▎ 摘　　要

Graphene oxides (GOs) or reduced GOs (rGOs) may offer extraordinary potential for chemical functionalization of graphene due to their unique electronic and structural properties. By means of dispersion-corrected density functional theory computations, we systematically investigated the Diels-Alder (DA) chemistry of GOs. Our computations showed that the dual nature of GOs as both a diene and a dienophile is stronger than that of pristine graphene. Interestingly, the interior bonds of a graphene surface modified by oxygen-containing groups could be functionalized by maleic anhydride (MA) and 2,3-dimethoxybutadiene (DMBD) through cycloaddition reactions, and the cycloaddition products of MA and DMBD are more favorable than the non-covalent complexes between these reagents and the GO surface. The feasibility of covalent functionalization of GOs as a diene and a dienophile strongly depends on the local structural environment of the oxygen groups, including the atomic arrangement and the number of these groups surrounding the reaction site. The exothermicities for (4+ 2) adducts of DMBD with GO are far larger than those of MA, which indicates that the dienophile character of the GO surface is stronger than its behavior as a diene.