Visible light-driven efficient palladium catalyst turnover in oxidative transformations within confined frameworks.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 35177599.
- Also identified by DOI 10.1038/s41467-022-28474-7 and PMC identifier 8854557.
- 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
Palladium catalyst turnover by reoxidation of a low-valent Pd species dominates the proceeding of an efficient oxidative transformation, but the state-of-the-art catalysis approaches still have great challenges from the perspectives of high efficiency, atom-economy and environmental-friendliness. Herein, we report a new strategy for addressing Pd reoxidation problem by the fabrication of spatially proximate Ir<sup>III</sup> photocatalyst and Pd<sup>II</sup> catalyst into metal-organic framework (MOF), affording MOFs based Pd/photoredox catalysts UiO-67-Ir-PdX<sub>2</sub> (X = OAc, TFA), which are systematically evaluated using three representative Pd-catalyzed oxidation reactions. Owing to the stabilization of single-site Pd and Ir catalysts by MOFs framework as well as the proximity of them favoring fast electron transfer, UiO-67-Ir-PdX<sub>2</sub>, under visible light, exhibits up to 25 times of Pd catalyst turnover number than the existing catalysis systems. Mechanism investigations theoretically corroborate the capability of MOFs based Pd/photoredox catalysis to regulate the competitive processes of Pd<sup>0</sup> aggregation and reoxidation in Pd-catalyzed oxidation reactions.