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.

Adsorption kinetics and thermodynamics of sodium butyl xanthate onto bornite in flotation

In this paper,the effect of sodium butyl xanthate(NaBX)adsorption on the surface of bornite at different pH on flotation was studied by adsorption kinetic and thermodynamic.The flotation results demonstrated that the recovery was the highest when pH was 9 in NaBX solution(4×10^?5 mol/L).The adsorption kinetics showed the reaction of NaBX on the bornite conformed to the second order kinetic equation;it belonged to the multimolecular layer adsorption of Freundlich model;the maximum adsorption rate constant was 0.30 g/(10^?6 mol·min),and the equilibrium adsorption capacity was 2.70×10^?6 mol/g.Thermodynamic calculation results indicated that the adsorption process was spontaneous chemisorption,and the adsorption products of NaBX on bornite surface were cupric butyl xanthate,ferric butyl xanthate and dixanthogen,which were confirmed by infrared spectrum measurements.

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.

Ghezeljeh nanoclay as a new natural adsorbent for the removal of copper and mercury ions: Equilibrium, kinetics and thermodynamics studies

Heavy metal determination was carried out by applying the solid phase extraction （SPE） method in batch mode followed by atomic absorption spectroscopy （AAS） and inductively coupled plasma atomic emission spectrosco py （ICP-AES） from aqueous solutions using Ghezeljeh montmorillonite nanoclay as a new natural adsorbent. The Ghezeljeh clay is characterized by using Fourier Transform Infrared （FT-IR） Spectroscopy, Scanning Electron Mi- croscopy-Energy Dispersive Spectrometry （SEM-EDS） and X-ray Diffractometry （XRD） and X-ray Fluorescence （XRF）. The results of XRD and FT-IR of nanoclay confirm that montmorillonite is the dominant mineral phase. Based on SEM images of Ghezeljeh clay, it can be seen that the distance between the plates is Nano. The effects of varying parameters such as initial concentration of metal ions, pH and type of buffer solutions, amount of ad- sorbent, contact time, and temperature on the adsorption process were examined. The effect of various interfer- ing ions was studied. The adsorption data correlated with Freundlich, Langmuir, Dubinin-Radushkevich （D-R）, and Temkin isotherms. The Langmuir and Freundlich isotherms showed the best fit to the equilibrium data for Hg（II）, but the equilibrium nature of Cu（ll） adsorption has been described by the Langmuir isotherm. The kinetic data were described with pseudo-first-order, pseudo-second-order and double-exponential models, The adsorp- tion process follows a pseudo-second-order reaction scheme, Calculation of AGσ, △Hσ and ASσ showed that tilenature of Hg（II） ion sorption onto the Ghezeljeh nanoclay was endothermic and was favored at higher temper- attire, and the nature of Cu（II） ion sorption was exothermic and was favored at lower temperature,

Synthesis of a novel functional group-bridged magnetized bentonite adsorbent:Characterization,kinetics,isotherm,thermodynamics and regeneration

A novel magnetic adsorbent was synthesized by magnetizing bentonite by APTES-Fe_3O_4 via a functional groupbridged interaction. The characterization of APTES-Fe_3O_4/bentonite was conducted via transmission electron microscope(TEM), X-ray diffraction(XRD), Fourier transform infrared spectrophotometer(FT-IR), thermal gravimetric analysis(TGA), vibrating sample magnetometer(VSM), zeta potential analysis and Brunner–Emmet–Teller(BET). The APTES-Fe_3O_4/bentonite was assessed as adsorbents for methylene blue(MB) with a high adsorption capacity(91.83 mg·g^(-1)). Factors affecting the adsorption of MB(such as p H, equilibrium time, temperature and initial concentration) were investigated. The adsorption process completely reaches equilibrium after 120 min and the maximum sorption is achieved at p H 8.0. The adsorption trend follows the pseudosecond order kinetics model. The adsorption data gives good fits with Langmuir isotherm model. The parameter factor RLfalls between 0 and 1, indicating the adsorption of MB is favorable. The adsorption process is endothermic with positive ΔH^0 values. The positive values of ΔG^0 confirm the affinity of the adsorbent towards MB, and suggest an increased randomness at the solid–liquid interface during the adsorption process. Regeneration of the saturated adsorbent was easily carried out via gamma-irradiation.

