Reaction pathways and roles of N-alkylmorpholine in amine·alane transamination: A mechanistic study

The cost- and energy-effective regeneration of alane has attracted much attention because of its potential energy applications. Using N-alkylmorpholine·AlH₃ as intermediates, we have recently shown alane regeneration with improved yield, selectivity, and energy-efficiency. However, detailed interactions between AlH₃ and N-alkylmorpholine were not well-understood. Herein, we present spectroscopic and theoretical studies of the reaction pathways and roles of N-alkylmorpholine in transamination. Under reduced pressures, the 2:1 alane adduct (R₃N)₂·AlH₃ is initially transformed into its 1:1, unsaturated complex R₃N·AlH₃, which then forms an equilibrium with N-alkylmorpholine (L) to generate a mixed intermediate R₃N·AlH₃·L. Under the influence of vacuum and excess N-alkylmorpholine, R₃N·AlH₃·L loses an amine molecule (with higher volatility) to give L·AlH₃ as the final product. Using N-alkylpiperidine and 1,4-dioxane as models to mimic the coordination behaviors of the morpholine N and O atoms, we further showed the roles of N-alkylmorpholine in transamination, during which it formed the N-donating complex R₃N·AlH₃·^NL and, depending on steric hindrances of R₃N, the O-donating complex R₃N·AlH₃·^OL. These results highlight the effects of amine coordination modes and steric hindrances in the reactivity of their alane adducts and will provide information for the optimization of alane regeneration.     

Electrocatalytic hydrogen gas generation by cobalt molybdenum disulfide (CoMoS2) synthesized using alkyl-containing thiomolybdate precursors

Cobalt molybdenum disulfide, (CoMoS₂) catalysts are evaluated as active electrocatalysts for the production of hydrogen gas in acidic aqueous media. These highly-active hydrogen evolution reaction (HER) catalysts are obtained from pretreatment of ammonium tetrathiomolybdate (ATM) with different amines precursors, and characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM) and their surface areas are determined by Brunauer–Emmett–Teller (BET) surface area analyses. Electrochemical studies indicate that these CoMoS₂ materials exhibit enhanced catalytic performance for hydrogen gas production with overpotentials ranging from 0.127 to 0.144 V, which are significant less than CoMoS₂ synthesized directly from ATM under the same synthetic techniques (0.173 V). These CoMoS₂ catalysts are also stable in the presence of strong acidic media after a considerably long period of time (10 h) for maintaining their efficiencies for hydrogen gas evolution.     

Synthesis and characterization of g/Ni–SiO2 composite for enhanced hydrogen storage applications

Hydrogen is considered as one of the most important clean energy carriers for the future. Many experimental and theoretical investigations have focused on the adsorption and activation of H₂ on the metal surfaces. Metal oxides and semiconductors are suitable materials for this purpose. Gelatin assisted Ni loaded SiO₂ (g/Ni–SiO₂) was prepared and its structural properties, morphology, composition and surface properties were analyzed by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), Field emission scanning electron microscopy (FE-SEM), Elemental mapping and energy dispersive spectrum (EDS), High resolution transmission electron microscopy (HR-TEM) and Brunauer-Emmett-Teller (BET) surface area measurements. The prepared material was effectively utilized for H₂ storage applications at room temperature. The H₂ storage capacity of g/Ni–SiO₂ was twice that of pristine SiO₂. This may be due to large change in pore volume and pore diameter of g/Ni–SiO₂, which may enhances the H₂ storage capacity of the sample. The H₂ storage capacity of other materials such as ZnO, anatase TiO₂, g/TiO₂, g/ZnO, g/TiO₂–SO₄^2-, Sb doped TiO₂, Ag₂S/TiO₂, Sb₂O₃, CdS and SiO₂/CdS also studied and compared with g-Ni/SiO₂.     

A 70 MPa hydrogen-compression system using metal hydrides

The objective of this work was to develop a 70 MPa hydride-based hydrogen compression system. Two-stage compression was adopted with AB₂ type alloys as the compression alloys. Ti_0.95Zr_0.05Cr_0.8Mn_0.8V_0.2Ni_0.2 and Ti_0.8Zr_0.2Cr_0.95Fe_0.95V_0.1 alloys were developed for the compression system. With these two alloys, a 70 MPa two-stage hydride-based hydrogen compression system was designed and built with hot oil as the heat source, and composite materials formed by mixing hydrogen storage alloys with Al fiber were used to prevent hydride bed compaction and to prevent strain accumulation. The experimental results showed that Ti_0.95Zr_0.05Cr_0.8Mn_0.8V_0.2Ni_0.2 and Ti_0.8Zr_0.2Cr_0.95Fe_0.95V_0.1 alloys could well meet the requirements of compression system. Composite materials formed by mixing hydrogen storage alloys with Al fiber were an effective way to prevent strain accumulation for hydride compression. With cold oil (298 K) and hot oil (423 K) as the cooling and heating sources, the built compression system could convert hydrogen pressure from around 4.0 MPa to over 70 MPa.     

