A Novel, Fast-Responding, Indicator Ink for Thin Film Photocatalytic Surfaces

A new photocatalyst indicator ink based on methylene blue (MB) is described that allows the presence and activity of a thin (15 nm) photocatalytic film to be assessed in seconds. The ink is very stable (shelf life > 6 months) and the color change (blue to colorless) striking. The ink utilizes a sacrificial electron donor, glycerol, to trap the photogenerated holes, leaving the photogenerated electrons to react with MB to produce its. reduced, leuco, form (LMB). The efficacy of the MB ink is due to the presence of acid in its formulation, which curtails significantly. the otherwise usual, rapid reoxidation of LMB by ambient O-2.

Platinum Group Metals and Their Oxides in Semiconductor Photosensitisation BASIC PRINCIPLES, METAL PHOTODEPOSITION AND WATER PHOTOSPLITTING REACTIONS

The basic principles of semiconductor photochemistry, particularly using titania as a semiconductor photocatalyst, are discussed. When a platinum group metal or its oxide is deposited onto the surface of a sensitised semiconductor the overall efficiency of the reactions it takes part in are often improved, especially when the deposits are used as hydrogen and oxygen catalysts, respectively. Methods of depositing metal or metal oxide are examined, and a particular focus is given to a photodeposition process that uses a sacrificial electron donor. Platinum group metal and platinum group metal oxide coated semiconductor photocatalysts are prominent in heterogeneous systems that are capable of the photoreduction, oxidation and cleavage of water. There is a recent renaissance in work on water-splitting semiconductor-sensitised photosystems, but there are continued concerns over their irreproducibility, longevity and photosynthetic nature.

The water-gas shift reaction over CeO/CuO:Operando SSITKA-DRIFTS-mass spectrometry study of low temperature mechanism

An inverse CeO2/CuO catalyst has been investigated by operando steady-state isotopic transient kinetic analysis (SSITKA) in combination with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) under 3% CO +3% H2O reactant mixture at 473 K with the aim of determining intermediates involved in the water gas shift reaction at relatively low temperatures. Among the various species detected in the infrared spectra which may be involved in the reaction, i.e. formates, copper carbonyls and carbonates, a particular type of carbonate species is identified as a reaction intermediate on the basis of detailed analysis of the spectra during isotopic exchange in comparison with the change in the corresponding isotopically labelled CO2 product. 

Three-dimensional porous carbon nanofiber networks decorated with cobalt-based nanoparticles: A robust electrocatalyst for efficient water oxidation

Electrochemical water splitting used for generating hydrogen has attracted increasingly attention due to energy and environmental issues. It is a major challenge to design an efficient, robust and inexpensive electrocatalyst to achieve preferable catalytic performance. Herein, a novel three-dimensional (3D) electrocatalyst was prepared by decorating nanostructured biological material-derived carbon nanofibers with in situ generated cobalt-based nanospheres (denoted as CNF@Co) through a facile approach. The interconnected porous 3D networks of the resulting CNF@Co catalyst provide abundant channels and interfaces, which remarkably favor both mass transfer and oxygen evolution. The as-prepared CNF@Co shows excellent electrocatalytic activity towards the oxygen evolution reactions with an onset potential of about 0.445 V vs. Ag/AgCl. It only needs a low overpotential of 314 mV to achieve a current density of 10 mA/cm² in 1.0 M KOH. Furthermore, the CNF@Co catalyst exhibits excellent stability towards water oxidation, even outperforming commercial IrO<inf>2</inf> and RuO<inf>2</inf> catalysts.

Heterogeneous oxidation of pyrimidine and alkyl thioethers in ionic liquids over mesoporous Ti or Ti/Ge catalysts

Heterogeneous catalytic oxidation of a series of thioethers (2-thiomethylpyrimidine, 2-thiomethyl-4,6-dimethyl-pyrimidine, 2-thiobenzylpyrimidine, 2-thiobenzyl-4,6-dimethylpyrimidine, thioanisole, and n-heptyl methyl sulfide) was performed in ionic liquids by using MCM-41 and UVM-type mesoporous catalysts containing Ti, or Ti and Ge. A range of triflate, tetrafluoroborate, trifluoroacetate, lactate and bis(trifluoromethanesulfonyl)imide-based ionic liquids were used. The oxidations were carried out by using anhydrous hydrogen peroxide or the urea-hydrogen peroxide adduct and showed that ionic liquids are very effective solvents, achieving greater reactivity and selectivity than reactions performed in dioxane. The effects of halide and acid impurities on the reactions were also investigated. Recycling experiments on catalysts were carried out in order to evaluate Ti leaching and its effect on activity and selectivity.

