Visible light-driven efficient palladium catalyst turnover in oxidative transformations within confined frameworks

Jiawei Li; Liuqing He; Qiong Liu; Yanwei Ren; Huanfeng Jiang

doi:10.1038/s41467-022-28474-7

Visible light-driven efficient palladium catalyst turnover in oxidative transformations within confined frameworks

Nat Commun. 2022 Feb 17;13(1):928. doi: 10.1038/s41467-022-28474-7.

Authors

Jiawei Li^{1

2}, Liuqing He², Qiong Liu³, Yanwei Ren⁴, Huanfeng Jiang⁵

Affiliations

¹ Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, 510641, Guangzhou, People's Republic of China.
² College of Chemistry and Chemical Engineering, Central South University, 410083, Changsha, People's Republic of China.
³ Institute of Analysis, Guangdong Academy of Sciences (China National Analytical Center, Guangzhou), 510070, Guangzhou, People's Republic of China.
⁴ Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, 510641, Guangzhou, People's Republic of China. renyw@scut.edu.cn.
⁵ Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, 510641, Guangzhou, People's Republic of China. jianghf@scut.edu.cn.

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^III photocatalyst and Pd^II catalyst into metal-organic framework (MOF), affording MOFs based Pd/photoredox catalysts UiO-67-Ir-PdX₂ (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-PdX₂, 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 Pd⁰ aggregation and reoxidation in Pd-catalyzed oxidation reactions.