Photocatalytic organic synthesis in an NMR tube:CC coupling of phenoxyacetic acid and acrylamide

NMR was used to study the semiconductor photocatalytic (SPC) CC coupling of phenoxyacetic acid (PAA) with acrylamide (ACM) in an NMR tube photoreactor. Using an NMR tube with a sol-gel titania inner coating as a photoreactor, this reaction is relatively clean, forming only 1 product, 4-phenoxybutanamide (4-PB), in yields up to 78%. This SPC reaction is used to assess the activity of the sol-gel titania coating as a function of their annealing temperature, which alters the surface area and phase of the titania, and the general reusability of the TiO coated NMR tubes. The optimum temperature range for annealing the sol-gel titania films is between 450 °C and 800 °C, with the maximum yield and rate attained at 450 °C. Despite a decrease in the initial rates of formation of 4-PB above an annealing temperature of 450 °C, the final product yields remained similar, giving maximum yields within 60 min of irradiation. The reusability study reveals that the activity of the sol-gel titania can quickly deteriorate with repeated use due to the adsorption of yellow/brown coloured, insoluble, most likely organic polymeric, material and its screening effect on the underlying photocatalyst. The titania can, however, be restored to its original activity by a simple heat treatment at 450 °C for 30 min.

The hydraulics and resulting bed scour within the vicinity of Submerged Single Span Arch Bridges

As a consequence of climate change there is now a more frequent occurrence of extreme rainfall events where, with higher rates of urbanisation, the built environment has become increasingly affected by flooding.. This is of particular importance in relation to the stability of bridge structures that span rivers and canals etc. In November 2009, the UK and Ireland were subjected to extraordinarily severe weather conditions for several days. The rainfall was logged as the highest level of rainfall ever recorded within the UK, and as a direct consequence, unprecedented flooding occurred in Cumbria. This flooding led to the collapse of three road bridges which were generally 19th century masonry arch bridges, with relatively shallow foundations. In the UK, knowledge of the combined effect of bridge scouring and inundation has been not been particularly widely studied. Research carried out by Hamill et al [1] considered the hydraulic analysis of single arch bridges under flood conditions, but no consideration was given towards the likely damage to these structures due to scouring. Prior to this, Bierry and Delleur [2] produced a classic paper in predicting the discharge downstream of an inundated arch, focussing on predicting afflux as opposed to bridge scour. Further work on backwater effects was carried out by Martin-Vide & Prio [3] in semi-circular arch bridges. Both pressurized and free-surface flows at the bridge were investigated. Flows on a mobile bed in clear-water conditions were compared to those with a rigid bed, but no predictive equation for scour under pressurised conditions was considered. This paper will present initial findings from an experimental investigation into the effects of surcharged flow and subsequent scour within the vicinity of single span arch bridges. Velocities profiles will be shown within the vicinity of the arch, in addition to the depth of clear water scour, for a series of flows and model spans. The data will be presented, where results will be correlated to the most recent predictive equations that are proposed.

Quantum yield measurements for the photocatalytic oxidation of Acid Orange 7 (AO7) and reduction of 2,6-dichloroindophenol (DCIP) on transparent TiO2 films of various thickness

This work comprises the photoactivity assessment of transparent sol–gel TiO2 coatings of various thickness using two test systems. The initial rates of both photocatalytic reactions, namely the oxidative bleaching of Acid Orange 7 (AO7) and the reductive bleaching of 2,6-dichlorindophenol (DCIP) increase linearly with increasing titania film thickness as well as with increasing absorbed light flux. The latter work revealed quantum yields (QY) of 0.19% and 92% for the AO7 and DCIP test system, respectively. The low QY for the AO7 oxidation is due to the combination of a slow irreversible reduction of oxygen and also for the oxidation of AO7, thus favouring the high efficiency for electron–hole recombination that is typical for aqueous organic pollutants. In contrast, the very high QY for the photocatalysed reduction of DCIP is due to the presence of a vast excess of glycerol which traps the photogenerated holes efficiently and so allow time for the slower reduction of dye to take place. Furthermore, the oxidation of glycerol results in the generation of highly reducing R-hydroxyalkyl radicals that are able to also reduce DCIP. As a consequence of this ‘current doubling’ effect, the observed QY (92%) is much higher than the apparent theoretical value of 50%.

