Plasmon-induced photoelectrochemistry in the visible region was studied at gold nanoparticle-nanoporous TiO(2) composites (Au-TiO(2)) prepared by photocatalytic deposition of gold in a porous TiO(2) film. Photoaction spectra for both the open-circuit potential and short-circuit current were in good agreement with the absorption spectrum of the gold nanoparticles in the TiO(2) film. The gold nanoparticles are photoexcited due to plasmon resonance, and charge separation is accomplished by the transfer of photoexcited electrons from the gold particle to the TiO(2) conduction band and the simultaneous transfer of compensative electrons from a donor in the solution to the gold particle. Besides its low-cost and facile preparation, a photovoltaic cell with the optimized electron mediator (Fe(2+/3+)) exhibits an optimum incident photon to current conversion efficiency (IPCE) of 26%. The Au-TiO(2) can photocatalytically oxidize ethanol and methanol at the expense of oxygen reduction under visible light; it is potentially applicable to a new class of photocatalysts and photovoltaic fuel cells.
Nanoporous TiO(2) films loaded with gold and silver nanoparticles exhibit negative potential changes and anodic currents in response to visible light irradiation, so that the films would potentially be applicable to inexpensive photovoltaic cells, photocatalysts and simple plasmon sensors.
Glutathione‐protected Au25 as well as Aun (n = 15, 18, 22, 29, 33, 39) clusters adsorbed on TiO2 electrodes exhibit anodic photocurrents and negative shifts of photopotential in response to visible and/or near‐infrared light (400 < λ < 900 nm) on the basis of HOMO−LUMO and similar transitions, indicating that the electrodes are applicable to the conversion of light to electricity (see figure).
Ag-TiO(2) films exhibiting multicolor photochromism were prepared by photoelectrochemical reduction of Ag(+) to Ag nanoparticles in nanoporous TiO(2) films under UV light. Color of the Ag-TiO(2) film, initially brownish-gray, changes under a colored visible light to the color of the light and reverts to brownish-gray under UV light. Their chromogenic properties were improved by simultaneous irradiation for Ag deposition with UV and blue lights to suppress the formation of anisotropic Ag particles. Nonvolatilization of a color image was also achieved by removing Ag(+) that was generated during the irradiation with a colored light. Once nonvolatilized, the image can be reproduced by UV light, even after the image is discolored under white light. This new effect evidenced that nanopores in the TiO(2) film determine the resonance wavelengths of the Ag particles, as their molds. In addition, solvatochromic behavior of the Ag-TiO(2) film proved that nanospaces left around the Ag nanoparticles affect the resonance wavelengths of the Ag particles.
Electrons transfer from plasmonic nanoparticles to semiconductors by exploiting the energy of light, and this effect is applied to photovoltaics, photocatalysis, sensing, photochromisms, photoswitchable functionalities and nanofabrications.
TiO2 coatings are known to protect some metals, including type 304 stainless steel, from
corrosion on the basis of its reductive energy generated under UV irradiation. A TiO2 coating
is coupled with a WO3 coating as an electron pool, in which the reductive energy can be
stored. A WO3 film on a type 304 stainless steel plate can be charged by a UV-irradiated
TiO2 coating on the same plate, in a 3 wt % NaCl aqueous solution, pH 5. The charged WO3
coating can protect the stainless steel plate from the corrosion for a while even after the UV
light is turned off. Thus, the TiO2 coating protects the plate and charges the WO3 coating
during the day, and the charged WO3 coating protects the plate during the night. The charge−discharge cycles are repeatable. A TiO2−WO3 composite coating also has the same effects.
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