Synergetic Confinement and Electron-Catalysis Boost N₂ Hydrogenation in C₇₀F₇₀ Nanoreactor: A Theoretical Investigation

Reduction by one-electron activation or hydrogenation of N2 is extraordinarily difficult because of its extremely stable triple bond and symmetry-forbidden direct H2 addition. Demonstrated herein is reduction or hydrogenation of N2 in perfluorocarbon cage C70F70, a promising nanoreactor with synergetic confinement and electron-catalyzing effects. C70F70 pointing all dipolar C–F units toward its center not only traps reactants but also gives the cage and its guest species strong electron-hosting/binding abilities through lowering their orbital energies. Such a confinement effect can force one electron into the N2 π*-orbital, not only activating the N≡N bond but also making its frontier molecular orbitals symmetry matching with H2 and thus boosting its hydrogenation with a noticeable lowering of the energy barrier. The ability to initiate reduction reactions by absorbing electrons into the cage-reactor without surface adsorption and solid catalysts enables pathways that are not accessible using conventional electro-/photochemical processes.