Improved hydrogen storage properties of MgH2 with Ni-based compounds

The nanoscaled Ni-based compounds (Ni₃C, Ni₃N, NiO and Ni₂P) are synthesized by chemical methods. The MgH₂-X (X = Ni₃C, Ni₃N, NiO and Ni₂P) composites are prepared by mechanical ball-milling. The dehydrogenation properties of Mg-based composites are systematically studied using isothermal dehydrogenation apparatus, temperature-programmed desorption system and differential scanning calorimetry. It is experimentally confirmed that the dehydrogenation performance of the Mg-based materials ranks as following: MgH₂Ni₃C, MgH₂Ni₃N, MgH₂NiO and MgH₂Ni₂P. The onset dehydrogenation temperatures of MgH₂Ni₃C, MgH₂Ni₃N, MgH₂NiO and MgH₂Ni₂P are 160 °C, 180 °C, 205 °C and 248 °C, respectively. The four Mg-based composites respectively release 6.2, 4.9, 4.1 and 3.5 wt% H₂ within 20 min at 300 °C. The activation energies of MgH₂Ni₃C, MgH₂Ni₃N, MgH₂NiO and MgH₂Ni₂P are 97.8, 100.0, 119.7 and 132.5 kJ mol^?1, respectively. It' found that the MgH₂Ni₃C composites exhibit the best hydrogen storage properties. Moreover, the catalytic mechanism of the Ni-based compounds is also discussed. It is found that Ni binding with low electron-negativity element is favorable for the dehydrogenation of the Mg-based composites.     

Influence of annealing treatment on the hydrogen storage properties of La2−xTixMgNi9 (x = 0.2, 0.3) alloys

La_2−xTi_xMgNi₉ (x = 0.2, 0.3) alloys have been prepared by magnetic levitation melting under an Argon atmosphere, and the as-cast alloys were annealed at 800 °C, 900 °C for 10 h under vacuum. The effects of annealing on the hydrogen storage properties of the alloys were investigated systematically by XRD, PCT and electrochemical measurements. For the La_2−xTi_xMgNi₉ (x = 0.2, 0.3) alloys, LaNi₅, LaMg₂Ni₉ and LaNi₃ are the main phases and a Ti₂Ni phase appears at 900 °C. The effective hydrogen storage capacity increases from 1.10, 1.10 wt.% (as-cast) to 1.22, 1.16 wt.% (annealed 800 °C) and 1.31, 1.27 wt.% (annealed 900 °C), respectively. The annealing not only improves the hydrogen absorption/desorption kinetics but also increases the maximum discharge capacity and enhances the cycling stability. The La_1.8Ti_0.2MgNi₉ alloy annealed at 900 °C exhibits good electrochemical properties, and the discharge capacities decrease from 366.1 mA h/g to 219.6 mA h/g after 177 charge-discharge cycles.     

Effect of substituting Mn for Ni on the hydrogen storage and electrochemical properties of ReNi2.6−xMnxCo0.9 alloys

ReNi_2.6−xMn_xCo_0.9 (x = 0.0, 0.225, 0.45, 0.675, 0.90) alloys were prepared by induction melting. The effects of partially substituting Mn for Ni on the phase structure and electrochemical properties of the alloys were investigated systematically. In the alloys, (La, Ce)₂Ni₇ phase with a Ce₂Ni₇-type structure, (Pr, Ce)Co₃ phase with a PuNi₃-type structure, and (La, Pr)Ni₅ phase with a CaCu₅-type structure were the main phases. The (La,Pr)Ni phase appeared when x increased to 0.45, and the (La, Pr)Ni₅ phase disappeared with further increasing x (x > 0.45). The hydrogen-storage capacity of the ReNi_2.6−xMn_xCo_0.9 (x = 0.0, 0.225, 0.45, 0.675, 0.90) alloys initially increased and reached a maximum when Mn content was x = 0.45, and then decreased with further increasing Mn content. The ReNi_2.6−xMn_xCo_0.9 (x = 0.0, 0.225, 0.45, 0.675, 0.90) alloy exhibited a hydrogen-storage capacity of 0.81, 0.98, 1.04, 0.83 and 0.53 wt.%, respectively. Electrochemical studies showed that the maximum discharge capacity of the alloy electrodes initially increased from 205 mAh/g (x = 0.0) to 352 mAh/g (x = 0.45) and then decreased to 307 mAh/g (x = 90). The hydrogen absorption rate first increased and then decreased with addition of Mn element. The ReNi_2.15Mn_0.45Co_0.9 alloy showed faster hydrogen absorption kinetics than that of the other alloys. The presence of Mn element slowed hydrogen desorption kinetics.     

