Why Hydrogen Dissociation Catalysts do not Work for Hydrogenation of Magnesium

Abstract Provision of atomic hydrogen by hydrogen dissociation catalysts only moderately accelerates the hydrogenation rate of magnesium. They shed light on this well‐known but technically challenging fact through a combined approach using an unconventional surface science technique together with Density Functional Theory (DFT) calculations. The calculations demonstrate the drastic electronic structure changes during transformation of Mg to MgH₂, which make fractional hydrogen coverage on the surface, as well as substoichiometric hydrogen content in the bulk energetically unfavorable. Reflecting Electron Energy Loss Spectroscopy (REELS) is used to measure the surface and bulk plasmon during hydrogen sorption in magnesium. The measurements show that the hydrogenation proceeds via the growth of magnesium hydride without the presence of chemisorbed hydrogen on the metallic magnesium surface exactly as indicated by the calculations. This is due to the low stability of sub‐stoichiometric amounts of chemisorbed H correlating with the unfavorable charge state of Mg. They are merely bound to the unchanged adjacent Mg layers, thereby explaining the failure of classical hydrogenation catalysts, which effectively only hydrogenate Mg in their direct vicinity. The acceleration of hydrogen sorption kinetics in Mg must affect the polarization in the interface between Mg and MgH₂ during hydrogenation.