Achieving superior hydrogen storage properties via in-situ formed nanostructures: A high-capacity Mg–Ni alloy with La microalloying

Mg-based hydride is a promising hydrogen storage material, but its capacity is hindered by the kinetic properties. In this study, Mg–Mg₂Ni–LaH_x nanocomposite is formed from the H-induced decomposition of Mg₉₈Ni_1·67La_0.33 alloy. The hydrogen capacity of 7.19 wt % is reached at 325 °C under 3 MPa H₂, attributed to the ultrahigh hydrogenation capacity in Stage I. The hydrogen capacity of 5.59 wt % is achieved at 175 °C under 1 MPa H₂. The apparent activation energies for hydrogen absorption and desorption are calculated as 57.99 and 107.26 kJ/mol, which are owing to the modified microstructure with LaH_x and Mg₂Ni nanophases embedding in eutectic, and tubular nanostructure adjacent to eutectic. The LaH_2.49 nanophase can catalyze H₂ molecules to dissociate and H atoms to permeate due to its stronger affinity with H atoms. The interfaces of these nanophases provide preferential nucleation sites and alleviate the “blocking effect” together with tubular nanostructure by providing H atoms diffusion paths after the impingement of MgH₂ colonies. Therefore, the superior hydrogenation properties are achieved because of the rapid absorption process of Stage I. The efficient synthesis of nano-catalysts and corresponding mechanisms for improving hydrogen storage properties have important reference to related researches.     

B4C–TiB2 composites fabricated by hot pressing TiC–B mixtures: The effect of B excess

Previous research have reported that B₄C–TiB₂ composites could be prepared by the reactive sintering of TiC–B powder mixtures. However, due to spontaneous oxidation of raw powders, using TiC–B powder mixtures with a B/TiC molar ratio of 6: 1 introduced an intermediate phase of C during the sintering process, which deteriorated the hardness of the composites. In this report, the effects of B excess on the phase composition, microstructure, and mechanical properties of B₄C–TiB₂ composites fabricated by reactive hot pressing TiC–B powder mixtures were investigated. XRD and Raman spectra confirmed that lattice expansion occurred in B-rich boron carbide and B_xC–TiB₂ (x > 4) composites were obtained. The increasing B content improved the hardness and fracture toughness but decreased the flexural strength of B_xC–TiB₂ (x > 4) composites. When the molar ratio of B/TiC increased from 6.6:1 to 7.8:1, the Vickers hardness and the fracture toughness of the composites were enhanced from 26.7 GPa and 4.53 MPa m^1/2 to 30.4 GPa and 5.78 MPa m^1/2, respectively. The improved hardness was attributed to the microstructural improvement, while the toughening mechanism was crack deflection, crack bridging and crack branching.     

Performance of BaZrO3/Y2O3 dual-phase refractory applied to TiAl alloy melting

Vacuum induction melting is a potential process for the preparation of TiAl alloys with good homogeneity and low cost. But the crucial problem is a selection of high stability refractory. In this study, a BaZrO₃/Y₂O₃ dual-phase refractory was prepared and its performance for melting TiAl alloys was studied and compared with that of a Y₂O₃ refractory. The results showed the dual-phase refractory consisted of BaZr_1-xY_xO_3-δ and Y₂O₃(ZrO₂), exhibited a thinner interaction layer (30 μm) than the Y₂O₃ refractory (90 μm) after melting the TiAl alloy. Although the TiAl alloys melted in the dual-phase and Y₂O₃ refractory exhibited similar oxygen contamination (<0.1 wt%), the alloy melted in the dual-phase refractory had smaller Y₂O₃ inclusion content and size than that in the Y₂O₃ refractory, indicating that the dual-phase refractory exhibited a better melting performance than the Y₂O₃ refractory. This study provides insights into the process of designing highly stable refractory for melting TiAl alloys.     

