▎ 摘　　要

The hydrogen spillover mechanism on B-doped graphene was explicitly investigated by first-principles calculations. By the incorporation of boron into graphene, our theoretical investigation shows that B doping can substantially enhance the adsorption strength for both H atoms and the metal cluster on the substrate. The firmly bound catalytic metal on B-doped graphene can effectively dissociate H-2 molecules into H atoms, and the H atom is more likely to migrate from the bridge site of the H-saturated metal to the supporting graphene sheet. Further investigation on the BC3 sheet gives sufficiently low activation barriers for both H migration and diffusion processes; thus, more H atoms are expected to adsorb on BC3 substrate via H spillover under ambient conditions compared with the undoped graphene case. Our result is in good agreement with recent experimental findings that microporous carbon has an enhanced hydrogen uptake via boron substitution, implying that B doping with spillover is an effective approach in the modification of graphitic surface for hydrogen storage applications.