Photoelectrochemical (PEC) water splitting is a promising technology that uses light absorbing semiconductors to convert solar energy directly into a chemical fuel (i.e., hydrogen). PEC water splitting has the potential to become a key technology in achieving a sustainable society, if high solar to fuel energy conversion efficiencies are obtained with earth abundant materials. This review article discusses recent developments and discoveries in the mechanisms by which the localized surface plasmon resonance (LSPR) in metallic nanoparticles can increase or complement a neighbouring semiconductor in light absorption for catalytic water splitting applications. These mechanisms can mitigate the intrinsic optical limitations of semiconductors (e.g., metal oxides) for efficient solar water splitting. We identify four types of enhancement mechanisms in the recent literature: (i) light scattering, (ii) light concentration, (iii) hot electron injection (HEI), and (iv) plasmon-induced resonance energy transfer (PIRET). (i) Light scattering and (ii) light concentration are light trapping mechanisms that can increase the absorption of light with energies above the semiconductor optical band-edge. These two mechanisms are ideal to enhance the absorption of promising semiconductors with narrow bandgap energies that suffer from limited absorption coefficients and bulk charge recombination. On the other hand, (iii) HEI and the recently discovered (iv) PIRET are mechanisms that can enhance the absorption also below the semiconductor optical band-edge. Therefore, HEI and PIRET have the potential to extend the light utilization to visible and near-infrared wavelengths of semiconductors with excellent electrochemical properties, but with large bandgap energies. New techniques and theories that have been developed to elucidate the above mentioned plasmonic mechanisms are presented and discussed for their application in metal oxide photoelectrodes. Finally, other plasmonic and non-plasmonic effects that do not increase the device absorption, but affect the electrochemical properties of the semiconductor (e.g., charge carrier transport) are also discussed, since a complete understanding of these phenomena is fundamental for the design of an efficient plasmonic NP-semiconductor water splitting device.

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Ag nanoparticles (NPs) are deposited on BiVO4 photoanodes to study their effect on the photoelectrochemical (PEC) water splitting performance of the semiconductor. 15 nm light-absorbing NPs and 65 nm light scattering NPs were studied separately to compare their light trapping ability for enhancing the semiconductor's absorption through light concentration and light scattering, respectively. The 15 nm NPs enhanced the BiVO4 external quantum efficiency throughout the semiconductor's absorption range (e.g., ≈2.5 fold at λ=400 nm). However, when a hole scavenger was added to the electrolyte, no enhancement was observed upon NP deposition, indicating that the NPs only facilitate the injection of holes from the semiconductor surface to the electrolyte but do not enhance its absorption. On the other hand, the 65 nm scattering NPs not only facilitated hole injection to the electrolyte, but also enhanced the absorption of the semiconductor (by ≈6 %) through light scattering. Such a dual effect, i.e., of enhancing both the surface properties and the absorption of the semiconductor, makes light scattering Ag NPs an ideal decoration for PEC water splitting photoelectrodes.
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