Charge separation in facet-engineered chalcogenide photocatalyst: a selective photocorrosion approach.

Finding active sites for photocatalytic reduction and oxidation allows the mechanistic understanding of a given reaction, ensuring the rational design and fabrication of an efficient photocatalyst. Herein, using well-shaped Cu2WS4 decahedra as model photocatalysts, we demonstrated that photoinduced oxidative etching could be considered as an indication of the photooxidation reaction sites of chalcogenide photocatalyst as it only occurred on {101} facets of Cu2WS4 during photocatalytic hydrogen production. The photocatalytic reduction reaction, in contrast, was confined on its {001} facets. Based on this finding, the photocatalytic activity of Cu2WS4 decahedra could be further tailored by controlling the ratio of {001}/{101} facets. Thus, this work provides a general route to the determination of reactive sites on shaped chalcogenide photocatalysts.