Photochemical reduction of oxygen adsorbed to nanocrystalline TiO2 films: A transient absorption and oxygen scavenging study of different TiO2 preparations

Transient absorption spectroscopy (TAS) has been used to study the interfacial electron-transfer reaction between photogenerated electrons in nanocrystalline titanium dioxide (TiO2) films and molecular oxygen. TiO2 films from three different starting materials (TiO2 anatase colloidal paste and commercial anatase/rutile powders Degussa TiO2 P25 and VP TiO2 P90) have been investigated in the presence of ethanol as a hole scavenger. Separate investigations on the photocatalytic oxygen consumption by the films have also been performed with an oxygen membrane polarographic detector. Results show that a correlation exists between the electron dynamics of oxygen consumption observed by TAS and the rate of oxygen consumption through the photocatalytic process. The highest activity and the fastest oxygen reduction dynamics were observed with films fabricated from anatase TiO2 colloidal paste. The use of TAS as a tool for the prediction of the photocatalytic activities of the materials is discussed. TAS studies indicate that the rate of reduction of molecular oxygen is limited by interfacial electron-transfer kinetics rather than by the electron trapping/detrapping dynamics within the TiO2 particles.

Assessment of the effectiveness of the guard ring in obtaining a uni-directional flow in an in situ water permeability test

The non-destructive evaluation of the water permeability of concrete structures is a long standing challenge, principally due to the difficulty of achieving a uni-direction flow for computing the water permeability coefficient. The use of a guard ring (GR) was originally proposed for the in situ sorptivity test, but little information can be found for the water permeability test. In this study, the effect of a GR was carefully examined through the flow simulation, which was verified by carrying out experiments. It was observed that the GR can confine the flow near the surface, but cannot achieve a uni-directional flow across the whole depth of flow. To achieve a better performance, it is essential to consider the effects of the size of the inner seal and the GR and the significant interaction between these two. The analysis of the experimental data has indicated that the GR influences the flow for porous concretes, but there is no significant effect for dense concretes. Further investigation, validated using the flow-net theory, has shown a strong correlation between the water permeability coefficients obtained with the GR (K w-GR) and without it (K w-No GR), suggesting that one dimensional flow is not essential for interpreting data for site tests. Another practical issue was that more than 30 % of the tests with GR failed due to the difficulty of achieving a good seal between the inner and the outer chambers. Based on the work reported in this paper, a new water permeability test is proposed.

Experimental Design to Optimize High-Volume Ash Grout in the Presence of Welan Gum and Superplasticizer

Applications such as soil, rock and oil-well grouting all require enormous amounts of cement and are good examples of areas where a high volume of fly ash could partially replace cement to produce low-cost, environmentally safe and durable concrete. There is an increasing need to identify the rheological properties of cement grout using a simple test to determine the fluidity, and other properties of underwater grouts such as washout resistance and compressive strength. This paper presents statistical models developed using a fractorial design which was carried out to model the influence of key parameters on properties affecting the performance of underwater grout. Such responses of fluidity included mini-slump and flow time measured by Marsh cone, washout resistance, unit weight and compressive strength. The models are valid for mixes with 0.40 to 0.60 water-to-cementitious materials ratio, 0.02 to 0.08% of anti-washout admixture, by mass of binder, and 0.6 to 1.8% of superplasticizer, by mass of cementitious materials. The grout was made with 50% of pulverized-fuel ash replacement, by mass ofcementitious materials. Also presented are the derived models that enable the identification of underlying primary factors and their interactions that influence the modelled responses of underwater cement grout. Such parameters can be useful to reduce the test protocol needed for proportioning of underwater cement grout. This paper highlighted the influence of W/CM and dosage of antiwashout admixture and superplasticizer on fluidity, washout resistance and compressive strength and attempted also to demonstrate the usefulness of the models to improve understanding of trade-offs between parameters.

