In Situ Shape Change of Au Nanoparticles on TiO(2) by CdS Photodeposition: Its Near-Field Enhancement Effect on Photoinduced Electron Injection from CdS to TiO(2)

[Image: see text] Hemisphere-like gold nanoparticles (NPs) were loaded on TiO(2) (Au/TiO(2)) by the deposition–precipitation method. Subsequent photodeposition of CdS on the Au surface of Au/TiO(2) at 50 °C yields Au(core)–CdS(shell) hybrid quantum dots with a heteroepitaxial (HEPI) junction on TiO(2) (Au@#CdS/TiO(2)), whereas nonHEPI Au@CdS/TiO(2) was formed by CdS photodeposition at 25 °C. In the HEPI system, the shape of the Au core changes to an angular shape, whereas it remains in a hemisphere-like shape in the nonHEPI system. The hot photodeposition technique was applied to the Au NP-loaded mesoporous TiO(2) nanocrystalline film (Au/mp-TiO(2)). Using Au@CdS/mp-TiO(2) and Au@#CdS/mp-TiO(2) as the photoanodes, two-electrode quantum dot-sensitized photoelectrochemical cells were fabricated for hydrogen (H(2)) generation from water, and the performances of the cells were evaluated under illumination of simulated sunlight. In the photocurrent and the rate of H(2) evolution, the Au@#CdS/mp-TiO(2) photoanode cell surpasses the CdS/mp-TiO(2) and Au@CdS/mp-TiO(2) ones. Three-dimensional finite-difference time-domain calculations for the model systems indicated that the angular shape Au core generates an intense electric field at the corners and edges, extending the electric field distribution over the Au core–CdS shell interface. The striking shape effect on the cell performances can originate from the promotion of the CdS excitation and charge separation due to the near-field enhancement by the deformed Au core.