Rapid Charge Separation Boosts Solar Hydrogen Generation at the Graphene-MoS₂ Junction: Time-Domain Ab Initio...

Transition metal dichalcogenides and graphene hybrids hold great promise for photovoltaics and photocatalysts. Using a combination of time-domain density functional theory and nonadiabatic molecular dynamics, we investigate the interplay between forward and backward electron transfer (ET), as well as energy relaxation in a van der Waals graphene-MoS₂ heterojunction. We demonstrated that built-in potential formed at the polarized interface produces charge separation upon photoexcitation. The electron left on graphene is injected into MoS₂ on an ultrafast time scale, which is notably faster than energy losses to heat regardless of the initial state energy. Once the electron is relaxed to the conduction band edge state of MoS₂, it transfers back and recombines with the hole remaining on graphene on ultrafast time scales by considering quantum transitions among multiple k points. The obtained time scales for ET, back-ET, and energy relaxation agree well with experimental data. The study reveals that ET that is faster than energy loss makes the graphene-MoS₂ heterojunction efficient for optoelectronic applications.