Integration of bio-inspired lanthanide-transition metal cluster and P-doped carbon nitride for efficient photocatalytic overall water splitting.

ABSTRACT: Photosynthesis in nature uses the Mn₄CaO₅ cluster as the oxygen-evolving center to catalyze the water oxidation efficiently in photosystem II. Herein, we demonstrate bio-inspired heterometallic LnCo₃ (Ln = Nd, Eu and Ce) clusters, which can be viewed as synthetic analogs of the CaMn₄O₅ cluster. Anchoring LnCo₃ on phosphorus-doped graphitic carbon nitrides (PCN) shows efficient overall water splitting without any sacrificial reagents. The NdCo₃/PCN-c photocatalyst exhibits excellent water splitting activity and a quantum efficiency of 2.0% at 350 nm. Ultrafast transient absorption spectroscopy revealed the transfer of a photoexcited electron and hole into the PCN and LnCo₃ for hydrogen and oxygen evolution reactions, respectively. A density functional theory (DFT) calculation showed the cooperative water activation on lanthanide and O-O bond formation on transition metal for water oxidation. This work not only prepares a synthetic model of a bio-inspired oxygen-evolving center but also provides an effective strategy to realize light-driven overall water splitting.

SUBMITTER: Chen R 

PROVIDER: S-EPMC8433082 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature