Small-Molecule Activation Driven by Confinement Effects

Abstract

Electron-rich environments may arise from interactions between nanostructures at subnanometer separations and have been shown able to facilitate molecular dissociation of simple diatomic molecules. Electrons in these regions have energies close to the Fermi energy of the structures contributing to the electron-rich environment. These energies can be tuned to achieve specific interactions with the LUMO of molecules of interest. In this work, we focus on electron-rich regions generated between platinum nanoclusters and carbon nanotubes in the confined space defined by a nanopillared graphene (NPG) structure decorated with Pt22 nanoparticles. First, the reactivity of these regions is evaluated using density functional theory by comparing the bond strengths of O2, CO, and N2 adsorbed on Pt22 with that of the molecules adsorbed on similar surfaces in absence of surrounding electron-rich regions. Results show larger charge transfer to the adsorbed molecules in the presence of the electron-rich environments. The...