Deflagration characteristics of freely propagating flames in magnesium hydride dust clouds

The flame propagation processes of MgH_(2)dust clouds with four different particle sizes were recorded by a high-speed camera.The dynamic flame temperature distributions of MgH_(2)dust clouds were reconstructed by the two-color pyrometer technique,and the chemical composition of solid combustion residues were analyzed.The experimental results showed that the average flame propagation velocities of 23μm,40μm,60μm and 103μm MgH_(2)dust clouds in the stable propagation stage were 3.7 m/s,2.8 m/s,2.1 m/s and 0.9 m/s,respectively.The dust clouds with smaller particle sizes had faster flame propagation velocity and stronger oscillation intensity,and their flame temperature distributions were more even and the temperature gradients were smaller.The flame structures of MgH_(2)dust clouds were significantly affected by the particle sinking velocity,and the combustion processes were accompanied by micro-explosion of particles.The falling velocities of 23μm and 40μm MgH_(2)particles were 2.24 cm/s and 6.71 cm/s,respectively.While the falling velocities of 60μm and 103μm MgH_(2)particles were as high as 15.07 cm/s and 44.42 cm/s,respectively,leading to a more rapid downward development and irregular shape of the flame.Furthermore,the dehydrogenation reaction had a significant effect on the combustion performance of MgH_(2)dust.The combustion of H_(2)enhanced the ignition and combustion characteristics of MgH_(2)dust,resulting in a much higher explosion power than the pure Mg dust.The micro-structure characteristics and combustion residues composition analysis of MgH_(2)dust indicated that the combustion control mechanism of MgH_(2)dust flame was mainly the heterogeneous reaction,which was affected by the dehydrogenation reaction.

Improvement effect of reversible solid solutions Mg_(2)Ni(Cu)/Mg_(2)Ni(Cu)H_(4)on hydrogen storage performance of MgH_(2)

The hydrogen absorption/desorption kinetic properties of MgH_(2)can be effectively enhanced by doping specific catalysts.In this work,MOFs-derived NiCu@C nanoparticles(~15 nm)with regular core-shell structure were successfully prepared and introduced into MgH_(2)(denoted as MgH_(2)-NiCu@C).The onset and peak temperatures of hydrogen desorption of MgH_(2)-11 wt.%NiCu@C are 175.0℃and282.2℃,respectively.The apparent activation energy of dehydrogenated reaction is 77.2±4.5 kJ/mol for MgH_(2)-11 wt.%NiCu@C,which is lower than half of that of the as-milled MgH_(2).Moreover,MgH_(2)-11 wt.%NiCu@C displays great cyclic stability.The strengthening"hydrogen pumping"effect of reversible solid solutions Mg_(2)Ni(Cu)/Mg_(2)Ni(Cu)H_(4)is proposed to explain the remarkable improvement in hydrogen absorption/desorption kinetic properties of MgH_(2).This work offers a novel perspective for the design of bimetallic nanoparticles and beyond for application in hydrogen storage and other energy related fields.

Recent progress in thermodynamic and kinetics modification of magnesium hydride hydrogen storage materials

Hydrogen energy has emerged as a pivotal solution to address the global energy crisis and pave the way for a cleaner,low-carbon,secure,and efficient modern energy system.A key imperative in the utilization of hydrogen energy lies in the development of high-performance hydrogen storage materials.Magnesium-based hydrogen storage materials exhibit remarkable advantages,including high hydrogen storage density,cost-effectiveness,and abundant magnesium resources,making them highly promising for the hydrogen energy sector.Nonetheless,practical applications of magnesium hydride for hydrogen storage face significant challenges,primarily due to their slow kinetics and stable thermodynamic properties.Herein,we briefly summarize the thermodynamic and kinetic properties of MgH2,encompassing strategies such as alloying,nanoscaling,catalyst doping,and composite system construction to enhance its hydrogen storage performance.Notably,nanoscaling and catalyst doping have emerged as more effective modification strategies.The discussion focuses on the thermodynamic changes induced by nanoscaling and the kinetic enhancements resulting from catalyst doping.Particular emphasis lies in the synergistic improvement strategy of incorporating nanocatalysts with confinement materials,and we revisit typical works on the multi-strategy optimization of MgH2.In conclusion,we conduct an analysis of outstanding challenges and issues,followed by presenting future research and development prospects for MgH2 as hydrogen storage materials.

