation process. Particularly, metal hydrides have been found to have a series of optical, acoustic, and catalytic properties when scaled up to the nanoscale, and these properties are also widely used to promote disease treatment effects. From this new perspective, we comprehensively summarize the very recent research progress on metal-hydride-based disease treatment in this review. Ultimately, the challenges and prospects of such a burgeoning cancer theranostics modality are outlooked to provide inspiration for the further development and clinical translation of metal hydrides.

Enhancing hydrogen positions in X-ray structures of transition metal hydride complexes with dynamic quantum crystallography.

Hirshfeld atom refinement (HAR) is a method which enables the user to obtain more accurate positions of hydrogen atoms bonded to light chemical elements using X-ray data. When data quality permits, this method can be extended to hydrogen-bonded transition metals (TMs), as in hydride complexes. However, addressing hydrogen thermal motions with HAR, particularly in TM hydrides, presents a challenge. At the same time, proper description of thermal vibrations can be vital for determining hydrogen positions correctly. In this study, we employ tools such as SHADE3 and Normal Mode Refinement (NoMoRe) to estimate anisotropic displacement parameters (ADPs) for hydrogen atoms during HAR and IAM refinements performed for seven structures of TM (Fe, Ni, Cr, Nb, Rh and Os) and metalloid (Sb) hydride complexes for which both the neutron and the X-ray structures have been determined. A direct comparison between neutron and HAR/SHADE3/NoMoRe ADPs reveals that the similarity between neutron hydrogen ADPs and those estimated with NoMoRe or SHADE3 is significantly higher than when hydrogen ADPs are refined with HAR. Regarding TM-H bond lengths, traditional HAR exhibits a slight advantage over the other methods. However, combining NoMoRe/SHADE3 with HAR results in a minor decrease in agreement with neutron TM-H bond lengths. For the Cr complex, for which high-resolution X-ray data were collected, an investigation of resolution-related effects was possible.

Chemical Structure Comparison via Scanning Electron Microscopy of Spent Commercial Nickel-Metal Hydride Batteries.

Back-scattered electron imaging and X-ray elemental mapping were combined in a tabletop scanning electron microscope (SEM) to investigate cross-sections of three AA-type (mignon) nickel-metal hydride (NiMH) batteries from different manufacturers. All batteries underwent 500-800 charge/discharge cycles and reached their end of lifetime after several years as they could no longer hold any significant electric charge (less than 20% of nominal charge capacity), but none showed any short-circuiting. The types of degradation observed in this field study included electrode swelling, metallic nickel formation and carbon incorporation into pores in the positive electrodes and, in the negative electrodes, metal alloy segregation of different elements such as nickel, lanthanum and, in one case, sodium, as well as grain break-up and pore formation. All these phenomena could readily be observed at rather small magnifications. This will be important for the improvement of NiMH batteries, for which new generations with nominally slightly increased charge capacities are being marketed all the time.

State of the Art in Development of Heat Exchanger Geometry Optimization and Different Storage Bed Designs of a Metal Hydride Reactor.

The efficient operation of a metal hydride reactor depends on the hydrogen sorption and desorption reaction rate. In this regard, special attention is paid to heat management solutions when designing metal hydride hydrogen storage systems. One of the effective solutions for improving the heat and mass transfer effect in metal hydride beds is the use of heat exchangers. The design of modern cylindrical-shaped reactors makes it possible to optimize the number of heat exchange elements, design of fins and cooling tubes, filter arrangement and geometrical distribution of metal hydride bed elements. Thus, the development of a metal hydride reactor design with optimal weight and size characteristics, taking into account the efficiency of heat transfer and metal hydride bed design, is the relevant task. This paper discusses the influence of different configurations of heat exchangers and metal hydride bed for modern solid-state hydrogen storage systems. The main advantages and disadvantages of various configurations are considered in terms of heat transfer as well as weight and size characteristics. A comparative analysis of the heat exchangers, fins and other solutions efficiency has been performed, which makes it possible to summarize and facilitate the choice of the reactor configuration in the future.

