Multi-criteria analysis for screening of reversible metal hydrides in hydrogen gas storage and high pressure delivery applications

Metals and alloys forming reversible hydrides with hydrogen gas are potential building blocks for compact, solid state hydrogen storage systems. Based on the materials’ thermodynamic characteristics, their use as temperature-swing gas compression and delivery systems in the hydrogen economy is also possible. Given the wide variety of materials developed and tested at laboratory and pilot scales, a harmonized method of selecting the feasible material(s) for a particular real-life application is required. This study proposes a system selection framework based on a normalized, multi-criteria metric. Using calculated values of multi-criteria metric, multi-criteria screening and ranking of potential materials has been demonstrated for a particular use case. It is found that the alloy TiMn_1.52 having value of additive metric between 0.25 and 0.35 represents the best material for a single stage system. The alloy pair CaNi₅–Ti_1.5CrMn represents the best alternative for a two-stage system with additive metric values between 0.63 and 0.82. Energy and economic characteristics of the metal hydride gas compression and delivery systems are evaluated and compared with an equivalent mechanical compression system producing the same final effect (i.e., delivery of a given quantity of gas at a defined pressure).     

Theoretical prediction of structure,electronic and optical properties of VH2 hydrogen storage material

The vanadium hydrides have better hydrogen storage capacity in comparison to the other metal hydrides. Although the structure of VH₂ hydride has been reported, the structural stability, electronic and optical properties of VH₂ hydride are unclear. To solve these problems, we apply the first-principles method to study the structural stability, electronic and optical properties of VH₂ hydrides. Similar to the metal dihydrides, four possible VH₂ hydrides such as the cubic (Fm-3m), tetragonal (I4/mmm), tetragonal (P4₂/mnm) and orthorhombic (Pnma) are designed. The result shows that the cubic VH₂ hydride is a thermodynamic and dynamical stability. In particular, the tetragonal (I4/mmm) and the orthorhombic (Pnma) VH₂ hydrides are firstly predicted. It is found that these VH₂ hydrides show metallic behavior. The electronic interaction of V (d-state)-H (s-state) is beneficial to improve the hydrogen storage in VH₂ hydride. In addition, the formation of V–H bond can improve the structural stability of VH₂ hydride. Based on the analysis of optical properties, it is found that all VH₂ hydrides show the ultraviolet response. Compared to the tetragonal and orthorhombic VH₂ hydrides, the cubic VH₂ hydride has better storage optical properties. Therefore, we believe that the VH₂ hydride is a promising hydrogen storage material.     

Porous CoNiOOH nanosheets derived from the well-mixed MOFs as stable and highly efficient electrocatalysts for water oxidation

The development of efficient and stable electrocatalysts is of great significance for improving water splitting. Among them, transition metal oxyhydroxides show excellent performance in oxygen evolution reactions (OER), but there are certain difficulties in direct preparation. Recently, Metal–organic frameworks (MOFs) as precatalysts or precursors have shown promising catalytic performance in OER and can be decomposed under alkaline conditions. Therefore, using a mild and controllable way to convert MOFs into oxyhydroxides and retaining the original structural advantages is crucial for improving the catalytic activity. Herein, a rapid electrochemical strategy is used to activate well-mixed MOFs to prepare Co/Ni oxyhydroxide nanosheets for efficient OER catalysts, and the structural transformation in this process was investigated in detail by using scanning electron microscope, X-ray diffraction, Raman, X-ray photoelectron spectroscopy and electrochemical methods. It is discovered that electrochemical activation can promote ligand substitution of well-mixed MOFs to form porous oxyhydroxide nanosheets and tune the electronic structure of the metal (Co and Ni), which can lead to more active site exposure and accelerate charge transfer. In addition, the change of structure also improves hydrophilicity, as well as benefiting from the strong synergistic effect between multiple species, the optimal a-MCoNi–MOF/NF has excellent OER performance and long-term stability. More obviously, the porous CoNiOOH nanosheets are formed in situ during electrochemical activation process through structural transformation and acts as the active centers. This work provides new insights for mild synthesis of MOFs derivatives and also provides ideas for the preparation of highly efficient catalysts.     

