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.

Thermodynamics and kinetics insights into naphthalene hydrogenation over a Ni-Mo catalyst

Hydrocracking represents an important process in modern petroleum refining industry,whose performance mainly relies on the identity of catalyst.In this work,we perform a combined thermodynamics and kinetics study on the hydrogenation of naphthalene over a commercialized NiMo/HY catalyst.The reaction network is constructed for the respective production of decalin and methylindane via the intermediate product of tetralin,which could further undergo hydrogenation to butylbenzene,ethylbenzene,xylene,toluene,benzene,methylcyclohexane and cyclohexane.The thermodynamics analysis suggests the optimum operating conditions for the production of monoaromatics are 400℃,8.0 MPa,and 4.0 hydrogen/naphthalene ratio.Based on these,the influences of reaction temperature,pressure,hydrogen/-naphthalene ratio,and liquid hourly space velocity(LHSV)are investigated to fit the Langmuir-Hinshelwood model.It is found that the higher temperature and pressure while lower LHSV favors monoaromatics production,which is insensitive to the hydrogen/naphthalene ratio.Furthermore,the high consistence between the experimental and simulated data further validates the as-obtained kinetics model on the prediction of catalytic performance over this kind of catalyst.

Thermodynamic and kinetics of hydrogen photoproduction enhancement by concentrated sunlight with CO_(2) photoreduction by heterojunction photocatalysts

For achieving water splitting into hydrogen under sunlight for practical applications,the high efficiencies of the photoreduction of CO_(2) over TiO_(2)/Fe3O4 photocatalysts combined with hydrogenation of water splitting over Pt/TiO_(2) were investigated by practical concentrated solar energy compared with Hg lamp and Xe lamp.Based on AI analysis on the influence factors,the key parameters for TOC concentration were photocatalysts,Na2CO3 concentration and radiation intensity while the key parameters for hydrogen production were photocatalysts,radiation intensity,and TOC concentration.Accordingly,the mechanism of concentrated sunlight effects has been discussed from the view of thermodynamics and kinetics.The concentrated sunlight provides a simultaneous supply of sufficient electron–hole pairs and thermal energy.Water to hydrogen and CO_(2) reduction are both enhanced in concentrated sunlight due to endothermal reactions.Doping changes the internal electric field of p-n junction of in different possible ways,and thus composite photocatalysts with favorable formation of p-n junctions would enhance the charge separation by internal electric field.Moreover,photocatalysts are beneficial for providing more excited electrons at a time for achieving CO_(2) photoreduction at the surface region of the particles with higher density of radiation by concentrated solar energy.Subsequently,products from CO_(2) photoreduction,acting as sacrificial electron donors,improved hydrogen evolution in solar-mediated water splitting for prohibiting reverse reactions.

Optimizing mechanical properties of magnesium alloys by philosophy of thermo-kinetic synergy:Review and outlook

Although several strategies(including grain refinement,texture adjustment,precipitation hardening,etc.)have been verified to effectively improve the mechanical properties of lightweight magnesium(Mg)alloys,considerable efforts are still needed to be made to comprehensively understand the potential mechanisms controlling complex microstructures and deformation behaviors exhibited by the hexagonal close-packed host lattice of Mg,thus assisting the rational design of materials at a more physical level.As the cornerstone of this review,a universal rule,the so-called synergy of thermodynamics and kinetics(i.e.,thermo-kinetic diversity,correlation and connectivity),including a recently proposed theory of generalized stability(GS),is introduced to deepen our understanding on common behaviors in Mg alloys(i.e.,deformations(slip and twining modes),phase transformations(especially for precipitations)and interactions in between)at a new perspective.Guided by the GS theory,typical cases for Mg alloys design are qualitatively evaluated to reemphasize the traditional strengthening and toughening strategies mentioned above and to illuminate their exquisite coordination for breaking through the trade-off relationship between strength and ductility,corresponding to a typical thermo-kinetic pair(i.e.,high driving force(ΔG)-high GS).To produce the Mg alloys with superior strength-ductility balances,the potential capacity of this GS theory for guiding processing path design is discussed,finally。

Modeling and simulation of dynamic performance of horizontal steam-launch system

Based on theory of variable-mass system thermodynamics, the dynamic mathematic models of each component of the horizontal steam-launch system were established, and by the numerical simulation of the system launching process, the thermodynamics and kinetics characteristics of the system with three valves of different flow characteristics were got. The simulation results show that the values of the peak-to-average ratios of dimensionless acceleration with the equal percentage valve, the linear valve and the quick opening valve are 1.355, 1.614 and 1.722, respectively, and the final values of the dimensionless velocities are 0.843, 0.957 and 1.0, respectively. In conclusion, the value of the dimensionless velocity with the equal percentage valve doesn't reach the set value of 0.90 when the dimensionless displacement is 0.82, while the system with the linear valve can meet the launching requirement, as well as the fluctuation range of dimensionless acceleration is less than that of the quick opening valve. Therefore, the system with the linear valve has the best performance among the three kinds of valves.