Parametric Optimization of a Truncated Conical Metal Hydride Bed Surrounded by a Ring of PCM for Heat Recovery.

Metal hydride (MH) hydrogen storage needs an external heat source to release the stored hydrogen. To enhance the thermal performance of MHs, the incorporation of phase change materials (PCM) is a way to preserve reaction heat. This work proposes a new MH-PCM compact disk configuration (i.e., a truncated conical MH bed surrounded by a PCM ring). An optimization method is developed to find the optimal geometrical parameters of the MH truncated cone, which is then compared to a basic configuration (i.e., a cylindrical MH surrounded by a PCM ring). Moreover, a mathematical model is developed and used to optimize the heat transfer in a stack of MH-PCM disks. The optimum geometric parameters found (bottom radius of 0.2, top radius of 0.75 and tilt angle of 58.24) allow the truncated conical MH bed to reach a faster heat transfer rate and a large surface area of higher heat exchange. Compared to a cylindrical configuration, the optimized truncated cone shape enhances the heat transfer rate and the reaction rate in the MH bed by 37.68%.

Superatom-in-Superatom Nanoclusters: Synthesis, Structure, and Photoluminescence.

We report a new strategy in which a thiolate-protected Ag25 nanocluster can be doped with open d-shell group 8 (Ru, Os) and 9 (Ir) metals by forming metal hydride (RuH2 , OsH2 , IrH) superatoms with a closed d-shell. Structural analyses using various experimental and theoretical methods revealed that the Ag25 nanoclusters were co-doped with the open d-shell metal and hydride species to produce superatom-in-superatom nanoclusters, establishing a novel superatom doping phenomenon for open d-shell metals. The synthesized superatom-in-superatom nanoclusters exhibited dopant-dependent photoluminescence (PL) properties. Comparative PL lifetime studies of the Ag25 nanoclusters doped with 8-10 group metals revealed that both radiative and nonradiative processes were significantly dependent on the dopant. The former is strongly correlated with the electron affinity of the metal dopant, whereas the latter is governed predominantly by the kernel structure changed upon the doping of the metal hydride(s).

A Tailored Versatile and Efficient NHC-Based NNC-Pincer Manganese Catalyst for Hydrogenation of Polar Unsaturated Compounds.

The reactivity of metal-hydride complexes can be harnessed by the modification of ancillary ligands. With the aim of improving the hydride-donor ability of the key Mn-H intermediate and reducing steric hindrance, we herein report the rational design of a versatile and efficient NHC-based NNC-pincer Mn catalyst for hydrogenation reactions. This newly developed catalyst exhibited higher activity than the corresponding NNP-pincer Mn catalyst owing to its reduced steric hindrance and enhanced Mn-H σ-bonding orbital energy level through a π-antibonding interaction. Using this highly active NNC-pincer Mn catalyst, a rich array of polar unsaturated compounds (>80 examples) including esters, N-heteroarenes, amides, carbonates, and urea derivatives, were successfully hydrogenated under relatively mild conditions. This work represents a rare example of a general phosphine-free Mn-catalyzed hydrogenation system.

Proton Tunneling Distances for Metal Hydrides Formation Manage the Selectivity of Electrochemical CO2 Reduction Reaction.

A series of manganese polypyridine complexes were prepared as CO2 reduction electrocatalysts. Among these catalysts, the intramolecular proton tunneling distance for metal hydride formation (PTD-MH) vary from 2.400 to 2.696 Šwhile the structural, energetic, and electronic factors remain essentially similar to each other. The experimental and theoretical results revealed that the selectivity of CO2 reduction reaction (CO2 RR) is dominated by the intramolecular PTD-MH within a difference of ca. 0.3 Å. Specifically, the catalyst functionalized with a pendent phenol group featuring a slightly longer PTD-MH favors the binding of proton to the [Mn-CO2 ] adduct rather than the Mn center and results in ca. 100 % selectivity for CO product. In contrast, decreasing the PTD-MH by attaching a dangling tertiary amine in the same catalyst skeleton facilitates the proton binding on the Mn center and switches the product from CO to HCOOH with a selectivity of 86 %.

