Light-Driven Overall Water Splitting Enabled by a Photo-Dember Effect Realized on 3D Plasmonic Structures.

Photoelectric conversion driven by sunlight has a broad range of energy/environmental applications (e.g., in solar cells and water splitting). However, difficulties are encountered in the separation of photoexcited charges. Here, we realize a long-range (∼1.5 μm period) electric polarization via asymmetric localization of surface plasmons on a three-dimensional silver structure (3D-Ag). This visible-light-responsive effect-the photo-Dember effect, can be analogous to the thermoelectric effect, in which hot carriers are thermally generated instead of being photogenerated. The induced electric field can efficiently separate photogenerated charges, enabling sunlight-driven overall water splitting on a series of dopant-free commercial semiconductor particles (i.e., ZnO, CeO2, TiO2, and WO3) once they are combined with the 3D-Ag substrate. These photocatalytic processes can last over 30 h on 3D-Ag+ZnO, 3D-Ag+CeO2, and 3D-Ag+TiO2, thus demonstrating good catalytic stability for these systems. Using commercial WO3 powder as a reference, the amount of O2 generated with 3D-Ag+CeO2 surpasses even its recently reported counterpart in which sacrificial reagents had to be involved to run half-reactions. This plasmon-mediated charge separation strategy provides an effective way to improve the efficiency of photoelectric energy conversion, which can be useful in photovoltaics and photocatalysis.