Hydrogen storage in destabilized borohydride materials

Several new destabilized borohydride systems were prepared by mechanochemical synthesis and characterized to determine their suitability for hydrogen storage. The mixtures included: Mg(BH₄)₂/Ca(BH₄)₂; Mg(BH₄)₂/CaH₂/3NaH; and Mg(BH₄)₂/CaH₂; systems as well as a double cation hydride MnLi(BH₄)₃. Temperature programmed desorption, TPD, analyses showed that the desorption temperature of Mg(BH₄)₂ can be lowered by ball milling it with Ca(BH₄)₂. The resulting mixture absorbed and released hydrogen with the pressure composition temperature, PCT, isotherm displaying a well-defined plateau region. The other two systems; Mg(BH₄)₂/CaH₂ and Mg(BH₄)₂/CaH₂/NaH, can also absorb and release hydrogen. The desorption enthalpies are all in the 84–88 kJ/mol range. These systems, however, are only partially reversible and lose some of their hydrogen-holding capacity after the initial desorption. A plausible explanation for this is that the mechanisms involve the formation of a (B₁₂H₁₂)⁻²-containing intermediate which has a high kinetic barrier to re-hydrogenation. TPD analysis also showed that the double cation material, MnLi(BH₄)₃ can release hydrogen in the range of 130 °C but the process is irreversible. A Kissinger analysis of the first decomposition step in the differential thermal analysis, DTA, data showed that the activation energies for all the Mg(BH₄)₂-based borohydrides range from 115 to 167 kJ/mol.     

Structural study of a new B-rich phase obtained by partial hydrogenation of 2NaH + MgB2

The structure of an unknown crystalline phase observed during the hydrogen absorption reaction of the powder mixtures 2NaH + MgB₂ at high pressure has been studied by ab-initio structure determination from powder diffraction. The sequence of un-overlapped peaks extracted from the X-ray powder diffraction pattern could be indexed with a primitive cubic cell with lattice parameter a = 7.319 Å. The diffraction patterns of the peaks are matched with the Pa-3 space group. The stoichiometry of the hydrogen absorption reaction suggests the presence of a high-boron content phase in the compound under investigation. Assuming this phase to be composed only by boron atoms and therefore having a density similar to that found for boron polymorphs, the solution with a space group of Pa-3 leads to reasonable B–B interatomic distances.     

Metal hydride hydrogen storage and compression systems for energy storage technologies

Along with a brief overview of literature data on energy storage technologies utilising hydrogen and metal hydrides, this article presents results of the related R&D activities carried out by the authors. The focus is put on proper selection of metal hydride materials on the basis of AB₅- and AB₂-type intermetallic compounds for hydrogen storage and compression applications, based on the analysis of PCT properties of the materials in systems with H₂ gas. The article also presents features of integrated energy storage systems utilising metal hydride hydrogen storage and compression, as well as their metal hydride based components developed at IPCP and HySA Systems.     

Study on the dehydrogenation properties and reversibility of Mg(BH4)2AlH3 composite under moderate conditions

Mg(BH₄)₂ has been considered as one of the promising light metal complex hydrides due to its high hydrogen capacity and low cost. But its higher thermal stability (dehydrogenation at above 300 °C) needs to be improved for the practical application. In this study, the aluminum hydride AlH₃ was introduced into complex borohydride Mg(BH₄)₂ to synthesize a new Mg(BH₄)₂AlH₃ composite by ball milling method. It is found that the active Al¹ formed from the self-decomposition of AlH₃ can effectively improve the dehydrogenation properties of Mg(BH₄)₂, the Mg(BH₄)₂AlH₃ composite starts to release hydrogen at 130.8 °C with a total hydrogen capacity of 11.9 wt.%. The dehydrogenated products of the composite is composed of Mg₂Al₃ and B at 350 °C, resulting in the improved hydrogen desorption properties of Mg(BH₄)₂AlH₃ composite. The Mg₂Al₃ and B products would be further transformed into MgAlB₄ and Al at 500 °C. Moreover, the Mg₂Al₃ and B dehydrogenated products show better reversible hydrogen storage property than that of the MgAlB₄ and Al products. This research shows a way to alter hydrogen de/hydrogenation route and reversibility of Mg(BH₄)₂ complex hydride by compositing with AlH₃ and controlling the dehydrogenation temperature.     

