Solar-driven highly selective conversion of glycerol to dihydroxyacetone using surface atom engineered BiVO₄...

Dihydroxyacetone is the most desired product in glycerol oxidation reaction because of its highest added value and large market demand among all possible oxidation products. However, selectively oxidative secondary hydroxyl groups of glycerol for highly efficient dihydroxyacetone production still poses a challenge. In this study, we engineer the surface of BiVO₄ by introducing bismuth-rich domains and oxygen vacancies (Bi-rich BiVO_4-x) to systematically modulate the surface adsorption of secondary hydroxyl groups and enhance photo-induced charge separation for photoelectrochemical glycerol oxidation into dihydroxyacetone conversion. As a result, the Bi-rich BiVO_4-x increases the glycerol oxidation photocurrent density of BiVO₄ from 1.42 to 4.26 mA cm^-2 at 1.23 V vs. reversible hydrogen electrode under AM 1.5 G illumination, as well as the dihydroxyacetone selectivity from 54.0% to 80.3%, finally achieving a dihydroxyacetone production rate of 361.9 mmol m^-2 h^-1 that outperforms all reported values. The surface atom customization opens a way to regulate the solar-driven organic transformation pathway toward a carbon chain-balanced product.