Catalysis on Pristine 2D Materials via Dispersion and Electrostatic Interactions

Shape complementarity between catalyst and transition state structure is one of the cornerstones of chemical catalysis. Likewise, noncovalent interactions play a major role in catalysis. It has been predicted computationally and recently confirmed experimentally [Kroeger, A. A.; Hooper, J. F.; Karton, A. ChemPhysChem, 2020, 21, 1675-1681] that pristine graphene can efficiently catalyze chemical processes via jr-interactions and shape complementarity. Here we show that other two-dimensional materials with different electronic structures and chemical compositions (h-BN and graphane) can also catalyze chemical processes that proceed via planar transition state structures. These include the bowl-to-bowl inversions in corannulene and sumanene and the rotation about the C-C bond in substituted biphenyls. This catalytic activity is achieved through shape complementarity between planar nanomaterial and planar transition state structure, enabling disproportionate stabilization of the transition state structures over the nonplanar reactants and products. A DFT-based energy decomposition analysis shows that this catalytic activity is mainly driven by dispersion and electrostatic forces, which together outweigh the Pauli repulsion term. These findings enrich and expand the concept of catalysis by pristine 2D materials.