Crystal structure and DFT calculations of Cp2NbH(SiIMe2)(SiFMe2): an asymmetric bis(silyl) niobocene hydride complex.

An asymmetric bis(silyl) niobocene hydride complex, namely, bis(η5-cyclopentadienyl)(fluorodimethylsilyl)hydrido(iododimethylsilyl)niobium, [Nb(C5H5)2(C2H6FSi)(C2H6ISi)H] or Cp2NbH(SiIMe2)(SiFMe2), has been studied to determine the effect of the silyl ligand on the position of the hydride attached to the Nb atom. It has been shown that when a Group 17 atom is substituted onto one of the silyl ligands, there is a greater interaction between the hydride and this ligand, as demonstrated by a shorter Si...H distance. In the present work, we have investigated the effect when the silyl ligands are substituted by different Group 17 atoms. We present here the structure and DFT calculations of Cp2NbH(SiIMe2)(SiFMe2), showing that the position of the hydride is located between the two silyl ligands. The results from our investigation show that the hydride is closer to the silyl ligand that is substituted by fluorine.

Iridium-Catalyzed 1,3-Rearrangement of Allylic Alcohols.

The allylic alcohol structural motif is prevalent in many important molecules and valuable building blocks. The rearrangement reaction is one of the most important transformations, however there are only a few reports for the 1,3-rearrangement of allylic alcohols. Herein, a 1,3-rearrangement of allylic alcohols catalyzed by an Ir(III) dihydride complex is described. This reaction could provide the corresponding less accessible allylic alcohols regio- and stereoselectively from readily available E/Z mixtures of the substrates. Furthermore, a tandem alkene isomerization followed by 1,3-rearrangement of homoallylic alcohols was also realized. In addition, this rearrangement reaction could be used to synthesize the natural product Navenone B. Mechanistic investigation indicated that the reaction pathway involved a π-allyl-Ir(V) intermediate and that the dihydride in the iridium catalyst acts as a hydrogen switch to modulate the valence of the iridium center.

Optical Tunability and Characterization of Mg-Al, Mg-Ti, and Mg-Ni Alloy Hydrides for Dynamic Color Switching Devices.

Mg shows great potential as a metal hydride for switchable optical response and hydrogen detection due to its ability to stably incorporate significant amounts of hydrogen into its lattice. However, this thermodynamic stability makes hydrogen removal difficult. By alloying Mg with secondary elements, the hydrogenation kinetics can be increased. Here, we report the dynamic optical, loading, and stress properties of three Mg alloy systems (Mg-Al, Mg-Ti, and Mg-Ni) and present several novel phenomena and three distinct device designs that can be achieved with them. We find that these materials all have large deviations in refractive index when exposed to H2 gas, with a wide range of potential properties in the hydride state. The magnitude and sign of the optical property change for each of the alloys are similar, but the differences have dramatic effects on device design. We show that Mg-Ti alloys perform well as both switchable windows and broadband switchable light absorbers, where Mg0.87Ti0.13 and Mg0.85Ti0.15 can achieve a 40% transmission change as a switchable window and a 55% absorption change as a switchable solar absorber. We also show how different alloys can be used for dynamically tunable color filters, where both the reflected and transmitted colors depend on the hydrogenation state. We demonstrate how small changes in the alloy composition (e.g., with Mg-Ni) can lead to dramatically different color responses upon hydrogenation (red-shifting vs blue-shifting of the resonance). Our results establish the potential for these Mg alloys in a variety of applications relating to hydrogen storage, detection, and optical devices, which are necessary for a future hydrogen economy.

XPS Investigation on Improving Hydrogen Sorption Kinetics of the KSiH3 System by Using Zr-Based Catalysts.

