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Li–Mg–B–H reactive hydride composite (RHC) has attracted extensive attention over the past decades for its extremely high hydrogen storage capacity (11.5 wt%). But the sluggish desorption kinetics for the second step dehydrogenation reaction need to be further improved. Herein, short rod-like TMTiO 3 (TM = Co, Ni) bimetallic oxides, which contain two kinds of transition metal elements, were synthesized and introduced into Li–Mg–B–H RHC for the first time. The NiTiO 3 exhibits excellent catalytic effect on the hydrogen desorption kinetic performance of Li–Mg–B–H RHC, and the incubation period for the second step dehydrogenation reaction is eliminated completely by reducing the apparent activation energy for the generation of MgB 2 from 296 kJ/mol to 269 kJ/mol. The NiTiO 3 doped Li–Mg–B–H RHC can desorb about 9.0 wt% H 2 without obvious attenuation of kinetic performance in five cycles. Mechanism analyses reveal that the in-situ generated nano-sized MgNi 3 B 2 and TiB 2 species (∼5 nm) both meet the critical value (< 10%) of the edge-to-edge matching model (5.77% for MgNi 3 B 2 and 2.22% for TiB 2), which play a significant role in supporting the nucleation of MgB 2. Meanwhile, the extremely fine MgNi 3 B 2 and TiB 2 heterogeneous nucleation sites can inhibit the excessive growth for a single crystal nucleus of MgB 2. The heterogeneous nucleation and grain refinement mechanisms caused by the novel bimetallic oxide could provide alternative insights into designing an in-situ generated nano-sized catalytic hydrogen storage system with enhanced kinetics and cyclic stability for hydrogen-fueled applications. Image 1 • Short rod-like NiTiO 3 eliminates the incubation period of dehydrogenation. • In-situ generated MgNi 3 B 2 and TiB 2 nano-species support the nucleation of MgB 2. • Fine MgNi 3 B 2 and TiB 2 nucleation sites cause the grain refinement of MgB 2. [ABSTRACT FROM AUTHOR]

Tritium target is of crucial importance in relation to the development of neutron generator apparatus. However, the prevalent Ti target is now suffering from the intricate procedures for activation, limited tritium content at room temperature (RT) and poor ability to fix the helium. Herein, a succession of new type ZrCo(Ti) alloy targets were designed and fabricated by magnetron sputtering. Firstly, the influence of technological parameters (types of substrate, sputtering temperatures, sputtering time and annealing temperatures) on the assemblage and also the hydrogen storage properties of the ZrCo films were systemically studied. The results show that high sputtering temperature is benefit to acquiring high crystallinity of ZrCo films, but the substrates seem to have no significant effect on that. The thickness and grain size of ZrCo film are both positively related to the sputtering time. However, the hydrogen uptake capacities (0.14 wt%~0.79 wt%) for all the prepared ZrCo films are relatively low. After that, the composition and microstructure of the ZrCo films were further regulated and optimized. On the one hand, Zr 1-x Ti x Co films were constructed by introduction of Ti element, achieving a higher hydrogen absorption capacity (~0.7 wt%), but with weak thermal stability in the subsequent hydrogen desorption process (~80% of hydrogen escaped at 500 °C). On the other hand, the surface of the ZrCo film was modified by a thin layer of Ti, forming a serious of double-layer ZrCo/Ti films. The ZrCo/Ti composite films not only achieve extremely high hydrogen storage capacity (1.85 wt%), but also maintain strong thermal stability (only 15.7% of hydrogen escaped at 500 °C). These findings related to the ZrCo(Ti) films in this paper provide crucial reference for the development of tritiated ZrCo film targets, and spark inspiration even for the design of other new-type tritiated film target. • The influence of sputtering parameters on ZrCo films are revealed. • The crystallinity of ZrCo film can be improved when deposited at 800 °C. • The thickness and grain size are positively related to the sputtering time. • Zr 1-x Ti x Co shows similar hydrogen capacity but faster dynamics to ZrCo film. • ZrCo/Ti film exhibits high hydrogen capacity and strong thermal stability. [ABSTRACT FROM AUTHOR]