Kinetics and Thermodynamic Parameters of the CopperExchange on Na-montmorillonite Clay Mineral inSelected Solvents

The kinetics of Cu ion exchange on Na-montmorillonite clay mineral has been investigated at three temperatures, in three solvents: H2O, ethylene glycol and glycerol. Solvent effects on the reaction rate have been discussed. The thermodynamic activation parameters were calculated and discussed in terms of solvation effects. The determined isokinetic temperature indicates that the reaction is enthalpy controlled where the interaction between solvent and clay surface plays an important role. A reaction mechanism which describes the solvent effect on the rate of Cu ion exchange is proposed.

K^+ Adsorption Kinetics of Fluvo-Aquic and Cinnamon Soil Under Different Temperature

The K+ adsorption kinetics of fluvo-aquic soil and cinnamon soil under different temperatureswere studied. The results showed: 1) The first order equations were the most suitable forfitting the adsorption under various temperature levels with constant K+ concentration indisplacing fluid. With temperature increasing, the fitness of Elovich equation increased,while those of power equation and parabolic diffusion equation decreased; 2)the apparentadsorption rate constant ka and the product of ka multiplied by the apparent equilibriumadsorption qincreased when temperature increased, while the apparent equilibrium adsorptionqreduced; 3)temperature influenced hardly the reaction order, the order of concentrationand adsorpton site were always 1 under various temperatures, if they were taken intoaccount simultaneously, the adsorption should be a two-order reaction process; 4)theGibbs free energy change △G of potassium adsorption were negative, ranged from -4444.56to -2450.63Jmol-1,and increased with temperature increasing, while enthalpy change △H,entropy change △S, apparent adsorption activation Ea, adsorption activation energy E1and desorption activation energy E2 were temperature-independent; 5)the adsorption wasspontaneous process with heat releasing and entropy dropping, fluvo-aquic soil releasedmore heat than cinnamon soil.

Formation mechanism and control of MgO·Al_2O_3 inclusions in non-oriented silicon steel

On the basis of the practical production of non-oriented silicon steel, the formation of Mg O·Al2O3 inclusions was analyzed in the process of ＂basic oxygen furnace（BOF） → RH → compact strip production（CSP）＂. The thermodynamic and kinetic conditions of the formation of Mg O·Al2O3 inclusions were discussed, and the behavior of slag entrapment in molten steel during RH refining was simulated by computational fluid dynamics（CFD） software. The results showed that the Mg O/Al2O3 mass ratio was in the range from 0.005 to 0.017 and that Mg O·Al2O3 inclusions were not observed before the RH refining process. In contrast, the Mg O/Al2O3 mass ratio was in the range from 0.30 to 0.50, and the percentage of Mg O·Al2O3 spinel inclusions reached 58.4% of the total inclusions after the RH refining process. The compositions of the slag were similar to those of the inclusions; furthermore, the critical velocity of slag entrapment was calculated to be 0.45 m·s^-1 at an argon flow rate of 698 L·min^-1, as simulated using CFD software. When the test steel was in equilibrium with the slag, [Mg] was 0.00024wt%–0.00028wt% and [Al]s was 0.31wt%–0.37wt%; these concentrations were theoretically calculated to fall within the Mg O·Al2O3formation zone, thereby leading to the formation of Mg O·Al2O3 inclusions in the steel. Thus, the formation of Mg O·Al2O3 inclusions would be inhibited by reducing the quantity of slag entrapment, controlling the roughing slag during casting, and controlling the composition of the slag and the Mg O content in the ladle refractory.

Crystallization behaviors of ultrathin Al-doped HfO2 amorphous films grown by atomic layer deposition

In this work, ultrathin pure HfO_2 and Al-doped HfO_2films（about 4-nm thick） are prepared by atomic layer deposition and the crystallinities of these films before and after annealing at temperatures ranging from 550℃ to 750℃ are analyzed by grazing incidence x-ray diffraction. The as-deposited pure HfO_2 and Al-doped HfO_2 films are both amorphous. After550-℃ annealing, a multiphase consisting of a few orthorhombic, monoclinic and tetragonal phases can be observed in the pure HfO_2 film while the Al-doped HfO_2 film remains amorphous. After annealing at 650℃ and above, a great number of HfO_2 tetragonal phases, a high-temperature phase with higher dielectric constant, can be stabilized in the Al-doped HfO_2 film. As a result, the dielectric constant is enhanced up to about 35. The physical mechanism of the phase transition behavior is discussed from the viewpoint of thermodynamics and kinetics.

