Enhanced Hydrolysis of MgH₂ by Transition Metal Oxides and NaH: Performance, Mechanisms, and Optimization

Abstract

MgH₂ is recognized as a promising material for hydrogen production due to its high hydrogen density, abundant availability, and non-polluting hydrolysis by-products, making it a viable hydrogen source for fuel cells. This study, for the first time, investigates the hydrogen production performance of the MgH₂-MOx-NaH (M = Ti, Zr, Mo, Fe, V, Bi) system, which exhibits remarkable hydrolysis properties in aqueous solutions. A series of MgH₂-MOx-NaH composite powders were synthesized via mechanical ball milling. The results revealed that V₂O₅-NaH and Bi₂O₃-NaH significantly enhanced the hydrolysis performance of MgH₂ for hydrogen production. Specifically, Bi₂O₃-NaH and V₂O₅-NaH effectively refined MgH₂ particles and mitigated agglomeration during the milling process. Hydrolysis tests demonstrated that the conversion rate and the hydrogen generation rate (mHGR) of composites initially increased with ball milling time and then decreased. The maximum hydrolysis hydrogen production yield and conversion rate for MgH₂-Bi₂O₃-NaH and MgH₂-V₂O₅-NaH composites occurred at a ball milling duration of 10 hours, and reached up to 1354.1 mL g⁻¹ (88.5%) and 1273.5 mL g⁻¹ (81.8%), respectively, within 8 minutes. Kinetic tests of hydrolysis hydrogen production showed that the reaction rate and hydrogen conversion increased with elevated hydrolysis temperatures. The activation energies for the hydrolysis of MgH₂-MOx-NaH (M = Ti, Zr, Mo, Fe, V, Bi) were calculated from the hydrolysis-hydrogen production curves using the Arrhenius formula, yielding values of 41.32, 37.66, 36.40, 34.60, 30.80, and 27.17 kJ mol⁻¹, respectively. The lower activation energies for hydrolysis indicate improved reaction kinetics, suggesting that the incorporation of transition metal oxides and sodium hydride effectively enhances both the hydrolytic conversion and reaction rate of MgH₂.