Electrochemical Enhancement of Photocatalytic Disinfection on Aligned TiO2 and Nitrogen Doped TiO2 Nanotubes.

TiO2 photocatalysis is considered as an alternative to conventional disinfection processes for the inactivation of waterborne microorganisms. The efficiency of photocatalysis is limited by charge carrier recombination rates. When the photocatalyst is immobilized on an electrically conducting support, one may assist charge separation by the application of an external electrical bias. The aim of this work was to study electrochemically assisted photocatalysis with nitrogen doped titania photoanodes under visible and UV-visible irradiation for the inactivation of Escherichia coli. Aligned TiO2 nanotubes were synthesized (TiO2-NT) by anodizing Ti foil. Nanoparticulate titania films were made on Ti foil by electrophoretic coating (P25 TiO2). N-doped titania nanotubes and N,F co-doped titania films were also prepared with the aim of extending the active spectrum into the visible. Electrochemically assisted photocatalysis gave higher disinfection efficiency in comparison to photocatalysis (electrode at open circuit) for all materials tested. It is proposed that electrostatic attraction of negatively charged bacteria to the positively biased photoanodes leads to the enhancement observed. The N-doped TiO2 nanotube electrode gave the most efficient electrochemically assisted photocatalytic inactivation of bacteria under UV-Vis irradiation but no inactivation of bacteria was observed under visible only irradiation. The visible light photocurrent was only a fraction (2%) of the UV response.

A review on LED technology in water photodisinfection.

The increase in efficiency achieved by UV LED devices has led to a compelling increase in research reports on UV LED water treatment for consumption in the past few years. This paper presents an in-depth review based on recent studies on the suitability and performance of UV LED-driven processes for water disinfection. The effect of different UV wavelengths and their combinations was analysed for the inactivation of various microorganisms and the inhibition of repair mechanisms. Whereas 265 nm UVC LED present a higher DNA damaging potential, 280 nm radiation is reported to repress photoreactivation and dark repair. No synergistic effects have been proved to exist when coupling UVB + UVC whereas sequential UVA-UVC radiation seemed to enhance inactivation. Benefits of pulsed over continuous radiation in terms of germicidal effects and energy consumption were also analysed, but with inconclusive results. However, pulsed radiation may be promising for improving thermal management. As a challenge, the use of UV LED sources introduces significant inhomogeneities in the light distribution, pushing for the development of adequate simulation methods to ensure that the minimum target dose required for the target microbes is achieved. Concerning energy consumption, selecting the optimal wavelength of the UV LED needs a compromise between the quantum efficiency of the process and the electricity-to-photon conversion. The expected development of the UV LED industry in the next few years points to UVC LED as a promising technology for water disinfection at a large scale that could be competitive in the market in the near future.

Simultaneous photocatalytic oxidation of pharmaceuticals and inactivation of Escherichia coli in wastewater treatment plant effluents with suspended and immobilised TiO(2).

Simultaneous Escherichia coli inactivation and oxidation of pharmaceuticals in simulated wastewater treatment plant effluents has been investigated using a photocatalytic treatment with TiO(2) in suspension and immobilised onto a fixed-bed reactor. Non-photocatalytic reference experiments of dark adsorption and photolysis showed a higher sensitivity of E. coli towards the chemical composition of water in comparison with the concentration of pharmaceuticals that remains unaffected. Moreover, it must be underlined that the presence of pharmaceuticals (including antibiotics) did not seem to affect the bacterial viability at such low concentrations. Concerning photocatalytic experiments, both suspended and immobilised TiO(2) were able to simultaneously inactivate and oxidise both kinds of pollutants (bacteria and pharmaceuticals). The fixed-bed reactor showed similar activity to that of the slurry without deactivation after several cycles of reuse. That makes TiO(2) photocatalysis a quite interesting technology for the treatment of drinking water supplies or wastewater plant effluents, allowing the removal of emerging contaminants such as pharmaceuticals during the disinfection treatment.

High-performance low-cost solar collectors for water treatment fabricated with recycled materials, open-source hardware and 3d-printing technologies.