Nickel‒cobalt bimetallic catalysts prepared from hydrotalcite-like compounds for dry reforming of methane

Ni–Co/Mg(Al)O alloy catalysts with different Co/Ni molar ratios have been prepared from Ni- and Co-substituted Mg–Al hydrotalcite-like compounds (HTlcs) as precursors and tested for dry reforming of methane. The XRD characterization shows that Ni–Co–Mg–Al HTlcs are decomposed by calcination into Mg(Ni,Co,Al)O solid solution, and by reduction finely dispersed alloy particles are formed. H₂-TPR indicates a strong interaction between nickel/cobalt oxides and magnesia, and the presence of cobalt in Mg(Ni,Co,Al)O enhances the metal-support interaction. STEM-EDX analysis reveals that nickel and cobalt cations are homogeneously distributed in the HTlcs precursor and in the derived solid solution, and by reduction the resulting Ni–Co alloy particles are composition-uniform. The Ni–Co/Mg(Al)O alloy catalysts exhibit relatively high activity and stability at severe conditions, i.e., a medium temperature of 600 °C and a high space velocity of 120000 mL g^?1 h^?1. In comparison to monometallic Ni catalyst, Ni–Co alloying effectively inhibits methane decomposition and coke deposition, leading to a marked enhancement of catalytic stability. From CO₂-TPD and TPSR, it is suggested that alloying Ni with Co favors the CO₂ adsorption/activation and promotes the elimination of carbon species, thus improving the coke resistance. Furthermore, a high and stable activity with low coking is demonstrated at 750 °C. The hydrotalcite-derived Ni–Co/Mg(Al)O catalysts show better catalytic performance than many of the reported Ni–Co catalysts, which can be attributed to the formation of Ni–Co alloy with uniform composition, proper size, and strong metal-support interaction as well as the presence of basic Mg(Al)O as support.     

Synthesis and characterization of transition metal mixed oxide doped graphene embedded durable electrocatalyst for hydrogen evolution reaction

A promising electrocatalyst containing variable percentage of V₂O₅–TiO₂ mixed oxide in graphene oxide support was prepared by embedding the catalyst on Cu substrate through facile electroless Ni–Co–P plating for hydrogen evolution reaction. The solvothermal decomposition method was opted for tuning the crystalline characteristics of prepared material. The optimized mixed oxide was well characterized, active sites centres were identified and explained by X-ray diffraction, high resolution tunnelling electron microscopy, scanning electron microscopy coupled with energy dispersive X-ray and X-ray photon spectroscopy analysis. The structural and electronic characteristics of material was done by fourier transform infrared spectroscopy and the electrochemical behaviour of the prepared material was evaluated by using Tafel plot, electrochemical impedance analysis, linear sweep voltammetry, open circuit analysis and chronoamperometry measurements. The results show the enhanced catalytic activity of Ni–Co–P than pure Ni–P plate, due to synergic effect. Moreover, the prepared mixed oxide incorporated Ni–Co–P plate has a high activity towards HER with low over potential of 101 mV, low Tafel slope of 36 mVdec^?1, high exchange current density of 9.90 × 10^?2 Acm^?2.     

Development of a H2-permeable Pd60Cu40-based composite membrane using a reverse build-up method

A new reverse build-up method is developed to fabricate an economical H₂-permeable composite membrane. Sputtering and electroplating are used for the formation of a membrane comprised of a 3.7-μm-thick Pd₆₀Cu₄₀ (wt.%) alloy layer and a 13-μm-thick porous Ni support layer, respectively. The H₂-permeation measurements are performed under the flow of a gaseous mixture of H₂ and He at 300–320 °C and 50–100 kPa of H₂ partial pressure. The H₂/He selectivity values exceed 300. The activation energy at 300–320 °C is 10.9 kJ mol⁻¹. The H₂ permeability of the membrane is 1.25 × 10⁻⁸ mol m⁻¹ s⁻¹ Pa^−0.5 at 320 °C after 448 h. The estimated Pd cost of the proposed membrane is approximately 1/8 of the cost for a pure Pd₆₀Cu₄₀ membrane. This study demonstrates that the proposed method allows the facile production of low-cost, Pd-based membranes for H₂ separation.     

