Microstructure and hydrogen absorption/desorption properties of Mg24Y3M (M = Ni,Co, Cu,Al) alloys

Ternary alloys with the nominal composition of Mg₂₄Y₃M (M = Ni, Co, Cu, Al) have been fabricated by using vacuum induction melting method. Their microstructure and phase composition are characterized by using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The isothermal hydrogen absorption and desorption kinetics are measured by a Sievert's-type apparatus. The dehydrogenation behaviors of the full hydrogenated alloys are also analyzed by differential scanning calorimetry (DSC) method. Results show that each and every alloy has a distinct multiphase structure containing the main phase Mg₂₄Y₅ and some amount of Mg. Intermetallic compounds of YCo₂ and Al₂Y are detected in the M = Co and M = Al alloy, while long-period stacking ordered (LPSO) phase can be also observed in M = Ni and M = Cu alloy. The hydrogen absorption and desorption kinetics shows a decreased trend in the following order: (M = Ni) > (M = Al) > (M = Co) > (M = Cu). The M = Ni alloy has the best hydrogen storage performance among the investigated alloys. The dehydrogenation activation energy (E_a) of the M = Ni alloy decreases to 66 kJ/mol, and its decomposition peak temperature is also reduced to 313 °C. Moreover, the p–c–T (pressure-composition isotherms) curves of the studied alloys are also discussed.     

Structural characterization and hydrogen storage properties of the Ti31V26Nb26Zr12M5 (M = Fe,Co, or Ni) multi-phase multicomponent alloys

Structure and hydrogen storage properties of three Ti₃₁V₂₆Nb₂₆Zr₁₂M₅ multicomponent alloys with M = Fe, Co and Ni are investigated. The alloys synthesized by arc melting are characterized via X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The as-cast ingots present multi-phase dendritic structures composed mainly of BCC phases and small amounts of C14 Laves phases. Upon hydrogenation, each alloy absorbs around 1.9 H/M (number of hydrogen atoms per metal atoms) at room temperature. XRD of fully hydrogenated samples shows the formation of multi-phase structures composed of FCC and C14 hydrides. Thermo Desorption Spectroscopy (TDS) shows that the hydrogenated alloys present multi-step desorption processes with wide temperature ranges and low onset temperatures. XRD of partially hydrogenated samples indicate the presence of intermediate BCC hydrides. XRD of desorbed samples suggest reversible reactions of absorption/desorption: BCC + C14 alloy ? intermediate BCC hydride + C14 hydride ? FCC + C14 hydrides.     

Improved hydrogen storage behaviours of nanocrystalline and amorphous Mg2Ni-type alloy by Mn substitution for Ni

The nanocrystalline and amorphous Mg₂Ni-type alloys with nominal compositions of Mg₂Ni_1−xMn_x (x = 0, 0.1, 0.2, 0.3, 0.4) were synthesized by melt spinning technique. The structures of the as-cast and spun alloys were characterized by XRD, SEM and HRTEM. The hydrogen absorption and desorption kinetics of the alloys were measured by an automatically controlled Sieverts apparatus. The electrochemical hydrogen storage performances were tested by an automatic galvanostatic system. The results show that the as-spun (x = 0) alloy holds a typical nanocrystalline structure, whereas the as-spun (x = 0.4) alloy displays a nanocrystalline and amorphous structure, confirming that the substitution of Mn for Ni facilitates the glass formation in the Mg₂Ni-type alloy. The hydrogen absorption capacity of the alloys first increases then decreases with rising Mn content, but the hydrogen desorption capacity of the alloys grows with increasing Mn content. Furthermore, the substitution of Mn for Ni significantly improves the electrochemical hydrogen storage performances of the alloys, involving both the discharge capacity and the electrochemical cycle stability. With an increase in the amount of Mn from 0 to 0.4, the discharge capacity of as-spun (30 m/s) alloy grows from 116.7 to 311.5 mAh/g, and its capacity retaining rate at 20th charging and discharging cycle rises from 36.7 to 78.7%.     