Improving hydrogen storage thermodynamics and kinetics of Ce-Mg-Ni-based alloy by mechanical milling with TiF_(3)

Mg-based hydrides are too stable and the kinetics of hydrogen absorption and desorption is not satisfactory.An efficient way to improve these shortcomings is to employ reactive ball milling to synthesize the nanocomposite materials of Mg and additives.In this experiment,TiF_(3)was selected as an additive,and the mechanical milling method was employed to prepare the experimental alloys.The alloys used in this experiment were the as-cast Ce_(5)Mg_(85)Ni_(10),as-milled Ce_(5)Mg_(85)Ni_(10)and Ce_(5)Mg_(85)Ni_(10)+3 wt.%TiF3.The phase transformation,structural evolution,isothermal and non-isothermal hydrogenation and dehydrogenation performances of the alloys were inspected by XRD,SEM,TEM,Sievert apparatus,DSC and TGA.It revealed that nanocrystalline appeared in the as-milled samples.Compared with the as-cast alloy,ball milling made the particle dimension and grain size decrease dramatically and the defect density increase significantly.The addition of TiF_(3)made the surface of ball milling alloy particles markedly coarser and more irregular.Ball milling and adding TiF_(3)distinctly improved the activation and kinetics of the alloys.Moreover,ball milling along with TiF_(3)can decrease the onset dehydrogenation temperature of Mg-based hydrides and slightly ameliorate their thermodynamics.

Inclusion of CoTiO_(3) to ameliorate the re/dehydrogenation properties of the Mg–Na–Al system

For the first time,the MgH_(2)–NaAlH_(4)(ratio 4:1)destabilized system with CoTiO_(3) addition has been explored.The CoTiO_(3)-doped MgH_(2)–NaAlH_(4) sample begins to dehydrogenate at 130℃,which is declined by 40℃ compared to the undoped MgH_(2)–NaAlH_(4).Moreover,the de/rehydrogenation kinetics characteristics of the CoTiO_(3)-doped MgH_(2)–NaAlH_(4) were greatly ameliorated.With the inclusion of CoTiO_(3),the MgH_(2)–NaAlH_(4) composite absorbed 5.2 wt.%H_(2),higher than undoped MgH_(2)–NaAlH_(4).In the context of dehydrogenation,the CoTiO_(3)-doped MgH_(2)–NaAlH_(4) sample desorbed 2.6 wt.%H_(2),almost doubled compared to the amount of hydrogen desorbed from the undoped MgH_(2)–NaAlH_(4) sample.The activation energy obtained by the Kissinger analysis for MgH_(2) decomposition was significantly lower by 35.9 kJ/mol than the undoped MgH_(2)–NaAlH_(4) sample.The reaction mechanism demonstrated that new phases of MgCo and AlTi_(3) were generated in situ during the heating process and are likely to play a substantial catalytic function and be useful in ameliorating the de/rehydrogenation properties of the destabilized MgH_(2)–NaAlH_(4) system with the inclusion of CoTiO_(3).

Phase-field simulations of the effect of temperature and interface for zirconiumδ-hydrides

Hydride precipitation in zirconium cladding materials can damage their integrity and durability.Service temperature and material defects have a significant effect on the dynamic growth of hydrides.In this study,we have developed a phasefield model based on the assumption of elastic behaviour within a specific temperature range(613 K-653 K).This model allows us to study the influence of temperature and interfacial effects on the morphology,stress,and average growth rate of zirconium hydride.The results suggest that changes in temperature and interfacial energy influence the length-to-thickness ratio and average growth rate of the hydride morphology.The ultimate determinant of hydride orientation is the loss of interfacial coherency,primarily induced by interfacial dislocation defects and quantifiable by the mismatch degree q.An escalation in interfacial coherency loss leads to a transition of hydride growth from horizontal to vertical,accompanied by the onset of redirection behaviour.Interestingly,redirection occurs at a critical mismatch level,denoted as qc,and remains unaffected by variations in temperature and interfacial energy.However,this redirection leads to an increase in the maximum stress,which may influence the direction of hydride crack propagation.This research highlights the importance of interfacial coherency and provides valuable insights into the morphology and growth kinetics of hydrides in zirconium alloys.

