Reductive photocatalysis and smart inks

Semiconductor-sensitised photocatalysis is a well-established and growing area of research, innovation and commercialisation; the latter being mostly limited to the use of TiO2 as the semiconductor. Most of the work on semiconductor photocatalytic systems uses oxygen as the electron acceptor and explores a wide range of electron donors; such systems can be considered to be examples of oxidative photocatalysis, OP. OP underpins most current examples of commercial self-cleaning materials, such as: glass, tiles, concrete, paint and fabrics. OP, and its myriad of applications, have been reviewed extensively over the years both in this journal and elsewhere. However, the ability of TiO2, and other semiconductor sensitisers, to promote reductive photocatalysis, RP, especially of dyes, is significant and, although less well-known, is of growing importance. In such systems, the source of the electrons is some easily oxidised species, such as glycerol. One recent, significant example of a RP process is with respect to photocatalyst activity indicator inks. paiis, which provide a measure of the activity of a photocatalytic film under test via the rate of change of colour of the dye in the ink coating due to irreversible RP. In contrast, by incorporating the semiconductor sensitiser in the ink, rather than outside it, it is possible to create an effective UV dosimeter, based on RP, which can be used as a sun-burn warning indicator. In the above examples the dye is reduced irreversibly, but when the photocatalyst in an ink is used to reversibly photoreduce a dye, a novel, colourimetric oxygen-sensitive indicator ink can be created, which has commercial potential in the food packaging industry. Finally, if no dye is present in the ink, and the semiconductor photocatalyst-loaded ink film coats an easily reduced substrate, such as a metal oxide film, then it can be used to reduce the latter and so, for example, clean up tarnished steel. The above are examples of smart inks, i.e. inks that are active and provide either dynamic information (such as UV dose or O2 level) or a useful function (such as tarnish removal), and all work via a RP process and are reviewed here

Wavelet phase coherence analysis: Application to a quiet-sun magnetic element

A new application of wavelet analysis is presented that utilizes the inherent phase information residing within the complex Morlet transform. The technique is applied to a weak solar magnetic network region, and the temporal variation of phase difference between TRACE 1700 Angstrom and SOHO/SUMER C II 1037 Angstrom intensities is shown. We present, for the first time in an astrophysical setting, the application of wavelet phase coherence, including a comparison between two methods of testing real wavelet phase coherence against that of noise. The example highlights the advantage of wavelet analysis over more classical techniques, such as Fourier analysis, and the effectiveness of the former to identify wave packets of similar frequencies but with differing phase relations is emphasized. Using cotemporal, ground-based Advanced Stokes Polarimeter measurements, changes in the observed phase differences are shown to result from alterations in the magnetic topology.

Propagating waves and magnetohydrodynamic mode coupling in the quiet-sun network

High-cadence multiwavelength optical observations were taken with the Dunn Solar Telescope at the National Solar Observatory, Sacramento Peak, accompanied by Advanced Stokes Polarimeter vector magnetograms. A total of 11 network bright points (NBPs) have been studied at different atmospheric heights using images taken in wave bands centered on Mg I b(1) - 0.4 Angstrom, Halpha, and Ca II K-3. Wavelet analysis was used to study wave packets and identify traveling magnetohydrodynamic waves. Wave speeds were estimated through the temporal cross-correlation of signals, in selected frequency bands of wavelet power, in each wavelength. Four mode-coupling cases were identified, one in each of four of the NBPs, and the variation of the associated Fourier power with height was studied. Three of the detected mode-coupling, transverse-mode frequencies were observed in the 1.2-1.6 mHz range (mean NBP apparent flux density magnitudes over 99-111 Mx cm(-2)), with the final case showing 2.0-2.2 mHz (with 142 Mx cm(-2)). Following this, longitudinal-mode frequencies were detected in the range 2.6-3.2 mHz for three of our cases, with 3.9-4.1 mHz for the remaining case. After mode coupling, two cases displayed a decrease in longitudinal-mode Fourier power in the higher chromosphere.