Hydrogen storage properties of Ti2−xCrVMx (M = Fe,Co, Ni) alloys

In this work, quaternary alloys having compositions Ti_1.9CrVM_0.1 and Ti_1.8CrVM_0.2 (M = Fe, Co and Ni) have been studied in detail for their structural aspects and hydrogen absorption–desorption properties. All the alloys form bcc phase solid solutions and after hydrogen absorption the structures change to fcc. The pressure composition isotherms, hydrogen storage capacities and hydrogen absorption kinetics were studied using Sievert's type of volumetric setup. The Ti_1.9CrVFe_0.1, Ti_1.9CrVCo_0.1 and Ti_1.9CrVNi_0.1 alloys are found to absorb maximum 3.80, 3.68 and 3.91 wt.% of hydrogen respectively; whereas, Ti_1.8CrVCo_0.2 and Ti_1.8CrVNi_0.2 alloys show 3.52 and 3.67 wt.% of hydrogen at room temperature. All the alloys show fast hydrogen absorption kinetics at the room temperature. From differential scanning calorimetric measurements, it has been found that Fe, Ni and Co substitution in place of Ti decreased the hydrogen desorption temperature drastically compared to the parent alloy.     

Structure and hydrogen storage properties of La1-xPrxMgNi3.6Co0.4 (x = 0–0.4) alloys prepared by melt spinning

Melt spinning technology was applied to prepared La_1-xPr_xMgNi_3.6Co_0.4 (x = 0–0.4) alloys, and phase composition, micro-structure, morphology and hydrogen storage properties were systematically investigated. The results show that the alloys contain two phases, LaMgNi₄ and LaNi₅ which have been detected by XRD and SEM. The grain of the alloys is refined by increasing Pr content and the phase abundance changed obviously. The hydrogen absorption capacity (wt%) of the alloys is 1.663, 1.659, 1.60, 1.593 and 1.566, corresponding the Pr substation of x from 0 to 0.4. The hydrogenation cycle stability indicates that the hydrogen capacity declined severely with the hydrogenation cycles. It is attributed to the hydrogen-induced amorphization which is confirmed by the XRD results after hydrogenation cycles. In order to recover the hydrogen storage capacity after cycles, the annealing treatment at 673 K for 3 h was carried out. And the XRD and HRTEM results show that the amorphization structure after hydrogen absorption/desorption cycles is re-crystallized by annealing treatment.     

Hydrogen storage by Mg-based nanocomposites

Hydrogen storage materials research is entered to a new and exciting period with the advance of the nanocrystalline alloys, which show substantially enhanced absorption/desorption kinetics, even at room temperatures. In this work, hydrogen storage capacities and the electrochemical discharge capacities of the Mg₂(Ni, Cu)-, LaNi₅-, ZrV₂-type nanocrystalline alloys and Mg₂Ni/LaNi₅-, Mg₂Ni/ZrV₂-type nanocomposites have been measured. The electronic properties of the Mg₂Ni_1-xCu_x, LaNi₅ and ZrV₂ alloys were calculated. The nanocomposite structure reduced hydriding temperature and enhanced hydrogen storage capacity of Mg-based materials. The nanocomposites (Mg,Mn)₂Ni (50 wt%)-La(Ni,Mn,Al,Co)₅ (50 wt%) and (Mg,Mn)₂Ni (75 wt%)-(Zr,Ti)(V,Cr,Ni)_2.4 (25 wt%) materials releases 1.65 wt% and 1.38 wt% hydrogen at 25 °C, respectively. The strong modifications of the electronic structure of the nanocrystalline alloys could significantly influence hydrogenation properties of Mg-based nanocomposities.     