Understanding the catalysis of chromium trioxide added magnesium hydride for hydrogen storage and Li ion battery applications

This study explores how the chemical interaction between magnesium hydride(MgH_(2))and the additive CrO_(3) influences the hydrogen/lithium storage characteristics of MgH_(2).We have observed that a 5 wt.%CrO_(3) additive reduces the dehydrogenation activation energy of MgH_(2) by 68 kJ/mol and lowers the required dehydrogenation temperature by 80℃.CrO_(3) added MgH_(2) was also tested as an anode in an Li ion battery,and it is possible to deliver over 90%of the total theoretical capacity(2038 mAh/g).Evidence for improved reversibility in the battery reaction is found only after the incorporation of additives with MgH_(2).In depth characterization study by X-ray diffraction(XRD)technique provides convincing evidence that the CrO_(3) additive interacts with MgH_(2) and produces Cr/MgO byproducts.Gibbs free energy analyses confirm the thermodynamic feasibility of conversion from MgH_(2)/CrO_(3) to MgO/Cr,which is well supported by the identification of Cr(0)in the powder by X ray photoelectron spectroscopy(XPS)technique.Through high resolution transmission electron microscopy(HRTEM)and energy dispersive spectroscopy(EDS)we found evidence for the presence of 5 nm size Cr nanocrystals on the surface of MgO rock salt nanoparticles.There is also convincing ground to consider that MgO rock salt accommodates Cr in the lattice.These observations support the argument that creation of active metal–metal dissolved rock salt oxide interface may be vital for improving the reactivity of MgH_(2),both for the improved storage of hydrogen and lithium.

The dynamic catalysis of Ga/ZSM-5 catalysts for propane-CO_(2) coupling conversion to aromatics and syngas

Alkane coupling with CO_(2) by metal-containing zeolites catalysis is found to be a promising way to produce aromatics and syngas in recent years,but the real active sites and the role of CO_(2) are still unclear owing to the quick evolution of the metallic active sites and the complex reaction processes including direct propane aromatization,CO_(2) hydrogenation,reverse water-gas shift reaction,and propane-CO_(2) coupling aromatization.Herein,Ga/ZSM-5 catalysts were constructed to study the dynamic evolution of the metallic active sites and the role of CO_(2) during the propane and CO_(2) coupling reaction.After optimizing the reaction conditions,a notable propane conversion rate of 97.9%and an impressive aromatics selectivity of 80.6%in hydrocarbons can be achieved at the conditions of 550℃and CO_(2)/C_(3)H_(8) of 4.^(13)CO_(2)isotope experiments illustrate that C-atoms of CO_(2) can enter into CO(86.5%)and aromatics(10.8%)during the propane-CO_(2) coupling reaction process.In situ XANES and FTIR spectroscopies at 550℃and H_(2)/C_(3)H_(8) atmosphere reveal that GaO_(x) species can be gradually dispersed into[GaH_(2)]^(+)/[GaH]^(2+)on the Bronsted acid sites of ZSM-5 zeolite during H_(2) and/or C_(3)H_(8) treatment,which are the real active sites for propane-CO_(2) coupling conversion.In situ CO_(2)-FTIR experiments demonstrate that the[GaH_(2)]^(+)/[GaH]^(2+)species can react with CO_(2) and accelerate the propane and CO_(2) coupling process.This work not only presents a cost-effective avenue for CO_(2) utilization,but also contributes to the active site design for improved alkane and CO_(2) activation in coupling reaction system.

Tuning the electronic conductance of REH_(x)(RE=Nd,Ce,Pr)by structural deformation

Hydride ion(H-)conductors have drawn much attention due to their potential applications in hydrideion-based devices.Rare earth metal hydrides(REH_(x))have fast H-conduction which,unfortunately,is accompanied by detrimental electron conduction preventing their application as ion conductors.Here,REH_(x)(RE=Nd,Ce,and Pr)with varied grain sizes,rich grain boundaries,and defects have been prepared by ball milling and subsequent sintering.The electronic conductivity of the ball-milled REH_(x)samples can be reduced by 2-4 orders of magnitude compared with the non-ball-milled samples.The relationship of electron conduction and miscrostructures in REH_(x)is studied and discussed based on experimental data and previously-proposed classical and quantum theories.The H-conductivity of all REH_(x)is about 10^(-4)to 10^(-3)S cm^(-1)at room temperature,showing promise for the development of H-conductors and their applications in clean energy storage and conversion.

