Gold nanoparticle-functionalized niobium oxide perovskites as photocatalysts for visible light-induced aromatic alcohol oxidations

Spherical gold nanoparticles have been supported onto the surface of potassium niobium oxide perovskites, an underdeveloped class of semiconductor in photocatalytic organic transformations. The nanoparticle dopants of 9.5 nm in diameter and surface plasmon absorption at 530 nm are examined as possible visible light induced catalysts using alcohol photooxidation as the probe reaction. The nanomaterial-induced photooxidation of a series of aromatic alcohols is examined, in the absence of solvent, as a function of base, H2O2, and catalyst concentrations, as well as using multiple visible light sources. This experimental methodology affords extremely selective photooxidation to the carbonyl products (>99%) in as little as 2 h. Using the results obtained from the substitution of the aromatic alcohol, the proposed photocatalytic mechanism is suggested to rely heavily on plasmon-initiated electron transfer from the gold nanoparticle surface to the potassium niobium oxide perovskite and subsequent reductive decomposition of H2O2. This photodegradation step is proposed to favor the formation of ketyl radical species, a key intermediate in the visible light induced mechanism that undergoes both an electron and proton transfer to facilitate formation of the final, carbonyl products. Furthermore, the gold nanoparticle – potassium niobium oxide catalyst exhibits moderate reusability, highly desired in the realm of heterogeneous catalysis.