Theoretical Study on Hydrogen Storage Properties of Alkali Metal‐Modified Holey Graphdiyne

ABSTRACT Contemporary society faces the dual challenges of the energy crisis and environmental pollution. The exploration of low‐carbon and sustainable alternative energy sources has become a central focus of the global scientific and industrial communities. H 2 has been regarded as a crucial component of future energy systems because of its unique physicochemical properties and its clean and abundant production pathways. Consequently, research on H 2 storage materials has attracted global scientific attention. This study employs Density Functional Theory (DFT) to investigate the H 2 storage performance of alkali metal‐modified holey graphdiyne (HGY) systems. Owing to the small atomic radius and low atomic mass of Li atoms, high‐density Li decoration on the HGY framework was achieved, thereby significantly enhancing its hydrogen storage capacity. The results indicate that the 6Li@HGY system exhibits a hydrogen storage capacity of 12.8 wt.% and an average H 2 adsorption energy of −0.280 eV, suggesting favorable adsorption reversibility. During H 2 adsorption, two distinct mechanisms were identified: (1) proximal adsorption (Type I H 2 molecules) through electric field effects generated by Li‐substrate charge transfer, and (2) distal adsorption (Type II H 2 molecules) via induced polarization at positions farther from Li atoms. In conclusion, the Li‐decorated HGY system demonstrates remarkable potential for advanced hydrogen storage applications.