The effect of pH on the photonic efficiency of the destruction of methyl orange under controlled periodic illumination with UV-LED sources

The nature of photon interaction and reaction pH can have significant impacts on semiconductor photocatalysis. This paper describes the effect of pH on the photonic efficiency of photocatalytic reactions in the aqueous phase using TiO2 catalysts. The reactor was irradiated using periodic illumination with UV-LEDs through control of the illumination duty cycle (γ) through a series of light and dark times (Ton/Toff). Photonic efficiencies for methyl orange degradation were found to be comparable at high γ irrespective of pH. At lower γ, pH effects on photonic efficiency were very distinct across acidic, neutral and alkaline pH indicating an effect of complementary parameters. The results suggest photonic efficiency is greatest as illumination time, Ton approaches interfacial electron-transfer characteristic time which is within the range of this study or charge-carrier lifetimes upon extrapolation and also when electrostatic attraction between surface-trapped holes, {TiIVOH}ads+ and substrate molecules is strongest.

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

Development of a doped titania immobilised thin film multi tubular photoreactor

This paper describes a novel doped titania immobilised thin film multi tubular photoreactor which has been developed for use with liquid, vapour or gas phase media. In designing photocatalytic reactors measuring active surface area of photocatalyst within the unit is one of the critical design parameters. This dictate greatly limits the applicability of any semi-conductor photocatalyst in industrial applications, as a large surface area equates to a powder catalyst. This demonstration of a thin film coating, doped with a rare earth element, novel photoreactor design produces a photocatalytic degradation of a model pollutant (methyl orange) which displayed a comparable degradation achieved with P25 TiO2. The use of lanthanide doping is reported here in the titania sol gel as it is thought to increase the electron hole separation therefore widening the potential useful wavelengths within the electromagnetic spectrum. Increasing doping from 0.5% to 1.0% increased photocatalytic degradation by ∼17% under visible irradiation. A linear relationship has been seen between increasing reactor volume and degradation which would not normally be observed in a typical suspended reactor system. © 2012 Elsevier B.V.

Overview of the current ISO tests for photocatalytic materials

The current eight published ISO standards associated with semiconductor photocatalysis are considered. These standards cover: (1) air purification (specifically, the removal of NO, acetaldehyde and toluene), (2) water purification (the photobleaching of methylene blue and oxidation of DMSO) (3) self-cleaning surfaces (the removal of oleic acid and subsequent change in water droplet contact angle), (4) photosterilisation (specifically probing the antibacterial action of semiconductor photocatalyst films) and (5) UV light sources for semiconductor photocatalytic ISO work. For each standard, the background is first considered, followed by a brief discussion of the standard particulars and concluding in a discussion of the pros and cons of the standard, with often recommendations for their improvement. Other possible standards for the future which would either compliment or enhance the current ones are discussed briefly. 

The photocatalytic decomposition of microcystin-LR using selected titanium dioxide materials

Microcystins (cyclic heptapeptides) produced by a number of freshwater cyanobacteria are a potential cause for concern in potable water supplies due to their acute and chronic toxicity. TiO₂ photocatalysis is a promising technology for removal of these toxins from drinking water. It is, however, necessary to have a sufficient knowledge of how the catalyst materials cause the degradation of the toxins through the photocatalytic process. The present study reports microcystin degradation products of the photocatalytic oxidation by using a number of commercial TiO₂ powder (P25, PC50, PC500 and UV100) and granular (KO1, KO3, TiCat-C, TiCat-S) materials, so aiding the mechanistic understanding of this process. Liquid chromatography-mass spectrometry analysis demonstrated that the major destruction pathway of microcystin for all the catalysts tested followed almost the same pathway, indicating the physical properties of the catalysts had little effects on the degradation pathway of microcystin-LR. 