Ab initio calculations on energetics and electronic structures of cubic Mg3MNi2 (M = Al, Ti, Mn) hydrogen storage alloys

Mg₃MNi₂ (M = Al, Ti, Mn) ternary intermetallic compounds with cubic structure are a new type of potential hydrogen storage alloys. Using ab initio density functional theory (DFT) calculations, the energetics and electronic structures of Mg₃MNi₂ (M = Al, Ti, Mn) compounds are systematically investigated. The optimized structural parameters including lattice constants and internal atomic positions are close to experimental data determined from X-ray powder diffraction. The calculated results of formation enthalpy ΔH_form show that the stabilities of cubic Mg₃MNi₂ (M = Al, Ti, Mn) compound, compared with hexagonal Mg₂Ni, increase in the order of Mg₃MnNi₂, Mg₂Ni, Mg₃TiNi₂ and Mg₃AlNi₂, whereas the stabilities of their saturated Mg₃MNi₂H₃ (M = Al, Ti, Mn) hydrides, compared with monoclinic Mg₂NiH₄, decrease in the order of Mg₂NiH₄, Mg₃AlNi₂H₃, Mg₃TiNi₂H₃ and Mg₃MnNi₂H₃. Further calculations of hydrogen desorption enthalpy ΔH_des indicate that these cubic Mg₃MNi₂ (M = Al, Ti, Mn) compounds possess promising dehydrogenation properties for their relatively lower ΔH_des values. Among of them, the dehydrogenation ability of Mg₃TiNi₂ is the most pronounced. Analysis of electronic structures suggests that the strong covalent bonding interactions between Ni and M within cubic Mg₃MNi₂ (M = Al, Ti, Mn) are dominant and directly control the structural stabilities of these compounds.     

First-principles studies of the structures and properties of Al- and Ag-substituted Mg2Ni alloys and their hydrides

The structures and properties of hydrogen storage alloy Mg₂Ni, of aluminum and silver substituted alloys Mg_2−xM_xNi (M = Al and Ag, x = 0.16667), and of their hydrides Mg₂NiH₄, Mg_2−xM_xNiH₄ (M = Al and Ag, x = 0.125) have been calculated from first-principles. Results show that the primitive cell sizes of the intermetallic alloys and hydrides were reduced by substitution of Mg with Al or Ag. Also, the interaction of Ni–Ni was weakened by the substitution. A strong covalent interaction between H and Ni atoms forms tetrahedral NiH₄ units in Mg₂NiH₄. The NiH₄ unit near the Al/Ag atom became tripod-like NiH₃ in Mg_2−xM_xNiH₄ (M = Al, Ag), indicating that the hydrogen storage capacity was decreased by the substitution. The calculated enthalpies of hydrogenation for Mg₂Ni, Mg_2−xAl_xNi and Mg_2−xAg_xNi are −65.14, −51.56 and −53.63 kJ/mol H₂, respectively, implying that the substitution destabilizes the hydrides. Therefore, the substitution is an effective technique for improving the thermodynamic behavior of hydrogenation/dehydrogenation in magnesium-based hydrogen storage materials.     

Preparation of nanocrystalline metal (Cr,Al, Mn,Ce, Ni,Co and Cu) modified ferrite catalysts for the high temperature water gas shift reaction

Water gas shift reaction is an essential process of hydrogen production and carbon monoxide removal from syngas. Fe–Cr–Cu catalysts are typical industrial catalysts for high temperature water gas shift reaction but have environmental and safety concerns related to chromium content. In this work nanocrystalline metal (M)-modified ferrite catalysts (M = Cr, Al, Mn, Ce, Ni, Co and Cu) for replacement of chromium were prepared by coprecipitation method and the effects of promoters on the structural and catalytic properties of the iron based catalysts were studied. Prepared catalysts were characterized using X-ray diffraction (XRD), N₂ adsorption (BET), temperature-programmed reduction (TPR) and transmission electron microscopies (TEM) techniques. Temperature-programmed reduction measurements inferred that copper favors the active phase formation and significantly decreased the reduction temperature of hematite to magnetite. In addition, water gas shift activity results revealed that Fe–Al–Cu catalyst with Fe/Al = 10 and Fe/Cu = 5 weight ratios showed the highest catalytic activity among the prepared catalysts. Moreover, the effect of calcination temperature, GHSV and steam/gas ratio on the catalytic performance of this catalyst was investigated.     

