Analysis of hydrogen adsorption in the bulk and on the surface of magnesium nanoparticles

The stability of magnesium hydride (MgH _x ) nanoparticles (x = 0.5, …, 2) is investigated using ab initio calculations. It is shown that for a nanoparticle diameter of D ～ 5 nm, the internal pressure becomes lower than 3 kbar; for this reason, the structure of hydride nanoparticles coincides with the structure of this hydride in crystalline form. It is found that the phase of partly saturated MgH _x hydrides (x < 2) must decompose into the phase of pure hcp magnesium and the α phase of MgH₂. The frequencies of jumps of hydrogen atoms within the hcp phase of magnesium and in the α phase of MgH₂ are calculated; it is shown that slow diffusion of hydrogen in magnesium is due to the large height of potential barriers for motion of hydrogen within MgH₂. To attain high diffusion rates, the structures of Mg₅₃Sc and Mg₅₃Ti crystals and their hydrides are calculated. It is found that the frequency of jumps of H atoms in Mg₅₃ScH₁₀₈ near the Sc atoms does not noticeably change as compared to the frequency of jumps in the α phase of MgH₂, while the frequency of jumps in Mg₅₃TiH₁₀₈ near Ti atoms is higher by approximately a factor of 2.5 × 10⁶. This means that diffusion in manganese hydride with small admixtures of titanium atoms must be considerably eased. Chemical dissociation of hydrogen molecules on the (0001) surface of hcp magnesium, on the given surface with adjoined individual Ti atoms, and on the surface of a one-layer titanium cluster on the given surface of magnesium is investigated. It is found that dissociation of hydrogen at solitary titanium atoms, as well as on the surface of a Ti cluster, is facilitated to a considerable extent as compared to pure magnesium. This should also sharply increase the hydrogen adsorption rate in magnesium nanoparticles.