Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 14, Issue 19, Pages 7065-7075Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2cp40807d
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Funding
- Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy [DE-FG02-09ER16119]
- Welch Foundation [F-1436]
- National Science Foundation [0618242]
- University of Texas at Austin Cockrell School of Engineering
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Porous, nanostructured BiVO4 films are incorporated with Mo and W by simultaneous evaporation of Bi, V, Mo, and W in vacuum followed by oxidation in air. Synthesis parameters such as the Bi : V: Mo : W atomic ratio and deposition angle are adjusted to optimize the films for photoelectrochemical (PEC) water oxidation. Films synthesized with a Bi : V: Mo: W atomic ratio of 46 : 46 : 6 : 2 (6% Mo, 2% W) demonstrate the best PEC performance with photocurrent densities 10 times higher than for pure BiVO4 and greater than previously reported for Mo and W containing BiVO4. The films consist of a directional, nanocolumnar layer beneath an irregular surface structure. Backside illumination utilizes light scattering off the irregular surface structure resulting in 30-45% higher photocurrent densities than for frontside illumination. To improve the kinetics for water oxidation Pt is photo-deposited onto the surface of the 6% Mo, 2% W BiVO4 films as an electrocatalyst. These films achieve quantum efficiencies of 37% at 1.1 V vs. RHE and 50% at 1.6 V vs. RHE for 450 nm light.
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