Plasmon-mediated photocatalytic activity of wet-chemically prepared ZnO nanowire arrays

We report on measurements and simulations of the efficient sunlight-driven and visible-active photocatalysts composed of plasmonic metal nanoparticles and ZnO nanowire (NW) arrays fabricated via an all-wet-chemical route. Because of the coupling between the ZnO dielectric response and the excitation of the Ag or Au nanoparticles, efficient electronic excitation can be induced in the vicinity of the metal-ZnO interfaces because optically-excited plasmonic particles can not only concentrate the electromagnetic field at the ZnO/particle interface, but also act as efficient sources of plasmonic hot electrons to be injected into the conduction band of the ZnO catalyst. The catalytic activities of the fabricated ZnO NWs are examined by photodegradation of methylene blue and by photocurrent measurements in a photovoltaic configuration. Numerical electromagnetic simulations were used to understand the behavior of the light on the nanometer-scale to clarify the catalytic enhancement mechanisms in both the ultraviolet (UV) and visible (VIS) regions. In addition, simulation results indicated that a near-surface normal but slightly tilted ZnO NW array geometry would provide an increased optical path length and enhanced multiple scattering and absorption processes arising from the localized surface plasmon resonances of the nanoparticles. The results obtained here clarify the role of the plasmon resonance and provide us with useful knowledge for the development of metal-oxide nano-hybrid materials for solar energy conversion. Relation among (1) photocatalytic activity (2) nano-scale electromagnetic field distribution and (3) hot electron injection of metal loaded ZnO wires was elucidated.