The superior hydrogen storage properties makes the KSiH3 system a potential hydrogen storage material for practical applications. A theoretical capacity of 4.3 wt% bring this material to the front line of all the available hydrogen storage materials; however, the activation barrier of the reaction restricts the system to absorb and desorb hydrogen reversibly at elevated temperatures even if the thermodynamics suggest its room temperature operation. Several catalysts have already been tested to enhance its kinetic properties. In this work, the efforts were made to reduce the activation energy by using Zr-based catalysts to the KSi/KSiH3 system. The value of activation energy was found to be lowest (i.e., 87 kJ mol-1) for the ZrH2-added KSiH3 system. The mechanism of this improvement was investigated by using X-ray photoelectron spectroscopy (XPS).

Efficient Recovery of Rare Earth Elements and Zinc from Spent Ni-Metal Hydride Batteries: Statistical Studies.

Considering how important rare earth elements (REEs) are for many different industries, it is important to separate them from other elements. An extractant that binds to REEs inexpensively and selectively even in the presence of interfering ions can be used to develop a useful separation method. This work was designed to recover REEs from spent nickel-metal hydride batteries using ammonium sulfate. The chemical composition of the Ni-MH batteries was examined. The operating leaching conditions of REE extraction from black powder were experimentally optimized. The optimal conditions for the dissolution of approximately 99.98% of REEs and almost all zinc were attained through use of a 300 g/L (NH4)2SO4 concentration after 180 min of leaching time and a 1:3 solid/liquid phase ratio at 120 °C. The kinetic data fit the chemical control model. The separation of total REEs and zinc was conducted under traditional conditions to produce both metal values in marketable forms. The work then shifted to separate cerium as an individual REE through acid baking with HCl, thus leaving pure cerium behind.

Impact of Polymers on Magnesium-Based Hydrogen Storage Systems.

In the present scenario, much importance has been provided to hydrogen energy systems (HES) in the energy sector because of their clean and green behavior during utilization. The developments of novel techniques and materials have focused on overcoming the practical difficulties in the HES (production, storage and utilization). Comparatively, considerable attention needs to be provided in the hydrogen storage systems (HSS) because of physical-based storage (compressed gas, cold/cryo compressed and liquid) issues such as low gravimetric/volumetric density, storage conditions/parameters and safety. In material-based HSS, a high amount of hydrogen can be effectively stored in materials via physical or chemical bonds. In different hydride materials, Mg-based hydrides (Mg-H) showed considerable benefits such as low density, hydrogen uptake and reversibility. However, the inferior sorption kinetics and severe oxidation/contamination at exposure to air limit its benefits. There are numerous kinds of efforts, like the inclusion of catalysts that have been made for Mg-H to alter the thermodynamic-related issues. Still, those efforts do not overcome the oxidation/contamination-related issues. The developments of Mg-H encapsulated by gas-selective polymers can effectively and positively influence hydrogen sorption kinetics and prevent the Mg-H from contaminating (air and moisture). In this review, the impact of different polymers (carboxymethyl cellulose, polystyrene, polyimide, polypyrrole, polyvinylpyrrolidone, polyvinylidene fluoride, polymethylpentene, and poly(methyl methacrylate)) with Mg-H systems has been systematically reviewed. In polymer-encapsulated Mg-H, the polymers act as a barrier for the reaction between Mg-H and O2/H2O, selectively allowing the H2 gas and preventing the aggregation of hydride nanoparticles. Thus, the H2 uptake amount and sorption kinetics improved considerably in Mg-H.

The use of ultrapure molecular hydrogen enriched with atomic hydrogen in apparatuses of artificial lung ventilation in the fight against virus COVID-19.