N-doped M/CoO (M=Ni,Co, and Mn) hybrid grown on nickel foam as efficient electrocatalyst for the chemical-assisted water electrolysis

In this work, N-Ni₁Co₃Mn_0.4O/NF is synthesized as multifunctional electrocatalyst for hydrogen evolution (HER), urea oxidation reaction (UOR) and hydrazine oxidation reaction (HzOR). The optimal Ni/Co (molar ratio) and the amount of doping Mn are investigated, the sample with Ni/Co = 1:3 and the addition of 0.4 mmol Mn exhibits the best catalytic activity with the largest specific surface area. Then the two-electrode electrolyzers composed of N-Ni₁Co₃Mn_0.4O/NF are constructed, and the results from experiments show that the voltage required for overall hydrazine splitting (OHzS) at 100 mA cm^?2 is 0.272 V, 1.614 V lower than that of overall water splitting (OWS, 1.886 V), while the overall urea splitting (OUS) needs 1.669 V, 0.187 V lower than that of OWS, revealing the outstanding thermodynamic and kinetic advantages of OUS and OHzS. The superior performance may be attributed to the heterostructure between metal and metal oxide and N-doping, which can promote electron transfer and optimizes the decomposition of urea and hydrazine hydrate and hydrogen production, and the research on mechanism will be carried out in the future.     

Experimental study of the influences substitution from Ni by Co,Al and Mn on the hydrogen storage properties of LaNi3.6Mn0.3Al0.4Co0.7 alloy

The hydrogen storage properties of LaNi_3.6Mn_0.3Al_0.4Co_0.7 alloy were improved by the addition of Co, Mn and Al. The phase compositions and crystal structures of this alloy were characterized via X-ray diffraction and Scanning Electron Microscopy. The gravimetric study showed that the average size of the particles was about 10 μm. The isotherms of reactions and the hydrogen absorption capacity were measured in the temperature range of 20–40 °C. Hence, the enthalpy (ΔH) and entropy (ΔS) were also calculated. The obtained experimental results showed that this compound can absorb and desorb hydrogen in a reversible way in normal operating conditions (temperature T = 20 °C and pressure P = 6 bar). The hydrogen sorption measurements revealed the effect of the partial substitution of Ni by Al, Mn and Co on the crystal structure of our compound. This substitution led to a significant reduction of hysteresis between hydriding and dehydriding. Thus, the substitution of Ni by these elements led to a larger size of interstitial voids and, therefore, the possibility of a higher number of hydrogen atoms in the cell.     

Effect of Mn on the long-term cycling performance of AB5-type hydrogen storage alloy

Rare-earth AB₅-type hydrogen storage alloys are widely studied due to their extensive application potentials in hydrogen compressors, heat pump, Ni–MH batteries etc. However, their shortcomings such as plateau splitting and capacity degradation during hydrogen absorption/desorption hinder their practical applications. In this paper, we study the effect of Mn partial substitution for Ni on the plateau characteristics and long-term cycling performance of LaNi_5-xMn_x alloys. It is found that Mn addition expands the lattice interstitial for hydrogen accommodation, thus prohibiting the plateau splitting phenomenon. In addition, the substitution of Mn for Ni stabilizes the crystal structure of the alloys against hydrogen absorption/desorption, thus relieving the capacity degradation. The capacity retention of the alloys at the 1000th cycle (S₁₀₀₀) increases from 83.2% (x = 0) to 94.0% (x = 0.75). But when x reaches 1, the hydrogen desorption reversibility is reduced due to the low plateau pressure, resulting in a slight decrease in capacity retention.     