Variables to be considered when assessing the photocatalytic destruction of bacterial pathogens

The current study sought to assess the importance of three common variables on the outcome of TiO₂ photocatalysis experiments with bacteria. Factors considered were (a) ability of test species to withstand osmotic pressure, (b) incubation period of agar plates used for colony counts following photocatalysis and (c) chemical nature of suspension medium used for bacteria and TiO₂. Staphylococcus aureus, Escherichia coli, Salmonella ser. Typhimurium and Pseudomonas aeruginosa were found to vary greatly in their ability to withstand osmotic pressure, raising the possibility that osmotic lysis may be contributing to loss of viability in some photocatalytic disinfection studies. Agar plate incubation time was also found to influence results, as bacteria treated with UV light only grew more slowly than those treated with a combination of UV and TiO_2. The chemical nature of the suspension medium used was found to have a particularly pronounced effect upon results. Greatest antibacterial activity was detected when aqueous sodium chloride solution was utilised, with ∼1 × 10⁶ CFU mL^-1 S. aureus being completely killed after 60 min. Moderate activity was observed when distilled water was employed with bacteria being killed after 2 h and 30 min, and no antibacterial activity at all was detected when aqueous tryptone solution was used. Interestingly, the antibacterial activity of UV light on its own appeared to be very much reduced in experiments where aqueous sodium chloride was employed instead of distilled water. 

The photocatalytic destruction of the cyanotoxin, nodularin using TiO 2

Titanium dioxide (TiO₂) photocatalysis has been used to initiate the destruction of nodularin, a natural hepatotoxin produced by cyanobacteria. The destruction process was monitored using liquid chromatography-mass spectrometry analysis which has also enabled the identification of a number of the photocatalytic decomposition products. The reduction in toxicity following photocatalytic treatment was evaluated using protein phosphatase inhibition assay, which demonstrated that the destruction of nodularin was paralleled by an elimination of toxicity. 

Mechanistic studies of the photocatalytic oxidation of microcystin-LR: An investigation of byproducts of the decomposition process

Microcystins (cyclic heptapeptides) are produced by a number of freshwater cyanobacteria and cause concern in potable water supplies due to their acute and chronic toxicity. The present study reports the structural characterization of the degradation products of the photocatalytic oxidation of microcystin-LR, so aiding the mechanistic understanding of this process. TiO₂ photocatalysis is a promising technology for removal of these toxins from drinking water. However, before it can be adopted in any practical application it is necessary to have a sufficient knowledge of degradation byproducts and their potential toxicity. Liquid chromatography-mass spectrometry analysis demonstrated that the major destruction pathway of microcystin appears to be initiated via three mechanisms: UV irradiation, hydroxyl radical attack, and oxidation. UV irradiation caused geometrical isomerization of microcystin converting the (4E), (6E) of the Adda configuration to (4E), 6(Z) or 4(Z), 6(E). Hydroxyl radical attack on the conjugated diene structure of Adda moiety produced dihyroxylated products. Further oxidation cleaved the hydroxylated 4-5 and/or 6-7 bond of Adda to form aldehyde or ketone peptide residues, which then were oxidized into the corresponding carboxylic acids. Photocatalysis also hydrolyzed the peptide bond on the ring structure of microcystin to form linear structures although this appeared to be a minor pathway.

Processes influencing surface interaction and photocatalytic destruction of microcystins on titanium dioxide photocatalysts

Microcystins are a family of hepatotoxic peptides produced by freshwater cyanobacteria. Their occurrence in drinking water is of concern since chronic exposure to these toxins causes tumor promotion. It is therefore essential to establish a reliable treatment strategy that will ensure their removal from potable water. We have previously described the rapid destruction of microcystin-LR using TiO₂ photocatalysis, however, since there are at least 70 microcystin variants it is essential that the destruction of a number of microcystins be evaluated. In this study the dark adsorption and destruction of four microcystins was followed over a range of pH. All four microcystins were destroyed although the efficiency of their removal varied. The two more hydrophobic microcystins (-LW and -LF) were found to have high dark adsorption (98 and 91% at pH 4) in contrast to microcystin-RR, which was found to have almost no (only 2-3%) dark adsorption across all pH. 

Mechanistic and toxicity studies of the photocatalytic oxidation of microcystin-LR

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, a variety of by-products were generated. In this paper, we report a mechanistic study of the photocatalytic destruction of microcystin-LR. In particular, the toxicity by-products of the process have been studied using both brine shrimp and protein phosphatase bioassays. 

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.