Solar-to-Pharmaceutical Raw Material Production: Photoelectrochemical Naphthoquinone Formation Using Stabilized BiVO Photoanodes in Acid Media.

In the quest for efficient use of solar energy to produce high-value-added chemicals, we first achieved the photoelectrochemical (PEC) diketonization of naphthalene, using a BiVO/WO photoanode, to obtain naphthoquinone, an important pharmaceutical raw material with excellent efficiency by solar energy conversion. In the electrochemical (EC) reaction using F-doped SnO (FTO) substrates and a 0.5 M HSO HO-acetone (60 vol %) mixed solution containing 5 mM naphthalene, we produced a small amount of naphthoquinone evolution in the dark. However, naphthoquinone (η)'s Faradic efficiency and its evolution rate at 1.7 V were only 28.5% and 0.48 μmol·cm·h, respectively. The PEC reaction using a WO photoanode had very low efficiency for naphthalene diketonization, with low η and evolution rate values at 1.1 V of 0.3% and 0.039 μmol·cm·h, respectively. In contrast, the BiVO/WO photoanode strongly enhanced the PEC reaction, and the η and evolution rates at 1.1 V were boosted up to 37.5% and 4.7 μmol·cm·h, respectively. The evolution rate of the PEC reaction in the BiVO/WO photoanode was 10 times higher than that of the EC reaction with the FTO substrate regardless of the very low bias voltage. This result suggests that the BiVO-based photoanode was very efficient for the selective oxidation of naphthalene even in acid media because of the acetone-mixed electrolyte's anti-photocorrosion effect and the multilayering of WO and BiVO. At a naphthalene concentration of 20 mM, the naphthoquinone evolution rate reached its maximum value of 7.1 μmol·cm·h. Although η tended to decrease with the increase in the electric charge, it reached 100% at a low bias voltage of 0.7 V. An intensity-modulated photocurrent spectroscopy analysis indicated the rate constant of charge transfer at the photoanode surface to the naphthalene molecules was strongly enhanced at a low bias voltage of 0.7-1.1 V, resulting in the high η value. The acid-resistant BiVO/WO photoanode functioned in acetone-mixed electrolytes enabled the realization of a new PEC oxidation reaction driven by solar energy to produce high-value-added pharmaceutical raw materials.