Hydrogen Desorption below 150 °c in MgH2-TiH2 Composite Nanoparticles: Equilibrium and Kinetic Properties

Reversible hydrogen sorption coupled with the MgH2 <-> Mg phase transformation was achieved in the remarkably low 340-425 K temperature range using MgH2-TiH2 composite nanoparticles obtained by reactive gas-phase condensation of Mg Ti vapors under He/H-2 atmosphere. The equilibrium pressures determined by in situ measurements at low temperature were slightly above those predicted using enthalpy Delta H and entropy Delta S of bulk magnesium. A single van't Hoff fit over a range extended up to 550 K yields the thermodynamic parameters Delta H = 68.1 0.9 kJ/molH(2) and Delta S = 119 2 J/(Kmo1H2) for hydride decomposition. A desorption rate of 0.18 wt % H-2/min was measured at T = 423 K and p(H-2) approximate to 1 mbar, i.e., close to equilibrium, without using a Pd catalysts. The nanoparticles displayed a small absorption desorption pressure hysteresis even at low temperatures. We critically discuss the influence exerted by nanostructural features such as interface free energy, elastic clamping, and phase mixing at the single nanopartide level on equilibrium and kinetic properties of hydrogen sorption.