Unveiling the Destabilization of Sp3 and Sp2 Bonds in Transition Metal-Modified Borohydrides to Improve Reversible Dehydrogenation and Rehydrogenation

Borohydrides offer promise as potential carriers for hydrogen storage due to their high hydrogen concentration. However, the strong chemical bonding within borohydrides poses challenges for efficient hydrogen release during usage and restricts the re-hydrogenation process when attempting to regenerate the material. These high thermodynamic and kinetic barriers present obstacles in achieving reversible de-hydrogenation and re-hydrogenation of borohydrides, impeding their practical application in hydrogen storage systems. Employing density functional theory calculations, we conduct a comprehensive investigation into the influence of transition metals on both the BH4 cluster, a fundamental building block of borohydrides, and pure boron, which is formed as the end product following hydrogen release. Our research reveals correlations among the d-band center, work function, and surface energy of 3d and 4d transition metals. These correlations are directly linked to the weakening of bonding within the BH4 cluster when adsorbed on catalyst surfaces. On the other hand, we also explore how various intrinsic properties of transition metals influence the formation of boron vacancies and the hydrogen bonding process. By establishing a comprehensive correlation between the weakening of sp3 hybridization in the BH4 cluster and the sp2 hybridization in boron, we facilitate the identification and screening of optimal candidates capable of achieving reversible de-hydrogenation and re-hydrogenation in borohydrides.