▎ 摘　　要

The geometric stability and hydrogen capacity of Pd-decorated graphene with experimentally realizable boron dopants and various vacancy defects including single carbon vacancy (SV), "585"-type double carbon vacancy (585 DCV) and "555-777"-type double carbon vacancy (555-777 DCV) are investigated using the first-principles calculations based on density functional theory (DFT). It is found that among the four types of defective structures, Pd's binding energies on SV and 585 DCV defect graphene sheets exceed the cohesive energy of the Pd metal bulk, thus Pd atoms are well dispersed above defective graphene sheets and effectively prevent Pd clustering. Up to three H-2 molecules can bind to Pd atom on graphene with B dopants, SV and 555-777 DCV defects. For the cases of Pd-decorated graphene with B dopants and 555-777 DCV defect, a single H-2 or two H-2 are molecularly chemisorbed to Pd atom in the form of Pd-H-2 Kubas complex, where the stretched H-H bond is relaxed but not dissociated. Out of two adsorbed H-2, the third H-2 binds to Pd atom by small van der Waals (vdW) forces and the nature of bonding is very weak physisorption. Different from above two cases, three H-2 are all molecularly chemisorbed to Pd atom with stretched H-H bond for Pd-decorated SV defect graphene, the hybridization of the Pd-4d orbitals with the H-2-sigma orbitals and the electrostatic interaction between the Pd cation and the induced H-2 dipole both contribute to the H-2 molecules binding, and the binding energies of 0.25-0.41 eV/H-2 is in the range that can permit H-2 molecules recycling at ambient conditions. (C) 2014 Elsevier B.V. All rights reserved.