Electrocatalytic property of water oxidation reaction depends on charging state of intermediates on Ag-M (M = Fe,co, Ni,Cu) in alkaline media

DFT calculations are performed to investigate the water oxidation reaction intermediates on Ag₂M (M = Fe, Co, Ni, Cu), and Pt₃ clusters in alkaline media both in the gas and solution (water) phases in the neutral and charged states. The calculated results revealed that the neutral and anionic clusters were found to be more suitable catalysts than cationic clusters because of weakly bonded water oxidation reaction intermediates. In addition, the calculated structural parameters of the water oxidation intermediates with Ag₂M (M = Fe, Co, Ni, Cu) clusters revealed that M-OH bond strengths are found to be in the order of Cu < Ni < Co < Fe. Conclusively, Ag₂Cu cluster was determined to be the best electrocatalyst regarding oxygen evolution reaction via 4e transfer, which is consistent with results on larger Ag₂M clusters (13 atoms) and periodic Ag-M nanoalloys due to weaker binding energies of the water oxidation intermediates.     

Hydrogenation and dehydrogenation behaviours of nanocrystalline Mg20Ni10−xCux (x = 0−4) alloys prepared by melt spinning

In order to improve the hydriding and dehydriding kinetics of the Mg₂Ni-type alloys, Ni in the alloy was partially substituted by element Cu, and the nanocrystalline Mg₂Ni-type Mg₂₀Ni_10−xCu_x (x = 0, 1, 2, 3, 4) alloys were synthesized by melt-spinning technique. The structures of the as-cast and spun alloys were studied by XRD, SEM and HRTEM. The hydrogen absorption and desorption kinetics of the alloys were measured using an automatically controlled Sieverts apparatus. The results show that the substitution of Cu for Ni does not change the major phase Mg₂Ni. The hydrogen absorption capacity of the alloys first increases and then decreases with rising Cu content, but the hydrogen desorption capacity of the alloys grows with increasing Cu content. The melt spinning significantly improves the hydrogenation and dehydrogenation capacity and kinetics of the alloys.     

Hollow bimetallic M-Fe-P (M=Mn,Co, Cu) nanoparticles as efficient electrocatalysts for hydrogen evolution reaction

Searching for low-cost electrocatalysts with high activity towards the hydrogen evolution reaction (HER) is of great significance to enable large-scale hydrogen production via water electrolysis. In this study, by using inverse spinel MFe₂O₄(M = Mn, Fe, Co, Cu) nanoparticles (NPs) as the precursors, monodisperse bimetallic phosphide M-Fe-P NPs/C with hollow structures were readily obtained by a gas-solid annealing method. These hollow phosphide NPs displayed excellent HER activity in an acidic medium with a low loading amount of 0.2 mg cm⁻². In particular, the Co–Fe–P NPs/C shows highest HER activity that only requiring an overpotential of 97 mV to retain a current density of 10 mA cm⁻². A volcano relation between activity and incorporated elements was revealed. Incorporation of cation with high electronegativity stabilized the FeP active centres, while phase segregation resulted in the loss of activity for Cu–Fe–P NPs/C.     

Biogas dry reforming for hydrogen production over Ni-M-Al catalysts (M = Mg,Li, Ca,La, Cu,Co, Zn)

Biogas can be highlighted as a renewable raw material for the production of hydrogen. In this study, Ni-M-Al catalysts were evaluated to obtain hydrogen from the biogas reforming. The catalysts were synthesized by coprecipitation with Ni and Al with a molar percentage of 55 and 33%, respectively, varying the third component M = Mg, Li, Ca, La, Cu, Co, Zn, with a molar percentage of 11%. The reactions were carried out in a fixed bed tubular reactor using a synthetic biogas (70% of CH₄ and 30% of CO₂). The results showed that the CH₄ conversion increased with the temperature up to 700 °C for La11, Cu11, and Zn11 catalysts. CO₂ conversion increased for all catalysts in the range of 500–700 °C. The H₂/CO molar ratios observed in the reactions were higher than 1 due to the contribution of the CH₄ decomposition reaction. The catalyst containing La presented better stability in the reactions due to the stronger acid sites and high resistance to sintering. Carbon filaments were produced by all catalysts at 600 and 700 °C. Sintering was the main cause of deactivation of the catalysts, except for La11.     

