Fifteen commercial titania (titanium(IV) oxide; TiO 2 ) powders were modified with gold by photodeposition to prepare photocatalysts that work under irradiation with light in the visible range (vis). The gold-modified titania (Au/TiO 2 ) powders were characterized by diffuse reflectance spectroscopy (DRS), field-emission scanning electron microscopy (FE-SEM), scanning transmission microscopy (STEM) and X-ray powder diffraction analysis (XRD). It was shown that all tested powders could absorb visible light with an absorption maximum at localized surface plasmon resonance (LSPR) wavelengths (530-600 nm) and that the size and shape of gold nanoparticles determined absorption ranges.The photocatalytic activity of Au/TiO 2 powders was examined both under ultraviolet and vis irradiation (mainly >450 nm) for acetic acid and 2-propanol photooxidation. It was found that the activity depended strongly on gold and titania properties, such as particle size and shape, surface area and crystalline form. Under vis irradiation, large rutile particles loaded with gold particles of a wide range of sizes showed the highest level of photocatalytic activity, possibly due to greater light absorption ability in a wide wavelength range resulting from transverse and longitudinal LSPR of rod-like gold particles. Action spectrum analyses showed that visible light-induced oxidation of organic compounds by aerated gold-titania suspensions was initiated by excitation of LSPR absorption of gold. Although photocatalytic activity of nanosized gold particles under vis irradiation with a wavelength of ca. 430 nm and catalytic activity of goldmodified titania during dark reaction were also found, it was shown that the activities of 2 Au/TiO 2 particles originated from activation of LSPR of gold by light of wavelength of 530-650 nm. Participation of molecular oxygen as an electron acceptor and titania as a conductor of electrons was suggested by comparison with results obtained under deaerated conditions and results obtained using a system containing gold-deposited silica instead of gold-titania, respectively. On the basis of these results, the mechanism of visible light-induced oxidation of organic compounds on gold-titania is proposed. IntroductionTitanium(IV) oxide (TiO 2 ; titania) is an inexpensive particulate material that is readily available and has substantial photocatalytic activity, stability toward inorganic and organic compounds and non-toxicity. 1 However, one drawback of titania is that it can only be excited by ultraviolet light, i.e., with wavelengths shorter than ca. 400 nm.Therefore, only a very small portion of solar radiation (3-5%) can be utilized to drive chemical reactions. 2 Thus, extension of its absorption wavelength range to the visible region (vis) is an important issue. Another important issue is improvement of quantum efficiency, i.e., an efficiency of utilization of the photoexcited state of photocatalysts, since an electronic excited state of titania is deactivated by recombination of electrons and holes to lower qu...

Action spectrum analyses showed that visible light-induced oxidation of 2-propanol by aerated gold-modified titanium(IV) oxide (titania) suspensions is initiated by excitation of gold surface plasmon, and polychromatic irradiation experiments revealed that the photocatalytic reaction rate depends strongly on properties of titania, such as particle size, surface area and crystalline form (anatase or rutile) and on properties of gold deposits, such as size and shape.

Ag and CuO nanoparticles (NPs) synthesized on the surface of commercial TiO 2 (P25) by radiolytic reduction were characterized by diffuse reflectance spectroscopy (DRS), transmission electron microscopy (TEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), energydispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS). In the case of modification with silver and copper, results from HAADF-STEM, EDS, XPS, and XAS show that Ag@CuO nanoparticles (large silver cores decorated with small clusters of CuO) were obtained on TiO 2 −P25. The photocatalytic properties of bare and modified TiO 2 −P25 were studied for phenol photodegradation and for acetic acid oxidation under UV and visible irradiation. The mechanisms involved in photocatalysis were studied by time-resolved microwave conductivity (TRMC) and action spectra (AS). The electronic properties of the surface-modified TiO 2 −P25 were studied by TRMC to follow the charge-carrier dynamics. The modification with Ag nanoparticles or CuO nanoclusters induces an increase in the photocatalytic activity under both UV and visible light. The photocatalytic activity of Ag@CuO/P25 is higher under UV light but lower under visible light compared to the activity of CuO/P25 and Ag/P25. TRMC measurements show that surface modification of TiO 2 −P25 with Ag, CuO, and Ag@CuO nanoparticles plays a role in charge-carrier separation, increasing the activity under UV-light, and that Ag@CuO NPs are more efficient electron scavengers than Ag NPs and CuO nanoclusters. The localized surface plasmon resonance (LSPR) of Ag NPs and the narrow band gap of CuO induce an activity under visible light. The TRMC shows also responses under visible-light irradiation at different fixed wavelengths indicating that electrons are injected from Ag NPs in the conduction band (CB) of TiO 2 −P25. Moreover, under visible light, the photocatalytic activity of CuO/P25 is higher than that of plasmonic Ag/P25. CuO is able to activate TiO 2 −P25 in a wider range of wavelengths under visible-light irradiation, compared to the activation achieved by the presence of silver. The action spectra correlate with the absorption spectra for irradiation wavelengths in the range of 350−470 nm proving that decomposition of acetic acid is carried out by a photocatalytic mechanism.