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Water splitting on composite plasmonic-metal/semiconductor photoelectrodes: evidence for selective plasmon-induced formation of charge carriers near the semiconductor surface.

A critical factor limiting the rates of photocatalytic reactions, including water splitting, on oxide semiconductors is the high rate of charge-carrier recombination. In this contribution, we demonstrate that this issue can be alleviated significantly by combining a semiconductor photocatalyst with tailored plasmonic-metal nanostructures. Plasmonic nanostructures support the formation of resonant surface plasmons in response to a photon flux, localizing electromagnetic energy close to their surfaces. We present evidence that the interaction of localized electric fields with the neighboring semiconductor allows for the selective formation of electron/hole (e(-)/h(+)) pairs in the near-surface region of the semiconductor. The advantage of the formation of e(-)/h(+) pairs near the semiconductor surface is that these charge carriers are readily separated from each other and easily migrate to the surface, where they can perform photocatalytic transformations.