Development and characterisation of a Y2Ti2O7-based glass-ceramic as a potential oxidation protective coating for titanium suboxide (TiOx)

A silica-based glass-ceramic, with Y₂Ti₂O₇ as the major crystalline phase, is designed, characterised and tested as an oxidation-protective coating for a titanium suboxide (TiO_x) thermoelectric material at temperatures of up to 600 °C. The optimised sinter-crystallisation treatment temperatures are found to be 1300 °C and 855 °C for a duration of 30 min, and this treatment leads to a glass-ceramic with cubic Y₂Ti₂O₇ and CaAl₂Si₂O₈ as crystalline phases. An increase of ~270 °C in the dilatometric softening temperature is observed after devitrification of the parent glass, thus further extending its working temperature range.Excellent adhesion of the glass-ceramic coating to the thermoelectric material is maintained after exposure to a temperature of 600 °C for 120 h under oxidising conditions, thus confirming the effectiveness of the T1 glass-ceramic in protecting the TiO_x material.     

Bifunctional nanoporous ruthenium-nickel alloy nanowire electrocatalysts towards oxygen/hydrogen evolution reaction

A class of ruthenium-nickel alloy catalysts featured with nanoporous nanowires (NPNWs) were synthesized by a strategy combining rapid solidification with two-step dealloying. RuNi NPNWs exhibit excellent electrocatalytic activity and stability for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in which the RuNi-2500 NPNWs catalyst shows an OER overpotential of 327 mV to deliver a current density of 10 mA cm^?2 and the RuNi-0 NPNWs catalyst requires the overpotential of 69 mV at 10 mA cm^?2 showing the best HER activity in alkaline media. Moreover, the RuNi-1500 NPNWs catalyst was used as the bifunctional electrocatalyst in a two-electrode alkaline electrolyzer for water splitting, which exhibits a low cell voltage of 1.553 V and a long-term stability of 24 h at 10 mA cm^?2, demonstrating that the RuNi NPNWs catalysts can be considered as promising bifunctional alkaline electrocatalysts.     

Crystalline phase of TiO2 nanotube arrays on Ti–35Nb–4Zr alloy: Surface roughness,electrochemical behavior and cellular response

An investigation was made into the electrochemical, structural and biological properties of self-organized amorphous and anatase/rutile titanium dioxide (TiO₂) nanotubes deposited on Ti–35Nb–4Zr alloy through anodization-induced surface modification. The surface of as-anodized and heat-treated TiO₂ nanotubes was analyzed by field emission scanning electron microscopy (FE-SEM), revealing morphological parameters such as tube diameter, wall thickness and cross-sectional length. Glancing angle X-ray diffraction (GAXRD) was employed to identify the structural phases of titanium dioxide, while atomic force microscopy (AFM) was used to measure surface roughness associated with cell interaction properties. The electrochemical stability of TiO₂ was examined by electrochemical impedance spectroscopy (EIS) and the results obtained were correlated with the microstructural characterization. The in vitro bioactivity of as-anodized and crystallized TiO₂ nanotubes was also analyzed as a function of the presence of different TiO₂ polymorphic phases. The results indicated that anatase TiO₂ showed higher surface corrosion resistance and greater cell viability than amorphous TiO₂, confirming that TiO₂ nanotube crystallization plays an important role in the material's electrochemical behavior and biocompatibility.     

Interfacial microstructure and mechanical properties of Ti3SiC2 ceramic and TC11 alloy joint diffusion bonded with a Cu interlayer

Reliable joints of Ti₃SiC₂ ceramic and TC11 alloy were diffusion bonded with a 50 μm thick Cu interlayer. The typical interfacial structure of the diffusion boned joint, which was dependent on the interdiffusion and chemical reactions between Al, Si and Ti atoms from the base materials and Cu interlayer, was TC11/α-Ti + β-Ti + Ti₂Cu + TiCu/Ti₅Si₄ + TiSiCu/Cu(s, s)/Ti₃SiC₂. The influence of bonding temperature and time on the interfacial structure and mechanical properties of Ti₃SiC₂/Cu/TC11 joint was analyzed. With the increase of bonding temperature and time, the joint shear strength was gradually increased due to enhanced atomic diffusion. However, the thickness of Ti₅Si₄ and TiSiCu layers with high microhardness increased for a long holding time, resulting in the reduction of bonding strength. The maximum shear strength of 251 ± 6 MPa was obtained for the joint diffusion bonded at 850 °C for 60 min, and fracture primarily occurred at the diffusion layer adjacent to the Ti₃SiC₂ substrate. This work provided an economical and convenient solution for broadening the engineering application of Ti₃SiC₂ ceramic.