Visible-Light-Controlled Oxidation of Glucose using Titania-Supported Silver Photocatalysts

The visible-light-mediated photo-catalytic selective valorisation of glucose using TiO₂-supported Ag nanoparticles is shown for the first time. The optimisation of the catalyst composition, substrate-to-catalyst ratio and reaction medium proved that a near total suppression of the mineralisation pathway could be achieved with a selectivity to partial oxidation products and small-chain monosaccharides as high as 98 %. The primary products were determined to be gluconic acid, arabinose, erythrose, glyceraldehyde and formic acid. Under UVA light, the selectivity to organics decreases because of the production of CO₂ from mineralisation. A reaction mechanism is proposed based on an α-scission process combined with the Ruff degradation reaction, which explains the presence of the oxidation products, the smaller carbohydrates and formic acid. X-ray photoelectron spectroscopy, UV/Vis spectroscopy and microscopy studies showed the presence of plasmonic 4 nm particles of silver that were oxidised to silver oxide over the course of the reaction, and recycling studies revealed that this was not detrimental to activity.