Ultraviolet oscillations in the chromosphere of the quiet Sun

Quiet-Sun oscillations in the four Transition Region and Coronal Explorer (TRACE) ultraviolet passbands centered on 1700, 1600, 1216, and 1550 Angstrom are studied using a wavelet-based technique. Both network and internetwork regions show oscillations with a variety of periods and lifetimes in all passbands. The most frequent network oscillation has a period of 283 s, with a lifetime of 2-3 cycles in all passbands. These oscillations are discussed in terms of upwardly propagating magnetohydrodynamic wave models. The most frequent internetwork oscillation has a period of 252 s, again with a lifetime of 2-3 cycles, in all passbands. The tendency for these oscillations to recur in the same position is discussed in terms of "persistent flashers." The network contains greater oscillatory power than the internetwork at periods longer than 300 s in the low chromosphere. This value is shown to decrease to 250 s in the high chromosphere. The internetwork also displays a larger number of short-lifetime, long-period oscillations than the network, especially in the low chromosphere. Both network and internetwork regions contain a small number of nonrecurring long-lifetime oscillations.

Electron densities in the coronae of the Sun and Procyon from extreme-ultraviolet emission line ratios in Fe XI

New R-matrix calculations of electron impact excitation rates for Fe XI are used to determine theoretical emission line ratios applicable to solar and stellar coronal observations. These are subsequently compared to solar spectra of the quiet Sun and an active region made by the Solar EUV Rocket Telescope and Spectrograph (SERTS-95), as well as Skylab observations of two flares. Line blending is identified, and electron densities of 10(9.3), 10(9.7), greater than or equal to 10(10.8), and greater than or equal to 10(11.3) cm(-3) are found for the quiet Sun, active region, and the two flares, respectively. Observations of the F5 IV-V star Procyon, made with the Extreme Ultraviolet Explorer (EUVE) satellite, are compared and contrasted with the solar observations. It is confirmed that Procyon's average coronal conditions are very similar to those seen in the quiet Sun, with N-e = 10(9.4) cm(-3). In addition, although the quiet Sun is the closest solar analog to Procyon, we conclude that Procyon's coronal temperatures are slightly hotter than solar. A filling factor of 25(-12)(+38)% was derived for the corona of Procyon.

A review of the selective reduction of NOx, with hydrocarbons under lean-burn conditions with non-zeolitic oxide and platinum group metal catalysts

Research on the selective reduction of NOx with hydrocarbons under lean-burn conditions using non-zeolitic oxides and platinum group metal (PGM) catalysts has been critically reviewed. Alumina and silver-promoted alumina catalysts have been described in detail with particular emphasis on an analysis of the various reaction mechanisms that have been put forward in the literature. The influence of the nature of the reducing agent, and the preparation and structure of the catalysts have also been discussed and rationalised for several other oxide systems. It is concluded for non-zeolitic oxides that species that are strongly adsorbed on the surface, such as nitrates/nitrites and acetates, could be key intermediates in the formation of various reduced and oxidised species of nitrogen, the further reaction of which leads eventually to the formation of molecular nitrogen. For the platinum group metal catalysts, the different mechanisms that have been proposed in the literature have been critically assessed. It is concluded that although there is indirect, mainly spectroscopic, evidence for various reaction intermediates on the catalyst surface, it is difficult to confirm that any of these are involved in a critical mechanistic step because of a lack of a direct quantitative correlation between infrared and kinetic measurements. A simple mechanism which involves the dissociation of NO on a reduced metal surface to give N(ads) and O(ads), with subsequent desorption of N-2 and N2O and removal of O(ads) by the reductant can explain many of the results with the platinum group metal catalysts, although an additional contribution from organo-nitro-type species may contribute to the overall NOx reduction activity with these catalysts.

An investigation of catalysts for the on board synthesis of NH3. A possible route to low temperature NOx reduction for lean-burn engines

Platinum group metal catalysts have been investigated for the formation of NH3 from NO + H-2 at low temperatures in the absence and presence of CO. Although CO inhibits the formation of NH3, substantial amounts are still observed with a Pt catalyst. By combining Pt with a support (ceria-zirconia) that has low temperature NOx storage characteristics it has been shown in transient experiments that NH3 can be formed and stored in situ under rich conditions, and may then be used to reduce NOx under lean burn conditions.

Making hay while the sun shines? Socio-economic change, cereal production and climatic deterioration in Early Medieval Ireland

The Early Medieval period in Ireland (c. A.D. 400–1150) has been the subject of much archaeological and historical study. The recent application of various forms of archaeological sciences, as well as palaeoenvironmental studies, to the archaeological record have, however, added fresh impetus to this study area. It seems increasingly evident that significant changes to economy and society occurred during this period and were not recorded in detail in the contemporary documentary sources. This paper will attempt to outline those changes and to assess whether, or to what extent, they were influenced by climate change.