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

Rong Chen; Gui-Lin Zhuang; Zhi-Ye Wang; Yi-Jing Gao; Zhe Li; Cheng Wang; Yang Zhou; Ming-Hao Du; Suyuan Zeng; La-Sheng Long; Xiang-Jian Kong; Lan-Sun Zheng

doi:10.1093/nsr/nwaa234

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

Natl Sci Rev. 2020 Sep 14;8(9):nwaa234. doi: 10.1093/nsr/nwaa234. eCollection 2021 Sep.

Authors

Affiliations

¹ Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surface and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
² College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, China.
³ College of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, China.

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.

Keywords: bio-inspired; lanthanide-transition metal cluster; oxygen-evolving center; photocatalytic overall water splitting; synergistic effects.