The Application of Semiconductor Photocatalysis for the Removal of Cyanotoxins from Water and Design Concepts for Solar Photocatalytic Reactors for Large Scale Water Treatment

There has been a significant increase in the occurrence of cyanobacterial blooms in freshwaters over the past few decades due to escalating nutrient levels. These cyanobacteria release a range of toxins, for example microcystins which are chemically very stable. Many cyanotoxins are consequently very difficult to remove from water using existing treatment technologies. Semiconductor photocatalysis, however, has proven to be a very effective process for the removal of these compounds from water. In this chapter we consider the application of this highly versatile and exciting technology for the decomposition of cyanotoxins. Furthermore design concepts for solar photocatalytic reactors that could be utilized for the removal of these toxins are also considered

Photocatalytic evolution of hydrogen and oxygen from ceramic wafers of commercial titanias

Several commercial titania photocatalyst powders were formed into thin (ca. 350 mu m), 25 mm diameter ceramic wafers, sputter deposited with Pt on one side. The activities of each of the ceramic wafers were tested for hydrogen and oxygen evolution from aqueous sacrificial systems. The commercial sample PC50 (Millennium Chemicals, UK) yielded reproducible ceramic wafers with high activity for water photoreduction. Many of the ceramic wafers displayed low water photo-oxidation activities; however, these were greatly increased with addition of a NiO co-catalyst. In a selected case, hydrogen evolution activity was compared between a PC50 wafer and an identical weight of platinised PC50 powder suspension. (C) 2010 Elsevier B.V. All rights reserved.

Hydrogen peroxide enhanced photocatalytic oxidation of microcystin-lR using titanium dioxide

Cyanobacterial toxins present in drinking water sources pose a considerable threat to human health. Conventional water treatment systems have proven unreliable for the removal of these toxins and hence new techniques have been investigated. Previous work has shown that TiO₂ photocatalysis effectively destroys microcystin-LR in aqueous solutions, however non-toxic by-products were detected. It has been shown that photocatalytic reactions are enhanced by utilisation of alternative electron acceptors. We report here enhanced photocatalytic degradation of microcystin-LR following the addition of hydrogen peroxide to the system. It was also found that hydrogen peroxide with UV illumination alone was capable of decomposing microcystin-LR although at a much slower rate than found for TiO₂. No HPLC detectable by-products were found when the TiO₂/UV/H₂O₂ system was used indicating that this method is more effective than TiO₂/UV alone. Results however indicated that only 18% mineralisation occurred with the TiO₂/UV/H₂O₂ system and hence undetectable by-products must still be present. At higher concentrations hydrogen peroxide was found to compete with microcystin-LR for surface sites on the catalyst but at lower peroxide concentrations this competitive adsorption was not observed. Toxicity studies showed that both in the presence and absence of H₂O₂ the microcystin solutions were detoxified. These findings suggest that hydrogen peroxide greatly enhances the photocatalytic oxidation of microcystin-LR.

Suppression of Hydrogen Emission in a White-light Solar Flare

We present an analysis of an X-class flare that occurred on 11 June 2014 in active region NOAA 12087 using a newly developed high cadence Image
Selector operated by Astronomical Institute in Ondrejov, Czech Republic. This instrument provides spectra in the 350 - 440 nm wavelength range, which
covers the higher order Balmer lines as well as the Balmer jump at 364 nm. However, no detectable increase in these emissions were detected during
the flare, and support observations from SDO/EVE MEGS-B also show that the Lyman line series and recombination continuum were also suppressed,
particularly when compared to an M-class flare that occurred an hour earlier, and two other X-class flares on the preceding day. The X-class flare under
investigation also showed strong white light emission in SDO/HMI data, as well as an extremely hard electron spectrum ( 3.6), and
-ray emission,
from RHESSI data. This unique combination of datasets allows us to conclude that the white light emission from this flare corresponds to a black body
heated by high-energy electrons (and/or ions), as opposed to optical chromospheric emission from hydrogen.