The solvent-free amorphous Mg(BH 4) 2 composite was in-situ synthesized by ball milling LiBH 4 and MgCl 2. It is found that the onset dehydrogenation temperature of the as-synthesized composite is 126.9 °C, which is roughly 156 °C lower than that of pristine Mg(BH 4) 2. The activation energy of the amorphous Mg(BH 4) 2 and pristine Mg(BH 4) 2 for the first dehydrogenation step was calculated as 120.01 kJ/mol and 487.99 kJ/mol, respectively. Hence the kinetics improvement is certified by the lower E a value of the dehydrogenation process. When adding NbF 5 into the composite, the catalyzed composite exhibits better hydrogen storage properties compared to pristine and amorphous Mg(BH 4) 2. The catalyzed composite starts to release hydrogen at proximately 120 °C with a total capacity of 10.04 wt%. The reversibility of the catalyzed composite is also improved. The capacity of the catalyzed composite at the second cycle is 5.5 wt%. For the third and fourth cycles the catalyzed composite can still liberate 4 wt% H 2. Besides, the onset hydrogen desorption temperature during four cycles are extremely lower than those of pristine and amorphous Mg(BH 4) 2. The peaks of the intermediate MgB 12 H 12 is detected by FTIR as the regenerated hydrogenation product in the catalyzed composite. It can be speculated from the detailed analysis that there are mainly three reasons for the improved properties. Firstly, the additive NbF 5 is favorable to enhance the hydrogen storage properties by modifying the dehydrogenation path and producing MgF 2 and NbB 2 as new products. Secondly, the in-situ formation of amorphous Mg(BH 4) 2 is likely to improve the dehydrogenation properties of the samples due to its different reactivity comparing to crystal ones. Finally, LiCl can serve as buffer in the composite and thus improve the dehydrogenation properties. • Amorphous Mg(BH 4) 2 was in-situ synthesized by ball milling. • NbF 5 changes the dehydrogenation path of Mg(BH 4) 2 and produces MgF 2 and NbB 2. • MgB 12 H 12 is regenerated through hydrogenation process in the sample. • The chloride in the sample can serve as buffer during de/rehydrogenation. [ABSTRACT FROM AUTHOR]

Abstract Nowadays, catalytic doping has been regarded as one of the most promising and effective methods to improve the sluggish kinetics of magnesium hydride (MgH 2). Herein, we synthesized Ni/TiO 2 nanocomposite with the particle sizes about 20 nm by an extremely facile solvothermal method. Then, the Ni/TiO 2 nanocomposite was doped into MgH 2 to enhance its reversible hydrogen storage properties. A remarkably enhancement of de/rehydrogenation kinetics of MgH 2 can be achieved by doped with Ni/TiO 2 nanocomposite, compared to that solely doped with Ni or TiO 2 nanoparticles. The hydrogen desorption peak temperature of MgH 2 Ni/TiO 2 is 232 °C, which is 135.4 °C lower than that of ball-milled MgH 2 (367.4 °C). Moreover, the MgH 2 Ni/TiO 2 can desorb 6.5 wt% H 2 within 7 min at 265 °C and absorb ∼5 wt% H 2 within 10 min at 100 °C. In particular, the apparent activation energy of MgH 2 Ni/TiO 2 is obviously decreased from 160.5 kJ/mol (ball-milled MgH 2) to 43.7 ± 1.5 kJ/mol. Based on the analyses of microstructure evolution, it is proved that metallic Ni particles can react with Mg easily to form fine Mg 2 Ni particles after dehydrogenation, and the in-situ formed Mg 2 Ni will transform into Mg 2 NiH 4 in the subsequent rehydrogenation process. The significantly improved hydrogen absorption/desorption properties of MgH 2 Ni/TiO 2 can be ascribed to the synergistic catalytic effect of reversible transformation of Mg 2 Ni/Mg 2 NiH 4 which act as "hydrogen pump", and the multiple valence titanium compounds (Ti4+/3+/2+) which promote the electrons transfer of MgH 2 /Mg. Highlights • Ni/TiO 2 with particle sizes ∼20 nm was synthesized and doped into MgH 2. • MgH 2 Ni/TiO 2 starts to release hydrogen at 190 °C with ∼6.5 wt% H 2. • Enhanced hydrogen storage properties are due to synergistic catalytic mechanism. [ABSTRACT FROM AUTHOR]