Isothermal hydrogen absorption process of Pd-capped Mg films traced by ion beam techniques and optical methods

Pd-capped nanocrystalline Mg films were prepared by electron beam evaporation and hydrogenated under isothermal conditions to inves-tigate the hydrogen absorption process via ion beam techniques and in situ optical methods.Films were characterized by different techniques such as X-ray diffraction(XRD)and scanning electron microscopy(SEM).Rutherford backscattering spectrometry(RBS)and elastic recoil detection analysis(ERDA)provided a detailed compositional depth profile of the films during hydrogenation.Gas-solid reaction kinetics theory applied to ERDA data revealed a H absorption mechanism controlled by H diffusion.This rate-limiting step was also confirmed by XRD measurements.The diffusion coefficient(D)was also determined via RBS and ERDA,with a value of(1.1±0.1)·10^(−13)cm^(2)/s at 140℃.Results confirm the validity of IBA to monitor the hydrogenation process and to extract the control mechanism of the process.The H kinetic information given by optical methods is strongly influenced by the optical absorption of the magnesium layer,revealing that thinner films are needed to extract further and reliable information from that technique.

Unveiling a novel metal-to-metal transition in LuH_(2):Critically challenging superconductivity claims in lutetium hydrides

Following the recent report by Dasenbrock-Gammon et al.[Nature 615,244–250(2023)]of near-ambient superconductivity in nitrogendoped lutetium trihydride(LuH_(3-δ)N_(ε)),significant debate has emerged surrounding the composition and interpretation of the observed sharp resistance drop.Here,we meticulously revisit these claims through comprehensive characterization and investigations.We definitively identify the reported material as lutetium dihydride(LuH_(2)),resolving the ambiguity surrounding its composition.Under similar conditions(270–295 K and 1–2 GPa),we replicate the reported sharp decrease in electrical resistance with a 30%success rate,aligning with the observations by Dasenbrock-Gammon et al.However,our extensive investigations reveal this phenomenon to be a novel pressure-induced metal-to-metal transition intrinsic to LuH_(2),distinct from superconductivity.Intriguingly,nitrogen doping exerts minimal impact on this transition.Our work not only elucidates the fundamental properties of LuH_(2)andLuH_(3),but also critically challenges the notion of superconductivity in these lutetium hydride systems.These findings pave the way for future research on lutetium hydride systems,while emphasizing the crucial importance of rigorous verification in claims of ambient-temperature superconductivity.

Properties of radiation defects and threshold energy of displacement in zirconium hydride obtained by new deep-learning potential

Zirconium hydride(ZrH_(2)) is an ideal neutron moderator material. However, radiation effect significantly changes its properties, which affect its behavior and the lifespan of the reactor. The threshold energy of displacement is an important quantity of the number of radiation defects produced, which helps us to predict the evolution of radiation defects in ZrH_(2).Molecular dynamics(MD) and ab initio molecular dynamics(AIMD) are two main methods of calculating the threshold energy of displacement. The MD simulations with empirical potentials often cannot accurately depict the transitional states that lattice atoms must surpass to reach an interstitial state. Additionally, the AIMD method is unable to perform largescale calculation, which poses a computational challenge beyond the simulation range of density functional theory. Machine learning potentials are renowned for their high accuracy and efficiency, making them an increasingly preferred choice for molecular dynamics simulations. In this work, we develop an accurate potential energy model for the ZrH_(2) system by using the deep-potential(DP) method. The DP model has a high degree of agreement with first-principles calculations for the typical defect energy and mechanical properties of the ZrH_(2) system, including the basic bulk properties, formation energy of point defects, as well as diffusion behavior of hydrogen and zirconium. By integrating the DP model with Ziegler–Biersack–Littmark(ZBL) potential, we can predict the threshold energy of displacement of zirconium and hydrogen in ε-ZrH_(2).

