Graphene Catalysis Made Easy

Catalysis by pristine 2D materials is an emerging form of eco-friendly, heterogeneous catalysis. We review recent computational studies in the field of pristine-graphene catalysis, in which graphene efficiently catalyzes chemical processes via π-interactions and shape complementarity. These include the (1) bowl-to-bowl inversion of curved aromatic molecules (e.g., corannulene and sumanene), (2) enantiomerizations of biaryl compounds (e.g., biphenyl and binaphthyl derivatives), and (3) skeletal inversions of helicenes and cyclooctatetraene derivatives. A pristine graphene catalyst reduces the reaction barrier heights for these processes by amounts ranging from 10 to 50 kJ mol–1, which correspond to reaction rate enhancements by 2–10 orders of magnitude at room temperature. The graphene-catalyzed enantiomerization of BINOL has been confirmed experimentally through chiral HPLC measurements. We highlight potential applications of pristine-graphene catalysis in (1) the dynamic kinetic resolution of biaryls and (2) the directional self-assembly of bowl-shaped aromatic molecules across a graphene monolayer.