Out of Thin Air? Catalytic Oxidation of Trace Aqueous Aldehydes with Ambient Dissolved Oxygen

Water reuse is expanding due to increased water scarcity. Water reuse facilities treat wastewater effluent to a very high purity level, typically resulting in a product water that is essentially deionized water, often containing less than 100 μg/L organic carbon. However, recent research has found that low-molecular-weight aldehydes, which are toxic electrophiles, comprise a significant fraction of the final organic carbon pool in recycled wastewater in certain treatment configurations. In this manuscript, we demonstrate oxidation of trace aqueous aldehydes to their corresponding acids using a heterogeneous catalyst (5% Pt on C), with ambient dissolved oxygen serving as the terminal electron acceptor. Mass balances are essentially quantitative across a range of aldehydes, and pseudo-first-order reaction kinetics are observed in batch reactors, with k_obs varying from 0.6 h^-1 for acetaldehyde to 4.6 h^-1 for hexanal, while they are low for unsaturated aldehydes. Through kinetic and isotopic labeling experiments, we demonstrate that while oxygen is essential for the reaction to proceed, it is not involved in the rate-limiting step, and the reaction appears to proceed primarily through a base-promoted β-hydride elimination mechanism from the hydrated gem-diol form of the corresponding aldehyde. This is the first report we are aware of that demonstrates useful abiotic oxidation of a trace organic contaminant using dissolved oxygen.