New horizon in mechanochemistry—high-temperature,high-pressure mechanical synthesis in a planetary ball mill—with magnesium hydride synthesis as an example

A new route of materials synthesis, namely, high-temperature, high-pressure reactive planetary ball milling (HTPRM), is presented. HTPRM allows for the mechanosynthesis of materials at fully controlled temperatures of up to 450 °C and pressures of up to 100 bar of hydrogen. As an example of this application, a successful synthesis of magnesium hydride is presented. The synthesis was performed at controlled temperatures (room temperature (RT), 100, 150, 200, 250, 300, and 325 °C) while milling in a planetary ball mill under hydrogen pressure ($>$50 bar). Very mild milling conditions (250 rpm) were applied for a total milling time of 2 h, and a milling vial with a relatively small diameter (φ = 53 mm, V = ～0.06 dm³) was used. The effect of different temperatures on the synthesis kinetics and outcome were examined. The particle morphology, phase composition, reaction yield, and particle size were measured and analysed by scanning electron microscopy, X-ray diffraction, differential scanning calorimetry (DSC) techniques. The obtained results showed that increasing the temperature of the process significantly improved the reaction rate, which suggested the great potential of this technique for the mechanochemical synthesis of materials.     

Recent trends in the development of reactor systems for hydrogen production via methanol steam reforming

Hydrogen is currently receiving significant attention as an alternative energy resource, and among the various methods for producing hydrogen, methanol steam reforming (MSR) has attracted great attention because of its economy and practicality. Because the MSR reaction is inherently activated over catalytic materials, studies have focused on the development of noble metal-based catalysts and the improvement of existing catalysts with respect to performance and stability. However, less attention has been paid to the modification and development of innovative MSR reactors to improve their performance and efficiency. Therefore, in this review paper, we summarize the trends in the development of MSR reactor systems, including microreactors and membrane reactors, as well as the various structured catalyst materials appropriate for application in complex reactors. In addition, other engineering approaches to achieve highly efficient MSR reactors for the production of hydrogen are discussed.     

Analysis of operating limits and combustion state regulation for low-calorific value gases in industrial burners

The effective and efficient utilization of low-calorific value (LCV) gases has gained increasing attention in scientific research and industrial fields. In this study, the combustion characteristics of three LCV gases in practical devices are analyzed by using a nonadiabatic perfectly stirred reactor model. The complete steady-state solution in the temperature-residence time parameter space is obtained with arc-length continuation. The stable operation region is quantified by the eigenvalue analysis. The transition of solution curves is quantified with heat loss coefficient. Five key system parameters are systematically investigated on their effects on stability limits. With the combustion performance being quantified by a combustion state index, a combustion state regulation method is proposed to find the optimal regulation path of system parameters. Active subspace method is further applied to shorten the regulation step by identifying the active direction. The proposed method and findings are useful for optimal regulation of burning LCV gases in industrial burners.     

Nonlinearity in regulating the metal to insulator transition of ReNiO3 towards low temperature range

Among the existing material family of the correlated oxides, the rare earth nickelates (ReNiO₃) exhibit broadly adjustable metal to insulator transition (MIT) properties that enables correlated electronic applications, such as thermistors, thermochromics, and logical devices. Nevertheless, how to accurately control the critical temperature (T_MIT) of ReNiO₃ via the co-occupation of the rare-earth elements is yet worthy to be further explored. Herein, we demonstrate the non-linearity in adjusting the T_MIT of ReNiO₃ towards lower temperatures via introducing Pr co-occupation within ReNiO₃ (e.g., Pr_xNd_1-xNiO₃ and Pr_xSm_1-xNiO₃) as synthesized by KCl molten-salt assisted high oxygen pressure reaction approach. Although the T_MIT is effectively reduced via Pr substitution, it does not strictly follow a linear relationship, in particular, when there is large difference in the ionic radius of the co-occupation rare-earth elements. Furthermore, the most significant deviation in T_MIT from the expected linear relationship appears at an equal co-occupation ratio of the two different rare-earth elements, while the abruption in the variation of resistivity across T_MIT is also reduced. The present work highlights the importance to use adjacent rare-earth elements with co-occupation ratio away from 1:1 for achieving more linear adjustment in designing the metal to insulator transition properties for ReNiO₃.     

