Constructing a Photocatalyst for Selective Oxidation of Benzyl Alcohol to Benzaldehyde by Photo-Fenton-like Catalysis.

A photoactive metal-organic framework (MOF), [K(H 2 O)][Cu(DPNDI)][Cu(DPNDI)(CH 3 CN)(H 2 O)] [Cu 1.5 (DPNDI) 1.5 H 1.5 P 2 W 18 O 62 ]·2H 2 O ( Cu(Ι)W-DPNDI ), was prepared by combining a functional photosensitizer N , N '-bis(4-pyridylmethyl)naphthalene diimide (DPNDI), copper(I) ions, and an oxidation catalyst [P 2 W 18 O 62 ] 6- into a single framework via a hydrothermal process. Cu(Ι)W-DPNDI exhibited a stable structure, strong light absorption capacity, a suitable band gap, and photoelectric properties, which provided favorable conditions for photocatalysis. In the confined space, the well-aligned Cu(I) ions and POM polyanions played a synergetic effect in the electron-transfer process and reactive oxygen species generation. By coupling photocatalysis and heterogeneous Fenton-like catalysis, Cu(Ι)W-DPNDI displayed high efficiency for the selective oxidation of aromatic alcohols, with up to >99% selectivity and 75% yield.