Visualizing Overall Water Splitting on Single Microcrystals of Phosphorus-Doped BiVO4 by Photo-SECM

Particulate bismuth vanadate (BiVO4) has attracted considerable interest as a promising photo(electro)catalyst for visible-light-driven water oxidation; however, overall water splitting (OWS) has been difficult to attain because its conduction band is too positive for efficient hydrogen evolution. Using photoscanning electrochemical microscopy (photo-SECM) with a chemically modified nanotip, we visualized for the first time the OWS at a single truncated bipyramidal microcrystal of phosphorus-doped BiVO4. The tip simultaneously served as a light guide to illuminate the photocatalyst and an electrochemical nanoprobe to observe and quantitatively measure local oxygen and hydrogen fluxes. The obtained current patterns for both O-2 and H-2 agree well with the accumulation of photogenerated electrons and holes on {010} basal and {110} lateral facets, respectively. The developed experimental approach is an important step toward nanoelectrochemical mapping of the activity of photocatalyst particles at the subfacet level.

Automated summary

Using photoscanning electrochemical microscopy, the overall water splitting phenomenon of phosphorus-doped BiVO4 microcrystals was visualized for the first time, and the local oxygen and hydrogen fluxes were successfully measured. This study is significant for understanding the activity of photocatalysts.