Benchmark experiment of large-angle scattering reaction cross section of iron at 14 MeV using two shadow bars – Comparison of experimental results with ENDF/B-VIII –

ABSTRACT

It is important to perform neutron transport simulations with accurate nuclear data in the neutronics design of a fusion reactor. However, absolute values of large-angle scattering cross sections vary among nuclear data libraries even for well-examined nuclide of iron. Benchmark experiments focusing on large-angle scattering cross sections were thus performed to confirm the correctness of nuclear data libraries. The series benchmark experiments were performed at a DT neutron source facility, OKTAVIAN of Osaka University, Japan, by the unique experimental system established by the authors’ group, which can extract only the contribution of large-angle scattering reactions. This system consists of two shadow bars, target plate (iron), and neutron detector (niobium). Two types of shadow bars were used and four irradiations were conducted for one experiment, so that contribution of room-return neutrons was effectively removed and only large-angle scattering neutrons were extracted from the measured four Nb reaction rates. The obtained experimental results were compared with calculations for five nuclear data libraries including JENDL-4.0, JEFF.-3.3, FENDL-3.1, ENDF/B- VII, and recently released ENDF/B-VIII. It was found from the comparison that ENDF/B-VIII showed the best result, though ENDF/B-VII showed overestimation and others are in large underestimation at 14 MeV.     

Process Intensification of Living Cationic Polymerization of Isobutylene by a Flow Reaction System

Increasing the reaction temperature of the living cationic polymerization of isobutylene is crucial for industrial production due to the cost of refrigeration. The reaction temperature increase was achieved with an accelerated reaction rate using a flow reaction system. The polymerization conditions, including the flow reactor design, were based on the results of kinetic studies. Utilizing a milli‐scale flow reactor, polyisobutylene, which has a narrow molecular weight distribution, was obtained within a considerably short residence time at a high temperature. Furthermore, it was confirmed that the value of M_w/M_n correlates with the product of the Reynolds number and the angle of collision.     

Current advances concerning the most cited metal ions doped bioceramics and silicate-based bioactive glasses for bone tissue engineering

Studies related to biomaterials that stimulate the repair of living tissue have increased considerably, improving the quality of many people's lives that require surgery due to traumatic accidents, bone diseases, bone defects, and reconstructions. Among these biomaterials, bioceramics and bioactive glasses (BGs) have proved to be suitable for coating materials, cement, scaffolds, and nanoparticles, once they present good biocompatibility and degradability, able to generate osteoconduction on the surrounding tissue. However, the role of biomaterials in hard tissue engineering is not restricted to a structural replacement or for guiding tissue regeneration. Nowadays, it is expected that biomaterials develop a multifunctional role when implanted, orchestrating the process of tissue regeneration and providing to the body the capacity to heal itself. In this way, the incorporation of specific metal ions in bioceramics and BGs structure, including magnesium, silver, strontium, lithium, copper, iron, zinc, cobalt, and manganese are currently receiving enhanced interest as biomaterials for biomedical applications. When an ion is incorporated into the bioceramic structure, a new category of material is created, which has several unique properties that overcome the disadvantages of primitive material and favors its use in different biomedical applications. The doping can enhance handling properties, angiogenic and osteogenic performance, and antimicrobial activity. Therefore, this review aims to summarize the effect of selected metal ion dopants into bioceramics and silicate-based BGs in bone tissue engineering. Furthermore, new applications for doped bioceramics and BGs are highlighted, including cancer treatment and drug delivery.