Developing highly efficient, environmentally friendly, inexpensive, and readily available photocatalysts for Baeyer-Villiger (B-V) oxidation reactions is of significant importance. This study involved encapsulating Keggin-type H3PMo12O40 and H4SiW12O40 within a Cu-tr2pr framework to synthesis two novel isomorphic POM@MOFs (CT-PMo and CT-SiW), which is the first time that polyoxometalates (POMs) have been added to metal-organic frameworks (MOFs) constructed with the participation of tr2pr organic ligands. The modulation of photoelectrochemical properties and photocatalytic activity was achieved by regulating POMs. Photoelectrochemical testing revealed that CT-PMo exhibits stronger light absorption, faster charge transfer rates, lower resistance and reduced probability of recombination compared to CT-SiW. The photoinduced B-V oxidation reaction demonstrates that CT-PMo has higher catalytic activity, with a yield of 97.1% and turnover numbers and turnover frequencies of 971 and 923.0 h-1, respectively. CT-PMo is the first noble metal-free catalyst for the photoinduced B-V oxidation reaction based on the Mukaiyama method, exhibiting the highest turnover frequencies value along with outstanding structural stability and recyclability, offering broad industrial application prospects.
Cai et al. (Sun,) studied this question.