Integrating Single-Site Co Catalytic Center into Zr-MOF without Sacrificing Light-Harvesting Units for Enhanced Photocatalysis

Abstract

Metal-organic frameworks (MOFs) are promising photocatalysts for solar fuel production, but some conventional methods for introducing catalytic sites often sacrifice the visible-light-harvesting components. Herein, a Zr-MOF with single-site Co centers (NU-1000-NIS-Co) was constructed while preserving the intrinsic photosensitive units through a linker installation strategy. NH2-BDC linkers were pre-anchored as secondary building blocks within a mesoporous Zr-MOF (NU-1000), followed by Schiff base condensation reaction and Co coordination. The obtained NU-1000-NIS-Co demonstrated superior photocatalytic H2 evolution rate (190 μmol g -1 h -1 ), which is 1.53 times higher than that of NU-1000@Pt.Photoelectrochemical experiments and DFT calculations confirmed the efficient photogenerated electron transfer from TBAPy 4-visible-light absorbers to Co catalytic centers. This work presents a viable approach for developing noble-metal-free MOF photocatalysts with spatially separated functional components.