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.
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