Non–Noble–Metal POM@MOF for Enhancing the Visible Photoinduced Baeyer–Villiger Oxidation Reactions

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 H 3 PMo 12 O 40 and H 4 SiW 12 O 40 within a Cu–tr 2 pr 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 tr 2 pr 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.