Size Dependent Plasmonic Effect on BiVO(4) Photoanodes for Solar Water Splitting

Plasmonic nanostructures show great promise in enhancing the solar water splitting efficiency due to their ability to confine light to extremely small volumes inside semiconductors. While size plays a critical role in the plasmonic performance of Au nanoparticles (AuNPs), its influence on plasmon-assisted water splitting is still not fully understood. This holds especially true for low band gap semiconductors, for which interband excitations occur in wavelength regions that overlap with plasmonic resonances. Here, BiVO(4) films are modified with AuNPs of diameters varying from 10 to 80 nm to study the size dependence of the plasmonic effect. Plasmon resonance energy transfer (PRET) is found to be the dominant effect in enhancing the water splitting efficiency of BiVO(4). “Hot electron” injection effect is weak in the case of BiVO(4)/AuNP. This is attributed to the interband excitation of BiVO(4), which is unfavourable for the hot electrons accumulation in BiVO(4) conduction band. The resonant scattering effect also contributes to the enhanced water splitting efficiency for the larger diameter AuNPs. It is also for the first time found that higher PRET effect can be achieved at larger off-normal irradiation angle.