With the increasing demand for green energy, the design of effective hydrogen storage materials is becoming particularly important. In this work, the hydrogen storage performances of the metal atoms (Li, Ca, and Sc) decorated two–dimensional (2D) M-graphenes were investigated with density functional theory (DFT) calculations. The metal atoms can be substantially anchored on the M-graphene surface in single–atom formation revealed by the high binding energy, which is ascribed to the remarkable charge transfers between metal atom and M-graphene. Each metal atom can capture six H2 molecules at most in single–atom decorated M-graphene. The H2 adsorption energies are in the range from −0.139 to −0.375 eV, following an order of Sc@M-graphene > Ca@M-graphene > Li@M-graphene. The affinity ability of metal–decorated M-graphene for hydrogen can be enhanced by adding an external electric field. The multi–metal atoms decorated M-graphenes, Li4C16(H2)8, Ca4C16(H2)12, and Sc4C16(H2)12 complexes show high gravimetric densities (6.06 ∼ 6.78 wt%) and a favorable binding energy window (−0.167 to −0.418 eV), meeting the department of energy (DOE)’s criteria. The thermodynamic properties were in detail studied by considering temperature and pressure effects. AIMD simulations at different temperatures indicate that the efficient release of hydrogen can occur at room temperature. Our results show that the M-graphenes with Li, Ca, and Sc decorated have high hydrogen storage capacity and reversible hydrogen release performance. This work may be useful for designing novel 2D carbon–based materials for hydrogen storage.
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