Photo-generated dinuclear {Eu(II)}<sub>2</sub> active sites for selective CO<sub>2</sub> reduction in a photosensitizing metal-organic framework.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 30135431.
- Also identified by DOI 10.1038/s41467-018-05659-7 and PMC identifier 6105582.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Photocatalytic reduction of CO<sub>2</sub> is a promising approach to achieve solar-to-chemical energy conversion. However, traditional catalysts usually suffer from low efficiency, poor stability, and selectivity. Here we demonstrate that a large porous and stable metal-organic framework featuring dinuclear Eu(III)<sub>2</sub> clusters as connecting nodes and Ru(phen)<sub>3</sub>-derived ligands as linkers is constructed to catalyze visible-light-driven CO<sub>2</sub> reduction. Photo-excitation of the metalloligands initiates electron injection into the nodes to generate dinuclear {Eu(II)}<sub>2</sub> active sites, which can selectively reduce CO<sub>2</sub> to formate in a two-electron process with a remarkable rate of 321.9 μmol h<sup>-1</sup> mmol<sub>MOF</sub><sup>-1</sup>. The electron transfer from Ru metalloligands to Eu(III)<sub>2</sub> catalytic centers are studied via transient absorption and theoretical calculations, shedding light on the photocatalytic mechanism. This work highlights opportunities in photo-generation of highly active lanthanide clusters stabilized in MOFs, which not only enables efficient photocatalysis but also facilitates mechanistic investigation of photo-driven charge separation processes.