RESUMO
In this study, the effect of nanolayer-like-shaped MgFe2O4 that is synthesised via a simple hydrothermal method on the performance of MgH2 for hydrogen storage is studied. MgH2 + 10 wt% MgFe2O4 is prepared by using the ball milling method. The MgFe2O4-doped MgH2 sample started to release H2 at approximately 250 °C, 90 °C and 170 °C lower than the milled and pure MgH2 respectively. At 320 °C, the isothermal desorption kinetic study has shown that the doped sample has desorbed approximately 4.8 wt% H2 in 10 min while the milled MgH2 desorbed less than 1.0 wt% H2. For isothermal absorption kinetics, the doped sample can absorb approximately 5.5 wt% H2 in 10 min at 200 °C. Meanwhile, the undoped sample absorbs only 4.0 wt% H2 in the same condition. The activation energy of 10 wt% MgFe2O4-doped MgH2 composite is 99.9 kJ mol-1, which shows a reduction of 33.1 kJ mol-1 compared to the milled MgH2 (133.0 kJ mol-1). X-ray diffraction spectra display the formation of new species which are Fe and MgO after dehydrogenation, and these new species are believed to act as the real catalyst that plays a crucial role in improving the sorption performance of the MgFe2O4-doped MgH2 system by providing a synergetic catalytic effect.
RESUMO
The composite of MgH2/K2NiF6/carbon nanotubes (CNTs) is prepared by ball milling, and its hydrogenation properties are studied for the first time. MgH2 co-catalyzed with K2NiF6 and CNTs exhibited an improvement in the onset dehydrogenation temperature and isothermal de/rehydrogenation kinetics compared with the MgH2-K2NiF6 composite. The onset dehydrogenation temperature of MgH2 doped with 10 wt% K2NiF6 and 5 wt% CNTs is 245 °C, which demonstrated a reduction of 25 °C compared with the MgH2 + 10 wt% K2NiF6 composite. In terms of rehydrogenation kinetics, MgH2 doped with 10 wt% K2NiF6 and 5 wt% CNTs samples absorbed 3.4 wt% of hydrogen in 1 min at 320 °C, whereas the MgH2 + 10 wt% K2NiF6 sample absorbed 2.6 wt% of hydrogen under the same conditions. For dehydrogenation kinetics at 320 °C, the MgH2 + 10 wt% K2NiF6 + 5 wt% CNTs sample released 3.3 wt% hydrogen after 5 min of dehydrogenation. By contrast, MgH2 doped with 10 wt% K2NiF6 released 3.0 wt% hydrogen in the same time period. The apparent activation energy, Ea, for the dehydrogenation of MgH2 doped with 10 wt% K2NiF6 reduced from 100.0 kJ mol-1 to 70.0 kJ mol-1 after MgH2 was co-doped with 10 wt% K2NiF6 and 5 wt% CNTs. Based on the experimental results, the hydrogen storage properties of the MgH2/K2NiF6/CNTs composite is enhanced because of the catalytic effects of the active species of KF, KH and Mg2Ni that are formed in situ during dehydrogenation, as well as the unique structure of CNTs.
RESUMO
The effects of Na3FeF6 catalyst on the hydrogen storage properties of MgH2 have been studied for the first time. The results showed that for the MgH2 sample doped with 10 wt% Na3FeF6, the onset dehydrogenation temperature decreased to 255 °C, which was 100 °C and 162 °C lower than those of the as-milled and as-received MgH2 sample, respectively. The re/dehydrogenation kinetics were also significantly enhanced compared to the un-doped MgH2. The absorption kinetics showed that the as-milled MgH2 only absorbed 3.0 wt% of hydrogen at 320 °C in 2 min of rehydrogenation, but about 3.6 wt% of hydrogen was absorbed within the same period of time after 10 wt% Na3FeF6 was added to MgH2. The desorption kinetics showed that the MgH2 + 10 wt% Na3FeF6 sample could desorb about 3.8 wt% of hydrogen in 10 min at 320 °C. In contrast, the un-doped MgH2 sample desorbed only 0.2 wt% of hydrogen in the same period of time. The activation energy for the decomposition of the as-milled MgH2 was 167.0 kJ mol(-1), and this value decreased to 75.0 kJ mol(-1) after the addition of 10 wt% Na3FeF6 (a reduction by about 92.0 kJ mol(-1)). It is believed that the in situ formation of the active species of NaMgF3, NaF and Fe during the heating process could enhance the hydrogen storage properties of MgH2, due to the catalytic effects of these new species.