Effect of Bismuth on hydrogen storage properties of melt-spun LaNi4.7-x Al0.3Bix (x = 0.0, 0.1, 0.2, 0.3) ribbons

The LaNi₅ intermetallic compound is an AB5 type hydrogen storage alloy which exhibits low operating temperature, easy activation, low pressure and tolerance to impurities. In this study, LaNi_4.7-x Al_0.3Bi_x (x = 0.0, 0.1, 0.2, 0.3) alloys were produced by melt-spinning technique and the effects of Al and Bi additions on the microstructure, thermal and hydrogen storage properties of LaNi₅ were investigated. The results showed that substitution of Ni with Al led to a desired decrease in absorption/desorption plateau pressure and hysteresis without a decrease in hydrogen storage capacity. In contrast, Bi substitution with Ni increased the absorption/desorption plateau pressure, reduced the hydrogen capacity and increased pulverization resistance of the alloy due to the formation of BiLa and AlNi₃ intermetallic phases at the grain boundaries.     

Interfacial engineering of nickel/vanadium based two-dimensional layered double hydroxide for solid-state hydrogen storage in MgH2

As a high-density solid-state hydrogen storage material, magnesium hydride (MgH₂) is promising for hydrogen transportation and storage. Yet, its stable thermodynamics and sluggish kinetics are unfavorable for that required for commercial application. Herein, nickel/vanadium trioxide (Ni/V₂O₃) nanoparticles with heterostructures were successfully prepared via hydrogenating the NiV-based two-dimensional layered double hydroxide (NiV-LDH). MgH₂ + 7 wt% Ni/V₂O₃ presented more superior hydrogen absorption and desorption performances than pure MgH₂ and MgH₂ + 7 wt% NiV-LDH. The initial discharging temperature of MgH₂ was significantly reduced to 190 °C after adding 7 wt% Ni/V₂O₃, which was 22 and 128 °C lower than that of 7 wt% NiV-LDH modified MgH₂ and additive-free MgH₂, respectively. The completely dehydrogenated MgH₂ + 7 wt% Ni/V₂O₃ charged 5.25 wt% H₂ in 20 min at 125 °C, while the hydrogen absorption capacity of pure MgH₂ only amounted to 4.82 wt% H₂ at a higher temperature of 200 °C for a longer time of 60 min. Moreover, compared with MgH₂ + 7 wt% NiV-LDH, MgH₂ + 7 wt% Ni/V₂O₃ shows better cycling performance. The microstructure analysis indicated the heterostructural Ni/V₂O₃ nanoparticles were uniformly distributed. Mg₂Ni/Mg₂NiH₄ and metallic V were formed in-situ during cycling, which synergistically tuned the hydrogen storage process in MgH₂. Our work presents a facile interfacial engineering method to enhance the catalytic activity by constructing a heterostructure, which may provide the mentality of designing efficient catalysts for hydrogen storage.     

Hydrogen storage properties of nanocrystalline Mg2Ni prepared from compressed 2MgH2Ni powder

In the present work, nanocrystalline Mg₂Ni with an average size of 20–50 nm was prepared via ball milling of a 2MgH₂Ni powder followed by compression under a pressure of 280 MPa. The phase component, microstructure, and hydrogen sorption properties were characterized by using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), pressure-composition-temperature (PCT) and synchronous thermal analyses (DSC/TG). Compared to the non-compressed 2MgH₂Ni powder, the compressed 2MgH₂Ni pellet shows lower dehydrogenation temperature (290 °C) and a single-phase Mg₂Ni is obtained after hydrogen desorption. PCT measurements show that the nanocrystalline Mg₂Ni obtained from dehydrogenated 2MgH₂Ni pellet has a single step hydrogen absorption and desorption with fairly low absorption (?57.47 kJ/mol H₂) and desorption (61.26 kJ/mol H₂) enthalpies. It has very fast hydrogen absorption kinetics at 375 °C with about 3.44 wt% hydrogen absorbed in less than 5 min. The results gathered in this study show that ball milling followed by compression is an efficient method to produce Mg-based ternary hydrides.