Glycerol Electro-Oxidation to Dihydroxyacetone with Coupled Hydrogen Production via In Situ Optimization of Water Oxidation Intermediates.

In electrocatalytic water splitting, the selective oxidation of glycerol (GLY) to 1,3-dihydroxyacetone (DHA) presents a promising alternative to the oxygen evolution reaction (OER) and enables the concurrent production of valuable chemicals and hydrogen. However, controlling this selective oxidation is challenging due to similar reactivities of the hydroxyl groups of GLY. In this study, an electrocatalyst is synthesized by combining phosphated few-layer phosphorene (FLP-P) with bismuth-doped cobalt oxide (Bi-CoO). In the anodic reactions, the Bi center coordinates selectively with the secondary hydroxyl group of GLY; CoO forms the OER intermediates, and the phosphate groups on FLP-P stabilize the OER intermediates through a bifunctional mechanism. In situ Raman spectroscopy is employed to optimize the production of the OER intermediates for achieving 85% GLY conversion reaction and 89% DHA product selectivity in neutral medium. The simultaneous production of valuable chemicals and high-purity hydrogen exemplifies the advancement of green hydrogen production in water electrolysis.