Adsorption behavior of molybdenum onto D314 ion exchange resin

The adsorption behavior of molybdenum onto D314 was studied with the static adsorption method. The adsorption process was analyzed from thermodynamic and kinetic aspects. The experimental results show that the equilibrium adsorption data conform satisfactorily to the Langmuir equation. In the adsorption process of D314 for molybdenum, the enthalpy change ΔH is positive when temperature is in the range of 298-338 K, which indicates that the adsorption is an endothermic process, and the elevated temperature benefits to the adsorption. Kinetic analysis shows that the adsorption rate is controlled by intraparticle diffusion and chemical diffusion at the same time. The adsorption mechanism of molybdenum onto D314 was discussed based on IR spectra.

Progress in Research of Gas Hydrate

It is of great significance to study gas hydrate because of following reasons. （1） Most organic carbon in the earth reserves in the form of natural gas hydrate, which is considered as a potential energy resource for the survival of human being in the future. （2） A series of novel technologies are based on gas hydrate. （3） Gas hydrate may lead to many hazards including plugging of oil/gas pipelines, accelerating global warming up, etc. In this paper, the latest progresses in exploration and exploitation of natural gas hydrate, the development of hydrate-based technologies including gas separation, gas storage, CO2 sequestration via forming hydrate, as well as the prevention of hydrate hazards are reviewed. Additionally, the progresses in the fundamental study of gas hydrate, including the thermodynamics and kinetics are also reviewed. A prospect to the future of gas hydrate research and application is given.

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。

Effect of milling duration on hydrogen storage thermodynamics and kinetics of ball-milled Ce-Mg-Ni-based alloy powders

To improve the hydrogen storage performance of CeMg12-type alloys, partially substituting Mg with Ni in the alloy was conducted. The way to synthesize the target alloy powders was the mechanical milling method, by which the CeMg11-Ni ＋ x wt% Ni （x = 100, 200） alloy powders with nanocrystalline and amorphous structure were obtained. The influence of the milling time and Ni content on the hydrogen storage properties of the alloys was discussed. The X-ray diffractometer and high-resolution transmission electron microscope were used to investigate the microstructures of the ball-milled alloys. The hydrogenation/dehydrogenation dynamics were studied using a Sievert instrument and a differential scanning calorimeter which was linked with a H2 detector. The hydrogen desorption activation energies of the alloy hydrides were evaluated by Arrhenius and Kissinger equations. From the results point of views, there is a little decline in the thermo- dynamic parameters （enthalpy and entropy changes） with the increase in Ni content. However, the alloys desorption and absorption dynamics are improved distinctly. What is more, the variation of milling time results in a dramatic influence on the hydrogen storage performances of alloys. Various maximum values of the hydrogen capacities correspond to different milling time, which are 5.805 and 6.016 wt% for the CeMgllNi ＋ x wt% Ni （x = 100, 200） alloys, respectively. The kinetics tests suggest that the hydrogen absorption rates increase firstly and then decrease with prolonging the milling time. The improvement of the gaseous hydrogen storage kinetics results from the decrease in the activation energy caused by the increase in Ni content and milling time.

Thermodynamic and Kinetic Studies of Effective Adsorption of 2,4,6-trichlorophenol onto Calcine Mg/Al-CO_3 Layered Double Hydroxide

Adsorption of 2, 4, 6-trichlorophenol（TCP） onto the calcined Mg/Al-CO_3 layered double hydroxide（CLDH） was investigated. The prepared Mg/Al-CO_3 layered double hydroxide（LDH） and CLDH were characterized by powder X-ray diffraction（XRD） and thermo gravimetric analyzer-differential scanning calorimeters（TG-DSC）. Moreover, 2,4,6-trichlorophenol（TCP） was removed effectively（94.7% of removal percentage in 9h） under the optimized experimental conditions. The adsorption kinetics data fitted the pseudosecond-order model well. The Freundlich, Langmuir, and Tempkin adsorption models were applied to the experimental equilibrium adsorption data at different temperatures of solution. The adsorption data fitted the Freundlieh adsorption isotherm with good values of the correlation coefficient. A mechanism of the adsorption process is proposed according to the intraparticle diffusion model, which indicates that the overall rate of adsorption can be described as three steps.