Ballistic performance of titanium-based layered composites made using blended elemental powder metallurgy and hot isostatic pressing

Metal matrix composites tiles based on Ti-6Al-4V(Ti64)alloy,reinforced with 10,20,and 40(vol%)of either TiC or TiB particles were made using press-and-sinter blended elemental powder metallurgy(BEPM)and then bonded together into 3-layer laminated plates using hot isostatic pressing(HIP).The laminates were ballistically tested and demonstrated superior performance.The microstructure and properties of the laminates were analyzed to determine the effect of the BEPM and HIP processing on the ballistic properties of the layered plates.The effect of porosity in sintered composites on further diffusion bonding of the plates during HIP is analyzed to understand the bonding features at the interfaces between different adjacent layers in the laminate.Exceptional ballistic performance of fabricated structures was explained by a significant reduction in the residual porosity of the BEPM products by their additional processing using HIP,which provides an unprecedented increase in the hardness of the layered composites.It is argued that the combination of the used two technologies,BEPM and HIP is principally complimentary for the materials in question with the abilities to solve the essential problems of each used individually.

Nanostructured MXene-based materials for boosting hydrogen sorption properties of Mg/MgH_(2)

Hydrogen holds the advantages of high energy density,great natural abundance and zero emission,making it suitable for large scale and long term energy storage,while its safe and efficient storage is still challenging.Among various solid state hydrogen storage materials,MgH_(2) is promising for industrial applications due to its high gravimetric and volumetric hydrogen densities and the abundance of Mg on earth.However,the practical application of MgH_(2) has been limited by its stable thermodynamics and slow hydrogen desorption kinetics.Nanocatalysis is considered as a promising approach for improving the hydrogen storage performance of MgH_(2) and bringing it closer to the requirements of commercial applications.It is worth mentioning that the recently emerging two-dimensional material,MXene,has showcased exceptional catalytic abilities in modifying the hydrogen storage properties of MgH_(2).Besides,MXene possesses a high surface area,excellent chemical/physical stability,and negatively charged terminating groups,making it an ideal support for the"nanoconfinement"of MgH_(2) or highly active catalysts.Herein,we endeavor to provide a comprehensive overview of recent investigations on MXene-based catalysts and MXene supports for improving the hydrogen sorption properties of Mg/MgH_(2).The mechanisms of hydrogen sorption involved in Mg-MXene based composites are highlighted with special emphases on thermodynamics,kinetics,and catalytic behaviors.The aim of this work is to provide a comprehensive and objective review of researches on the development of high-performance catalysts/supports to improve hydrogen storage performances of Mg/MgH_(2) and to identify the opportunities and challenges for future applications.

Editorial for the special issue“Hydrogen Energy Production,Storage and Utilization”

Hydrogen energy has emerged as a significant energy source for accomplishing energy transformation and achieving carbon neutrality.Hydrogen production,storage and transportation are the key technologies to realize hydrogen energy application and carbon neutralization goal.Apart from the mature technologies of fossil fuel reforming and water electrolysis,new hydrogen production methods(such as solar photolysis,biomass conversion,thermochemical circulation,etc.)have garnered widespread attention and research interest.The lack of safe and efficient hydrogen storage and utilization technology for hydrogen fuel cell systems is the major obstacle to achieving hydrogen economy.In the past decades,global researchers have conducted extensive studies on enhancing the hydrogen storage performance of materials,such as alloy,metal hydride,complex hydride,carbon-based materials,etc.,as well as the technological development of fuel cell power generation systems using solid hydrogen storage materials as hydrogen storage carriers.The themed issue entitled“Hydrogen Energy Production,Storage and Utilization”includes 10 carefully selected papers that address the most recent developments in hydrogen production and storage materials,involving catalyst design,structure characterization,hydrogen ab-/desorption performance and mechanism,and fuel cell coupling system exploit.

Understanding the dehydrogenation properties of Mg(0001)/MgH_(2)(110)interface from first principles

Magnesium hydride is one of the most promising solid-state hydrogen storage materials for on-board application.Hydrogen desorption from MgH_(2) is accompanied by the formation of the Mg/MgH_(2) interfaces,which may play a key role in the further dehydrogenation process.In this work,first-principles calculations have been used to understand the dehydrogenation properties of the Mg(0001)/MgH_(2)(110) interface.It is found that the Mg(0001)/MgH_(2)(110) interface can weaken the Mg-H bond.The removal energies for hydrogen atoms in the interface zone are significantly lower compared to those of bulk MgH_(2).In terms of H mobility,hydrogen diffusion within the interface as well as into the Mg matrix is considered.The calculated energy barriers reveal that the migration of hydrogen atoms in the interface zone is easier than that in the bulk MgH_(2).Based on the hydrogen removal energies and diffusion barriers,we conclude that the formation of the Mg(0001)/MgH_(2)(110) interface facilitates the dehydrogenation process of magnesium hydride.

