Solar-to-Pharmaceutical Raw Material Production: Photoelectrochemical Naphthoquinone Formation Using Stabilized BiVO₄...

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 BiVO₄/WO₃ photoanode, to obtain naphthoquinone, an important pharmaceutical raw material with excellent efficiency by solar energy conversion. In the electrochemical (EC) reaction using F-doped SnO₂ (FTO) substrates and a 0.5 M H₂SO₄ H₂O-acetone (60 vol %) mixed solution containing 5 mM naphthalene, we produced a small amount of naphthoquinone evolution in the dark. However, naphthoquinone (η_NQ)'s Faradic efficiency and its evolution rate at 1.7 V_Ag/AgCl were only 28.5% and 0.48 μmol·cm^-2·h^-1, respectively. The PEC reaction using a WO₃ photoanode had very low efficiency for naphthalene diketonization, with low η_NQ and evolution rate values at 1.1 V_Ag/AgCl of 0.3% and 0.039 μmol·cm^-2·h^-1, respectively. In contrast, the BiVO₄/WO₃ photoanode strongly enhanced the PEC reaction, and the η_NQ and evolution rates at 1.1 V_Ag/AgCl were boosted up to 37.5% and 4.7 μmol·cm^-2·h^-1, respectively. The evolution rate of the PEC reaction in the BiVO₄/WO₃ 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 BiVO₄-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 WO₃ and BiVO₄. At a naphthalene concentration of 20 mM, the naphthoquinone evolution rate reached its maximum value of 7.1 μmol·cm^-2·h^-1. Although η_NQ tended to decrease with the increase in the electric charge, it reached 100% at a low bias voltage of 0.7 V_Ag/AgCl. 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_Ag/AgCl, resulting in the high η_NQ value. The acid-resistant BiVO₄/WO₃ 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.