Removal of diclofenac from aqueous solution with multi-walled carbon nanotubes modified by nitric acid

Modified multi-walled carbon nanotubes(MWCNTs) were used as adsorbents for removal of diclofenac. The reaction conditions were examined. Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherm models were applied to determine appropriate equilibrium expression. The results show that the experimental data fit the Freundlich equation well. Thermodynamic parameters show that the adsorption process is spontaneous and exothermic. The kinetic study indicates that the adsorption of diclofenac can be well described with the pseudo-second-order kinetic model and the process is controlled by multiple steps.

Preparation of Waste Coffee-grounds Carbon and Study on Phenol Adsorption Ability

The waste coffee-grounds carbon(WCGC)was prepared with H_(3)PO_(4)treated using waste coffee-grounds as precursor.Its adsorption ability was studied using phenol as test molecule.The influence of H_(3)PO_(4)treated,calcined temperature,the initial phenol concentration,the doge of carbon and original pH values on phenol adsorption ability were investigated.Characterization of WCGC was performed by N_(2)adsorption isotherms,Fourier transform infrared spectroscopy(FT-IR),scanning electron microscopy(SEM),and X-ray diffraction(XRD)techniques.First,the second order and Weber-Morris model reaction rate models were used to estimate the WCGC adsorption ability.The results show that the produced WCGC(700℃,2 h)has been graphitized and the layered structure increased BET surface to 435.98 m^(2)/g and adsorption phenol ability.The initial phenol concentration is 50 mg/L,the amount of WCGC(700℃,2 h)is 0.2 g,and the phenol adsorption rate is 97%after 270 min and no intermediate product formation.The adsorption kinetics of the selected WCGC is best fitted by the Weber-Morris model.

Synthesis, adsorption and selectivity of inverse emulsion Cd(Ⅱ) imprinted polymers

Inverse emulsion polymerization was employed to synthesize inverse emulsion Cd（Ⅱ） imprinted polymers （IEⅡ P）. The morphology and functional groups of IEⅡP were characterized by SEM,FTIR and TG. Static adsorption experiments and competitive adsorption test were used to evaluate the adsorption ability of IEⅡP. The adsorption capacity of polymers could reach 86.7 mg·g^-1 under the optimal adsorption conditions. The pseudo second order kinetic model and Langmuir isotherm model could be used to analyze the experimental data well. The adsorption process of IEⅡP was chemical adsorption process and monomolecular type. Thermodynamic parameters showed that the adsorption process was endothermic and could occur spontaneously. The selectivity coefficients k of Cd^2＋/v, Cd^2＋/Zn^2＋ and Cd^2＋/Cu^2＋ were 2.4998, 1.2437 and 4.6882, respectively. The proposed method provides a new thought for removing Cd（Ⅱ） in water samples.

Adsorptive potential of Acacia nilotica based adsorbent for chromium(Ⅵ) from an aqueous phase

The objective of this research was to enhance adsorption capacity of Acacia nilotica （keekar） sawdust for the abatement of chromium bearing wastewater and to investigate the effect of process parameters on adsorption capacity. The sawdust was activated by acid wash and functionalized subsequently with formaldehyde. Functionalization of activated sawdust raised its chromium removal efficiency of almost 10% as compared to its adsorption removal efficiency of HCl treated sawdust in a batch adsorption study. Adsorption kinetic data provided better fitting with pseudo second order model. Maximum adsorption capacity calculated through the best fitting Langmuir model was 6.34 mg·g^-1 and 8.2 mg·g^-1 for HCl treated and formaldehyde functionalized sawdust adsorbents, respectively. The adsorption of Cr（VI） was endothermic when studied by varying temperature from 20℃ to 50℃ for both activated and functionalized adsorbents.

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.

A THEORETICAL STUDY OF THE THERMODYNAMIC AND KINETIC PROPERTIES FOR THE REACTION OF FORMYL CYANIDE DECOMPOSITION

We compute the thermodynamic and the kinetic properties for the reaction: HCOCN→HCH+CO using the statistical theory and the transition-state theory.The equi- librium constants and the rate coefficients of this reaction are also reported here,and the half lives of formyl cyanide at different temperatures are first estimated in this work.