Unraveling the synergy between metal–organic frameworks and co-catalysts in photocatalytic water splitting

Abstract

We investigate the synergy occurring in photocatalytic water splitting between the metal–organic framework MIL-125-NH₂ and two co-catalysts, namely NiO and Ni₂P, by calculating their band edge alignment with respect to the redox levels of liquid water. For the NiO/H₂O and Ni₂P/H₂O interfaces, we employ an explicit atomistic description of water and perform molecular dynamics simulations considering both molecular and dissociated water adsorbed at the co-catalyst surface. For the MIL-125-NH₂/NiO and MIL-125-NH₂/Ni₂P interfaces, we rely on the concept of charge neutrality and use a scheme combining the electron affinities and the charge neutrality levels of the interface components. We provide a description of the underlying fundamental processes that is consistent with photoluminescence and intrinsic activity experiments and that supports NiO and Ni₂P as suitable co-catalysts for MIL-125-NH₂ as far as the hydrogen evolution reaction is concerned.