Direct Liquid Injection Chemical Vapor Deposition of Molybdenum-Doped Bismuth Vanadate Photoelectrodes for Efficient Solar Water Splitting

The direct liquid injection chemical vapor deposition (DLI-CVD) method is used to grow pristine and molybdenum (Mo)-doped monoclinic scheelite phase bismuth vanadate (BVO) photoelectrodes. Superior photoelectrochemical (PEC) performance is achieved with ∼200 ± 50 nm thick pristine and 8 at. % Mo-doped BVO films grown at 550 °C. Photocurrent densities as high as ∼1.65 and 3.25 mA/cm² are obtained for pristine and optimum 8% Mo-doped BVO electrodes, respectively, at 1.23 V vs reversible hydrogen electrode (RHE) under visible light AM 1.5G (100 mW/cm²) in 0.5 M phosphate buffer electrolyte in the presence of 0.1 M Na₂SO₃ hole scavenger. Somewhat lower photocurrent densities of ∼1.5 and 2.4 mA/cm² are obtained for pristine and optimum 8% Mo-doped BVO electrodes, respectively, in the absence of Na₂SO₃. Onset potential values as low as ∼0.1 and 0.3 V vs RHE are achieved with pristine and Mo-doped BVO films for sulfite and water oxidation, respectively. The increased photocurrent density with Mo doping is attributed to enhanced charge carrier density and film conductivity as confirmed by PEC and Mott–Schottky analyses. Because of the dense high quality polycrystalline structure, the DLI-CVD fabricated Mo-doped BVO electrodes exhibit substantial stability under water and sulfite oxidation conditions without any protective layer and/or oxygen evolution cocatalysts. Scanning electrochemical microscopy (SECM) studies confirm the low porosity of Mo:BVO films and production of oxygen in a local area of Mo:BVO electrode under light illumination.