▎ 摘　　要

We have studied the electronic characteristics of covalently functionalized graphene by nitrene chemistry using first-principles density functional calculations. The perfluorophenylazide functionalization leads to a band-gap opening in graphene and transition from a semimetallic to a semiconducting state. The [2 + 1] cycloaddition-induced gap is shown to be attributed to the modification of the pi conjugation that depends on the concentration of aziridine adducts. The implications of tailoring the band structure of functionalized graphene for future graphene-based device applications are discussed.