Effect of Fe substitution on first hydrogenation kinetics of TiFe-based hydrogen storage alloys after air exposure

This study investigated how Fe substitution with Ni, Co, Cu, Mn, and Cr affected the first hydrogenation behavior of air-exposed TiFe-based hydrogen storage alloys. The alloy ingots were crushed into powders and exposed to air for 1 h to analyze the first hydrogenation kinetics. Although Fe was substituted with up to 30% of Ni, Co, and Cu, the alloys had a single TiFe phase. In addition, the TiFe_0·7Ni_0·2Co_0.1 and TiFe_0·7Co_0·2Ni_0.1 alloys also had a single TiFe phase in spite of the simultaneous substitution. The composition of the oxide layer changed by the addition of Ni, Co, and Cu, but the alloys did not absorb hydrogen. In the TiFe_0·8Mn_0.2 and TiFe_0·8Cr_0.2 alloys, a dual-phase microstructure consisting of TiFe and Mn/Cr-rich C14 Laves phase was formed, with a larger amount in TiFe_0·8Cr_0.2. Both samples absorbed hydrogen after air exposure without any thermal activation process. Comparing the first hydrogenation kinetics, TiFe_0·8Cr_0.2 had a shorter incubation time and faster hydrogen absorption rate than TiFe_0·8Mn_0.2.     

High selective and efficient Fe2–N6 sites for CO2 electroreduction: A theoretical investigation

Developing high efficient and cheap electrocatalysts for carbon dioxide reduction reaction (CO₂RR) is the key to achieve CO₂ transformation into clean energy. Herein, a series of transition metal dimer and nitrogen codoped graphene (M₂N₆-Gra, M = Cr–Cu) acting as electrocatalysts for CO₂RR are investigated based on the density functional method. For M₂N₆-Gra (M = Cr, Mn), the selectivity is poor and CO poisoning is serious. Fe₂N₆-Gra is the best CO₂RR catalyst due to the good selectivity and catalytic activity. The calculated overpotential is very small, i.e., 0.03 V for COOH channel, 0.05 V for HCOO channel. Hydrogen evolution reaction is also refrained on the Fe₂N₆-Gra surface, which further supports its high catalytic performance. For M₂N₆-Gra (M = Co, Ni, Cu), the catalytic activity is poor due to large overpotentials. These results indicate that if designed carefully, the transition metal dimer and nitrogen codoped graphene would be good candidate for the high efficient and selective CO₂RR catalyst.     

Electrocatalytic activity of crystalline Ni–Co–M (M = Cr,Mn, Cu) alloys on the oxygen evolution reaction in an alkaline environment

Ternary Ni₆₀Co₃₀M₁₀ (M = Cr, Mn, Cu) crystalline alloys have been characterized by means of microstructural and electrochemical techniques in view of their possible applications as electrocatalytic materials for oxygen evolution reaction (OER). The electrochemical efficiency of the electrodes has been studied on the basis of electrochemical data obtained from steady-state polarization and electrochemical impedance spectroscopy (EIS) techniques in 1 M NaOH solution at 298 K. The results were compared with those obtained on a Ni₆₀Co₄₀ commercial alloy. The overall experimental data indicate that alloying Ni–Co with Cr, Mn and Cu leads to an increase of electrocatalytic activity in oxygen evolution with respect to the Ni–Co alloy. High catalytic efficiencies were achieved on Ni₆₀Co₃₀Mn₁₀ and Ni₆₀Co₃₀Cr₁₀ electrodes, the latter being the best electrocatalyst for the OER.