Synthesis and characterization of MoO3: application to the photo production of oxygen under visible light

Abstract

One of the most striking features of molybdenum oxide is the versatility of its catalytic properties, which are determined by the valence states of molybdenum and its coordination. It may be anticipated that MoO₃ surface must contain catalytic sites which are active in different types of elementary steps. MoO₃ was successfully synthesized by hydrothermal route at 400 °C, acquiring n-type conduction, due to oxygen deficiency. The single phase, elucidated by X-ray diffraction, crystallizes in an orthorhombic unit cell (Space Group (SG) Pbnm, N° 62) with a crystallite size of 12 nm. MoO₃ is a direct band gap semiconductor with a forbidden band value of 2.93 eV where the electrical conduction occurs by low polaron hopping between mixed valences Mo^+6/+5 with an activation energy of 0.14 eV. The thermo-power indicates n-type conduction, and confirmed by the capacitance-potential measurement; the latter gives an electrons density of 1.87 × 10²⁰/cm³and a mobility of 1.77 × 10⁻⁶ m²/V.s. The flat band potential V_fb (0.11 V_SCE) is determined from the capacitance measurement. The physical and chemical characterizations are correlated for the construction of the potential diagram in order to assess the photo electrochemical properties of MoO₃ for the oxygen evolution. The valence band, is located above the O₂/H₂O potential ( ~ 1.3 V_SCE), allowing O₂ evolution upon visible light and the oxide is photocathodically protected against corrosion. An evolution rate of 0.13 mL/(mg. h) is obtained within 20 min. at optimal conditions (100 mg of catalyst and 50 °C).