Transition metal (Co, Ni) nanoparticles wrapped with carbon and their superior catalytic activities for the reversible hydrogen storage of magnesium hydride.

Magnesium hydride (MgH2) exhibits long-term stability and has recently been developed as a safe alternative to store hydrogen in the solid state, due to its high capacity of 7.6 wt% H2 and low cost compared to other metal hydrides. However, the high activation energy and poor kinetics of MgH2 lead to inadequate hydrogen storage properties, resulting in low energy efficiency. Nano-catalysis is deemed to be the most effective strategy in improving the kinetics performance of hydrogen storage materials. In this work, robust and efficient architectures of carbon-wrapped transition metal (Co/C, Ni/C) nanoparticles (8-16 nm) were prepared and used as catalysts in the MgH2 system via ball milling to improve its de/rehydrogenation kinetics. Between the two kinds of nano-catalysts, the Ni/C nanoparticles exhibit a better catalytic efficiency. MgH2 doped with 6% Ni/C (MgH2-6%Ni/C) exhibits a peak dehydrogenation temperature of 275.7 °C, which is 142.7, 54.2 and 32.5 °C lower than that of commercial MgH2, milled MgH2 and MgH2 doped with 6% Co/C (MgH2-6%Co/C), respectively. MgH2 doped with 6% Ni/C can release about 6.1 wt% H2 at 250 °C. More importantly, the dehydrogenated MgH2-6%Ni/C is even able to uptake 5.0 wt% H2 at 100 °C within 20 s. Moreover, a cycling test of MgH2 doped with 8% Ni/C demonstrates its excellent hydrogen absorption/desorption stability with respect to both capacity (up to 6.5 wt%) and kinetics (within 8 min at 275 °C for dehydrogenation and within 10 s at 200 °C for rehydrogenation). Mechanistic research reveals that the in situ formed Mg2Ni and Mg2NiH4 nanoparticles can be regarded as advanced catalytically active species in the MgH2-Ni/C system. Meanwhile, the carbon attached around the surface of transition metal nanoparticles can successfully inhibit the aggregation of the catalysts and achieve the steadily, prompting de/rehydrogenation during the subsequent cycling process. The intrinsic catalytic effects and the uniform distributions of Mg2Ni and Mg2NiH4 result in a favorable catalytic efficiency and cycling stability. Nano-catalysts with this kind of morphology can also be applied to other metal hydrides to improve their kinetics performance and cycling stability.

Building robust architectures of carbon-wrapped transition metal nanoparticles for high catalytic enhancement of the 2LiBH4-MgH2 system for hydrogen storage cycling performance.

Nanoscale catalyst doping is regarded as one of the most effective strategies to improve the kinetics performance of hydrogen storage materials, but the agglomeration of nanoparticles is usually unavoidable during the repeated de/rehydrogenation processes. Herein, hierarchically structured catalysts (Fe/C, Co/C and Ni/C) were designed and fabricated to overcome the agglomeration issue of nanocatalysts applied to the 2LiBH4-MgH2 system for the first time. Uniform transition metal (TM) nanoparticles (∼10 nm) wrapped by few layers of carbon are synthesized by pyrolysis of the corresponding metal-organic frameworks (MOFs), and introduced into the 2LiBH4-MgH2 reactive hydride composites (RHCs) by ball milling. The particular features of the carbon-wrapped architecture effectively avoid the agglomeration of the TM nanoparticles during hydrogen storage cycling, and high catalysis is maintained during the subsequent de/rehydrogenation processes. After de/rehydrogenation cycling, FeB, CoB and MgNi3B2 can be formed as the catalytically active components with a particle size of 5-15 nm, which show a homogeneous distribution in the hydride matrix. Among the three catalysts, in situ-formed MgNi3B2 shows the best catalytic efficiency. The incubation period of the Fe/C, Co/C and Ni/C-doped 2LiBH4-MgH2 system between the two dehydrogenation steps was reduced to about 8 h, 4 h and 2 h, respectively, which is about 8 h, 12 h and 14 h shorter than that of the undoped 2LiBH4-MgH2 sample. In addition, the two-step dehydrogenation peak temperatures of the Ni/C-doped 2LiBH4-MgH2 system drop to 323.4 °C and 410.6 °C, meanwhile, the apparent activation energies of dehydrogenated MgH2 and LiBH4 decrease by 58 kJ mol(-1) and 71 kJ mol(-1), respectively. In particular, the cycling hydrogen desorption of the Ni/C-doped 2LiBH4-MgH2 sample exhibits very good stability compared with the undoped sample. The present approach, which ideally addresses the agglomeration of nanoparticles with efficient catalysis on the RHCs, provides a new inspiration to practical hydrogen storage application for high performance complex hydrides.

Active species of CeAl(4) in the CeCl(3)-doped sodium aluminium hydride and its enhancement on reversible hydrogen storage performance.

By directly doping CeAl(4) into sodium aluminium hydride, which probably serves as the active species in the hydriding and dehydriding processes of CeCl(3)-doped NaAlH(4), a high reversible hydrogen capacity of 4.77-4.92 wt% (close to expected capacity of 5.13 wt%) can be achieved in less than 20 min under moderate conditions.