Stacking Modes-Induced Chemical Reactivity Differences on Chemical Vapor Deposition-Grown Trilayer Graphene

Trilayer graphene (TLG) synthesized by chemical vapor deposition (CVD), in particular the twisted TLG, exhibits sophisticated electronic structures that depend on their stacking modes. Here, we computationally and experimentally demonstrate the chemical reactivity differences of CVD-TLG induced by the stacking modes and corroborated by a photoexcited phenyl-grafting reaction. The experimental results show that the ABA stacking TLGs have the most inert chemical property, yet 30°-30° stacking twisted TLGs are the most active. Further, density functional theory calculations have shown that the chemical reactivity difference can be quantitatively explained by the differences in the number of hot electrons generated in their valence band during irradiation. The activity difference is further verified by the calculated adsorption energy of phenyl on the TLGs. Our work provides insight into the chemistry of TLG and addresses the challenges associated with selective functionalization of TLG with phenyl groups. The understandings developed in this project can also guide the future development of TLG-based functional devices.