Defect-Engineered Beryllium Dinitride (BeN2) Monolayer with Light-Metal Decoration for Reversible High-Capacity Hydrogen Storage

Abstract

Hydrogen (H2) possesses the highest gravimetric energy density of any chemical fuel and is the most abundant element in the universe. However, its extremely low volumetric energy density at standard conditions imposes a fundamental materials challenge for safe, efficient, and reversible storage. Here, we report a defect-engineered 2D beryllium dinitride (BeN2) monolayer that enables stable light-metal functionalization for high-capacity H2 storage. A 2 x 2 supercell containing two intrinsic beryllium vacancies accommodates four Li, Na, and K atoms without clustering, exhibiting strong average metal-vacancy binding energies of -3.80, -2.94, and -3.18 eV, respectively. Ab initio molecular dynamics simulations at 400 K confirm the thermal stability of the metal-decorated frameworks and the suppression of metal aggregation. The vacancy-stabilized alkali-metal centers generate localized charge polarization that facilitates the adsorption of up to 20 H2 molecules per supercell, with average adsorption energies of -0.182 eV (Li), -0.191 eV (Na), and -0.171 eV (K), making the adsorption reversible under near-ambient conditions. The corresponding gravimetric H2 storage capacities reach 11.64, 9.82, and 8.49 wt percent, respectively, significantly exceeding the US Department of Energy (DOE) ultimate target of 6.50 wt percent. Moreover, thermodynamic analysis further confirms favorable adsorption-desorption behavior within practical operating windows. These results establish vacancy-defected light-metal decorated BeN2 as a viable design strategy for high-density, reversible H2 storage, providing a scalable framework for engineering polar lightweight materials for energy storage applications.