Anatase and rutile crystallites were isolated from Degussa (Evonik) P25 by selective dissolution with a hydrogen peroxide-ammonia mixture and diluted hydrofluoric acid, respectively, and used as standard samples for calibration curves of X-ray diffraction analyses.The results showed that P25 contains more than 70% anatase with a minor amount of rutile and a small amount of amorphous phase. The composition anatase/rutile/amorphous could be determined by analysis of P25 mixed with an internal standard, nickel(II) oxide.However, it was also found that the composition of P25 used in this study was inhomogeneous and changed depending on the position of sampling from the same package.Comparison of activities of original P25 and reconstructed P25 with those of isolated anatase and rutile particles suggested a less probable synergetic effect of the co-presence of anatase and rutile.

Visible light-driven water splitting using cheap and robust photocatalysts is one of the most exciting ways to produce clean and renewable energy for future generations. Cutting edge research within the field focuses on so-called “Z-scheme” systems, which are inspired by the photosystem II–photosystem I (PSII/PSI) coupling from natural photosynthesis. A Z-scheme system comprises two photocatalysts and generates two sets of charge carriers, splitting water into its constituent parts, hydrogen and oxygen, at separate locations. This is not only more efficient than using a single photocatalyst, but practically it could also be safer. Researchers within the field are constantly aiming to bring systems toward industrial level efficiencies by maximizing light absorption of the materials, engineering more stable redox couples, and also searching for new hydrogen and oxygen evolution cocatalysts. This review provides an in-depth survey of relevant Z-schemes from past to present, with particular focus on mechanistic breakthroughs, and highlights current state of the art systems which are at the forefront of the field.

Tungsten oxide loaded with nanoparticulate platinum is demonstrated to exhibit high activity for the decomposition of organic compounds both in liquid and gas phases; the activity was almost comparable to that of TiO2 under UV light irradiation and much higher than that of nitrogen-doped TiO2 under visible irradiation.

A two-step photocatalytic water splitting (Z-scheme) system consisting of a modified ZrO(2)/TaON species (H(2) evolution photocatalyst), an O(2) evolution photocatalyst, and a reversible donor/acceptor pair (i.e., redox mediator) was investigated. Among the O(2) evolution photocatalysts and redox mediators examined, Pt-loaded WO(3) (Pt/WO(3)) and the IO(3)(-)/I(-) pair were respectively found to be the most active components. Combining these two components with Pt-loaded ZrO(2)/TaON achieved stoichiometric water splitting into H(2) and O(2) under visible light, achieving an apparent quantum yield of 6.3% under irradiation by 420.5 nm monochromatic light under optimal conditions, 6 times greater than the yield achieved using a TaON analogue. To the best of our knowledge, this is the highest reported value to date for a nonsacrificial visible-light-driven water splitting system. The high activity of this system is due to the efficient reaction of electron donors (I(-) ions) and acceptors (IO(3)(-) ions) on the Pt/ZrO(2)/TaON and Pt/WO(3) photocatalysts, respectively, which suppresses undesirable reverse reactions involving the redox couple that would otherwise occur on the photocatalysts. Photoluminescence and photoelectrochemical measurements indicated that the high activity of this Z-scheme system results from the moderated n-type semiconducting character of ZrO(2)/TaON, which results in a lower probability of undesirable electron-hole recombination in ZrO(2)/TaON than in TaON.

The photoelectrochemical properties of porous BiVO4 thin-film electrodes on conducting glass for H2 production from water under visible light were investigated. BiVO4 films were prepared by the metal-organic decomposition method, and particles were 90-150 nm in diameter. Under visible-light irradiation, H2 and O2 evolved in a stoichiometric ratio (H2/O2 = 2) from an aqueous solution of Na2SO4 with an external bias. The photocurrent increased with addition of methanol. The band structure of BiVO4 was investigated by open-circuit potential, flat-band potential, X-ray photoelectron spectroscopy, and calculations based on density functional theory. The top of the valence-band potential of BiVO4 was shifted negatively compared to the potentials of the conventional oxide semiconductors without Bi. We surmise that hybridization between the O-2p and Bi-6s orbitals might contribute to the negative shift of the BiVO4 valence band. Treatment with an aqueous solution of AgNO3 improved the photocurrent of the BiVO4 electrode significantly. The maximum incident photon-to-current conversion efficiency at 420 nm was 44%. This value was the highest among mixed-oxide semiconductor electrodes under visible light irradiation. AgNO3 treatment also improved the stability of the photocurrent. The Ag+ ion in/on the BiVO4 catalyzed the intrinsic photogeneration of oxygen with the holes.

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...

The porous oxynitride TaON film electrode prepared on conducting glass (FTO) showed significantly high quantum efficiency (IPCE = ca. 76% at 400 nm at 0.6 V vs Ag/AgCl) in an aqueous Na(2)SO(4) solution, after loading of IrO(2) x nH(2)O nanoparticles as a cocatalyst for water oxidation. Overall water splitting into H(2) and O(2) under visible light was demonstrated using an IrO(2) x nH(2)O-loaded TaON photoanode combined with a Pt electrode under an externally applied bias (0.6-1 V).

The stoichiometric splitting of water into H2 and O2 (H2/O2 = 2) under visible light irradiation (lambda > 420 nm) took place for the first time using a mixture of Pt-WO3 and Pt-SrTiO3 (Cr-Ta-doped) photocatalysts and an IO3-/I- shuttle redox mediator.