Removal of Heteroaromatic Sulfur Compounds by a Non-noble Metal Fe Single-atom Adsorbent

Sulfur-containing compounds(SCCs)must be removed from fuels before use.In this study,a novel non-noble metal Fe single-atom adsorbent(SA-Fe/CN)was synthesized using a core-shell strategy and applied for the adsorptive removal of benzothiophene(BT)and dibenzothiophene(DBT).The adsorption isotherms,thermodynamics,kinetics,and adsorption-regeneration cycles of DBT and BT on SA-Fe/CN were studied.SA-Fe/CN exhibited a significant capacity to adsorb DBT,and the isothermal equilibrium was well described by the Langmuir isotherm.The Gibbs free energy values were negative(ΔG^(0)<0),indicating that the adsorption of DBT and BT was favored and spontaneous.The adsorption process conformed to the pseudo-second-order kinetic model with high R^(2) values(0.9994,0.9987).The adsorption capacity of SA-Fe/CN for DBT and BT reached 163.21 mg/g and 90.35 mg/g,respectively,due to the highly active sites of the single atom and electrostatic interaction with the sulfide.Therefore,SA-Fe/CN may be a promising adsorbent for SCC removal.

Thermo-kinetic characteristics on stabilizing hetero-phase interface of metal matrix composites by crystal plasticity finite element method

Using dislocation-based constitutive modeling in three-dimension crystal plasticity finite element(3D CPFE)simulations,co-deformation and instability of hetero-phase interface in different material systems were herein studied for polycrystalline metal matrix composites(MMCs).Local stress and strain fields in two types of 3layer MMCs such as fcc/fcc Cu-Ag and fcc/bcc Cu-Nb have been predicted under simple compressive deformations.Accordingly,more severe strain-induced interface instability can be observed in the fcc/bcc systems than in the fcc/fcc systems upon refining to metallic nanolayered composites(MNCs).By detailed analysis of stress and strain localization,it has been demonstrated that the interface instability is always accompanied by high-stress concentration,i.e.,thermodynamic characteristics,or high strain prevention i.e.,kinetic characteristics,at the hetero-phase interface.It then follows that the thermodynamic driving forceG and the kinetic energy barrier Q during dislocation and shear banding can be adopted to classify the deformation modes,following the so-called thermo-kinetic correlation.Then by inserting a high density of high-energy interfaces into the Cu-Nb composites,such thermo-kinetic integration at the hetero-phase interface allows a successful establishment of MMCs with the high△G-high Q deformation mode,which ensures high hardening and uniform strain distri-bution,thus efficiently suppressing the shear band,stabilizing the hetero-phase interface,and obtaining an exceptional combination in strength and ductility.Such hetero-phase interface chosen by a couple of thermodynamics and kinetics can be defined as breaking the thermo-kinetic correlation and has been proposed for artificially designing MNCs.

Integrated unified phase-field modeling(UPFM)

For a long time,the phase-field method has been considered a mesoscale phenomenological method that lacks physical accuracy and is unable to be closely linked to the mechanical or functional properties of materials.Some misunderstandings existing in these viewpoints need to be clarified.Therefore,it is necessary to propose or adopt the perspective of“unified phase-field modeling(UPFM)”to address these issues,which means that phase-field modeling has multiple unified characteristics.Specifically,the phase-field method is the perfect unity of thermodynamics and kinetics,the unity of multi-scale models from microto meso and then to macro,the unity of internal or/and external driving energy with order parameters as field variables,the unity of multiple physical fields,and thus the unity of material composition design,process optimization,microstructure control,and performance prediction.It is precisely because the phase-field approach has these unified characteristics that,after more than 40 years of development,it has been increasingly widely applied in materials science and engineering.

Research progress in Mg-based hydrogen storage alloys

Magnesium and magnesium-based alloy hydrides remain attractive hydrogen storage materials owing to high hydrogen capacity and rich reserves in the earth＇s crust. A high stability of hydride and sluggish hydriding/dehydriding kinetics at practical temperatures for the materials drove researchers into alloying with other elements, using different preparation techniques, using catalyst and thin film hydride to improve the hydrogen absorption/desorption properties. In this review, the development of these approaches and their effects on the thermodynamic and kinetics properties of magnesium and magnesium-based alloy hydrides were descript in details.