COVID-19 is a disease caused by the SARS-CoV virus. It stands for severe acute respiratory syndrome, which affects the lungs. The process of replication and progression of the COVID-19 virus causes the formation of an excessive amount of reactive oxygen species and inflammation. Many studies have been carried out that have demonstrated that hydrogen has strong anti-inflammatory properties. It reduces hypotension and other symptoms by reducing inflammation and oxidative stress. Oxygen mixture, enriched with Hydrogen, - helps to reduce the resistance of the respiratory tract and frees up access to the pulmonary alveolus, which improves the penetration of oxygen into the lungs. Since hydrogen is an antioxidant, it helps to reduce the burden on the immune system, helps to maintain the body's health and its ability to quickly recover. When electrolysers are used to produce an oxygen-hydrogen mixture, alkaline mist and other impurities can enter the patient's lungs and cause poisoning and chemical burns. For this reason, the use of atomic hydrogen obtained from metal hydride sources for ventilation of the lungs will be more effective for treating COVID-19 than a molecular hydrogen-oxygen mixture from an electrolyzer. A functional diagram of a metal hydride source of atomic hydrogen to an artificial lung ventilator is shown. It is possible to create a series of hydrogen storage tanks of various capacities.

Mechanistic Insight into the Synergetic Interaction of Ammonia Borane and Water on ZIF-67-Derived Co@Porous Carbon for Controlled Generation of Dihydrogen.

Regarding dihydrogen as a clean and renewable energy source, ammonia borane (NH3BH3, AB) was considered as a chemical H2-storage and H2-delivery material due to its high storage capacity of dihydrogen (19.6 wt %) and stability at room temperature. To advance the development of efficient and recyclable catalysts for hydrolytic dehydrogenation of AB with parallel insight into the reaction mechanism, herein, ZIF-67-derived fcc-Co@porous carbon nano/microparticles (cZIF-67_nm/cZIF-67_µm) were explored to promote catalytic dehydrogenation of AB and generation of H2(g). According to kinetic and computational studies, zero-order dependence on the concentration of AB, first-order dependence on the concentration of cZIF-67_nm (or cZIF-67_µm), and a kinetic isotope effect value of 2.45 (or 2.64) for H2O/D2O identify the Co-catalyzed cleavage of the H-OH bond, instead of the H-BH2NH3 bond, as the rate-determining step in the hydrolytic dehydrogenation of AB. Despite the absent evolution of H2(g) in the reaction of cZIF-67 and AB in the organic solvents (i.e., THF or CH3OH) or in the reaction of cZIF-67 and water, Co-mediated activation of AB and formation of a Co-H intermediate were evidenced by theoretical calculation, infrared spectroscopy in combination with an isotope-labeling experiment, and reactivity study toward CO2-to-formate/H2O-to-H2 conversion. Moreover, the computational study discovers a synergistic interaction between AB and the water cluster (H2O)9 on fcc-Co, which shifts the splitting of water into an exergonic process and lowers the thermodynamic barrier for the generation and desorption of H2(g) from the Co-H intermediates. With the kinetic and mechanistic study of ZIF-67-derived Co@porous carbon for catalytic hydrolysis of AB, the spatiotemporal control on the generation of H2(g) for the treatment of inflammatory diseases will be further investigated in the near future.

Unraveling the Synergistic Catalytic Effects of TiO2 and Pr6O11 on Superior Dehydrogenation Performances of α-AlH3.

The pivotal steps for the practical application of dehydrogenation of aluminum hydride (AlH3) have been to decrease the temperature and increase the content of AlH3. Herein, the initial dehydrogenation temperature of AlH3 decreased to 43 °C with the amount of released hydrogen of 8.3 wt % via introducing TiO2 and Pr6O11 with synergistic catalysis effects, and its apparent activation energy of the dehydrogenation reaction decreased to 56.1 kJ mol-1, which is 52% lower than that of pure AlH3. These differences in performances of the samples are further evaluated by determining the electron density of Al-H bonds during dehydrogenation. The multiple valence state conversions of TiO2 and Pr6O11 promoted the electron transfer of H in AlH3, and a novel dehydrogenation pathway of PrH2.37 formed simultaneously, which could accelerate the breakage of Al-H bonds. The density functional theory calculations further exhibit that there are fewer electrons around H in AlH3 and the Al-H bond energy is weaker at the atomic levels, which is more conducive to the release of hydrogen. A higher hydrogen storage capacity and a lower dehydrogenation temperature make AlH3 one of the most promising hydrogen source media for mobile applications.