Aqueous Photocatalytic Glycerol Oxidation to Formic Acid Coupled to H₂O₂ Production with an Anthraquinone Dye

Abstract The photocatalytic oxidation of glycerol into formic acid (FA) is reported employing a 9,10‐anthraquinone‐2,6‐disulphonate disodium salt (AQDS) photocatalyst. The system operates in water, in the absence of additives, using O₂ as the oxidant and irradiating with blue light (λ = 415 nm). In 22 h, conversion of glycerol up to 79% leads to 30% yield of FA (turnover number of 15 for AQDS), with 79% selectivity among the products in solution and a quantum yield of 1.2%. The oxidation of glycerol is coupled to the reduction of oxygen to hydrogen peroxide (up to 16±5 mm), a high‐added value photosynthetic product. A mechanistic investigation combining electron paramagnetic resonance (EPR) spectroscopy, transient absorption spectroscopy (TAS), and time‐dependent density‐functional theory (TD‐DFT) calculations reveals a photoinduced hydrogen atom abstraction involving the triplet excited state ^3*AQDS and the glycerol substrate (k = 1.02(±0.03)×10⁷ m⁻¹·s⁻¹, H/D kinetic isotope effect = 2.00±0.16). The resulting ketyl radical of AQDS follows fast deprotonation to the radical anion AQDS^•–, that further reacts with oxygen (k = 1.2×10⁸ m⁻¹·s⁻¹), ultimately leading to the production of H₂O₂.