Magnesium nickel hydride monocrystalline nanoparticles for reversible hydrogen storage

Although Mg-based hydrides are extensively considered as a prospective material for solid-state hydrogen storage and clean energy carriers,their high operating temperature and slow kinetics are the main challenges for practical application.Here,a Mg-Ni based hydride,Mg_(2)NiH_(4) nanoparticles(~100 nm),with dual modification strategies of nanosizing and alloying is successfully prepared via a gas-solid preparation process.It is demonstrated that Mg_(2)NiH_(4) nanoparticles form a unique chain-like structure by oriented stacking and exhibit impressive hydrogen storage performance:it starts to release H2 at~170℃ and completes below 230℃ with a saturated capacity of 3.32 wt%and desorbs 3.14 wt% H_(2) within 1800 s at 200℃.The systematic characterizations of Mg_(2)NiH_(4) nanoparticles at different states reveal the dehydrogenation behavior and demonstrate the excellent structural and hydrogen storage stabilities during the de/hydrogenated process.This research is believed to provide new insights for optimizing the kinetic performance of metal hydrides and novel perspectives for designing highly active and stable hydrogen storage alloys.

High Harmonic Spectroscopy Retrieves Electronic Structure of High-pressure Superconductors

High pressure has revealed surprising physics and creates novel states in condensed matter.Exciting examples include near-roomtemperature superconductivity(T_(c)>200 K)in highlypressured hydrides such as H_(3)S and LaH_(10).

Preparation and characterization of aluminum foams with ZrH_2 as foaming agent

Aluminum foams were fabricated by melt-based route using ZrH2 as a foaming agent. The factors which affected the foaming of aluminum foams during casting process were investigated. The powdered zirconium hydride with content of 0.6%-1.4% （mass fraction） was added to the molten pure aluminum and the foaming condition was controlled in a temperature range from 933 to 1 013 K, Ca amount of 1.5%-3.0% （mass fraction）, stirring time of 0.5-2.5 min and holding time of 1.5-4.0 min to obtain homogeneous aluminum foams. The fabricated aluminum foams were characterized by XRD, SEM and Image-pro plus. The mechanical properties of the aluminum foams with different relative density were tested. The result indicates that the foaming agent （ZrH2） is suitable for the preparation of small aperture aluminum foams with average pore diameter of 1 mm. Inter-metallic compounds and Al2O3 have effect on the melt viscosity. The aluminum foams experience linear elastic, platforms and densification process and had a higher efficiency of energy absorption.

Formation mechanism of MgB_2 in 2LiBH_4+MgH_2 system for reversible hydrogen storage

The formation conditions of MgB2 in 2LiBH4 ＋ MgH2 system during dehydrogenation were investigated and its mechanism was discussed. The results show that direct decomposition of LiBH4 is suppressed under relative higher initial dehydrogenation pressure of 4.0×10^5 Pa, wherein LiBH4 reacts with Mg to yield MgB2, and 9.16% （mass fraction） hydrogen is released within 9.6 h at 450 ℃. However, under relatively lower initial dehydrogenation pressure of 1.0×10^2 Pa, LiBH4 decomposes independently instead of reacting with Mg, resulting in no formation of MgB2, and 7.91% hydrogen is desorbed within 5.2 h at 450 ℃. It is found that the dehydrogenation of 2LiBH4 ＋ MgH2 system proceeds more completely and more hydrogen desorption amount can be obtained within a definite time by forming MgB2. Furthermore, it is proposed that the formation process of MgB2 includes incubation period and nucleus growth process. Experimental results show that the formation process of MgB2, especially the incubation period, is promoted by increasing initial dehydrogenation pressure at constant temperature, and the incubation period is also influenced greatly by dehydrogenation temperature.