Enhanced Visible-Light Photocatalytic H₂ Evolution in Cu₂O/Cu₂Se Multilayer Heterostructure Nanowires Having {111}...

It is rather challenging to develop photocatalysts based on narrow-band-gap semiconductors for water splitting under solar irradiation. Herein, we synthesized the Cu₂O/Cu₂Se multilayer heterostructure nanowires exposing {111} crystal facets by a hydrothermal reaction of Se with Cu and KBH₄ in ethanol amine aqueous solution and subsequent annealing in air. The photocatalytic H₂ production activity of Cu₂O/Cu₂Se multilayer heterostructure nanowires is dramatically improved, with an increase on the texture coefficient of Cu₂O(111) and Cu₂Se(111) planes, and thus the exposed {111} facets may be the active surfaces for photocatalytic H₂ production. On the basis of the polar structure of Cu₂O {111} and Cu₂Se {111} surfaces, we presented a model of charge separation between the Cu-Cu₂Se(111) and O-Cu₂O(1̅ 1̅ 1̅) polar surfaces. An internal electric field is created between Cu-Cu₂Se(111) and O-Cu₂O(1̅ 1̅ 1̅) polar surfaces, because of spontaneous polarization. As a result, this internal electric field drives the photocreated charge separation. The oxidation and reduction reactions selectively occur at the negative O-Cu₂O(1̅ 1̅ 1̅) and the positive Cu-Cu₂Se(111) surfaces. The polar surface-engineering may be a general strategy for enhancing the photocatalytic H₂-production activity of semiconductor photocatalysts. The charge separation mechanism not only can deepen the understanding of photocatalytic H₂ production mechanism but also provides a novel insight into the design of advanced photocatalysts, other photoelectric devices, and solar cells.