Photoinduced Water–Heptazine Electron-Driven Proton Transfer : Perspective for Water Splitting with g-C₃N₄

Heptazine-assembled polymeric carbon nitride (CN) materials have fascinated the research community as a photocatalyst for hydrogen evolution while less attention has been devoted to the mechanistic features of the host materials. Using excited-state nonadiabatic dynamics simulations, the molecular-level picture of the decomposition of heptazine hydrogen bonded to water molecule(s) (heptazine–water complex) into heptazinyl and hydroxyl biradical products is revealed. Dynamics simulations show that hydrogen detachment from the water molecule to the heptazine occurs within tens of femtoseconds and suggest that excited-state deactivation via N–H······O–H electron-driven proton transfer (EDPT) is the dominant and most relevant excited-state deactivation process in heptazine–water complexes leading to conical intersection. The observation of photorelaxation-induced water splitting by heptazine is proof of the water-splitting reaction principle, which presents further challenges for computational and experimental investigations of the deactivation of heptazinyl and OH biradical products for efficient hydrogen evolution.