Solar technologies constitute an excellent alternative for water treatment in low-income countries where the poverty of a large part of the population hinders their access to safe water. From a technical point of view, the use of compound parabolic collectors (CPC) has been consolidated in the last decades. However, the relatively high cost of tooling conventional manufacturing processes for these collectors makes them difficult to afford in the most impoverished regions. This work presents the development of low-cost CPC and parabolic through solar collectors (PTC) by 3D printing of the structure and the use of recycled reflective materials. Besides, open-source hardware has been used to control system operation, including a supplementary UV LED system to compensate for the operation under low solar irradiance. Regarding the tested reflective materials, an optimum is obtained using an aluminium adhesive sheet that leads to an efficiency of 80% compared to a commercial CPC made of high-quality anodised aluminium, being the cost 20 times lower. On the other hand, incorporating a low-cost solar tracking system in a printed PTC reactor could lead to efficiencies up to 300% compared to the commercial CPC, while the cost was 4.5 times lower. Finally, the LED compensation system was successfully validated, allowing the operation with a constant treatment capacity during operation in cloudy conditions. In conclusion, the developed collectors are high-performance solar water treatment systems with a significantly lower investment cost, making them affordable worldwide.

Modification of chiral dimethyl tartrate through transesterification: immobilization on POSS and enantioselectivity reversal in sharpless asymmetric epoxidation.

Modification of dimethyl tartrate has been investigated through transesterification with aminoalcohols to provide reactive functionalities for the covalent bonding of chiral tartrate to polyhedral oligomeric silsesquioxanes. The transesterification of dimethyl tartrate has been widely studied using different catalytic systems and reaction conditions. Through the proper selection of both the catalytic system and the reaction conditions, it is possible to achieve monosubstituted or bis-substituted tartrate derivatives as sole products. All the intermediate chiral tartrate-derived ligands were successfully used in the homogeneous enantioselective epoxidation of allylic alcohols providing moderate enantiomeric excess over the products. Attached amine groups have been used to support the modified tartrate ligands on to a haloaryl-functionalized silsesquioxane moiety. This final chiral tartrate ligand displays reverse enantioselectivity in the asymmetric epoxidation of allylic alcohols with regard to the starting dimethyl tartrate ligand, both molecules having the same chiral sign. However, the POSS-containing ligand can be easily recovered in almost quantitative yield and reused in asymmetric epoxidation reactions. In addition, recovered silsesquioxane-pendant ligand, though displaying decreasing catalytic activity in recycling epoxidation tests, showed very stable enantioselective behavior.

Photocatalytic inactivation of E. faecalis in secondary wastewater plant effluents.

Photocatalytic inactivation of Enterococcus faecalis using TiO(2) suspensions was investigated and compared to the inactivation of the most commonly used faecal indicator strain Escherichia coli. In contrast to the inactivation in pure deionized water, disinfection of effluents from the biological process of an urban wastewater plant showed a longer initial lag phase and higher survival fractions after several hours of irradiation. Moreover, the fluctuation of the composition of the effluents strongly affects the overall inactivation rate, not directly related to changes in the values of organic matter content. Additionally, it was found that E. faecalis seems to be more resistant than E.coli towards the photocatalytic treatment. These results could be related to the differences in the cell wall structure of both microorganisms. The main conclusion of this work is that attention must be paid when transferring results obtained for model organism to real bacteria consortia and from laboratory experiments with deionized water to effluents from sewage plants.

Solar photocatalytic disinfection with immobilised TiO(2) at pilot-plant scale.

The photocatalytic disinfection efficiency has been investigated for two immobilized TiO(2) catalytic systems (wall reactor and fixed-bed reactor) in a solar pilot plant. Their performances have been compared with the use of a slurry reactor and the solar disinfection without catalyst. The use of photocatalytic TiO(2) wall reactors does no show clear benefits over the solar disinfection process in the absence of catalyst. The reason is that the efficiency of the solar disinfection is so high that the presence of titania in the reactor wall reduces the global efficiency due to the competition for the absorption of photons. As expected, the maximum efficiency was shown by the slurry TiO(2) reactor, due to the optimum contact between bacteria and catalyst. However, it is noticeable that the use of the fixed-bed reactor leads to inactivation rate quite close to that of the slurry, requiring comparable accumulated solar energy of about 6 kJ L(-1) to achieve a 6-log decrease in the concentration of viable bacteria and allowing a total disinfection of the water (below the detection limit of 1 CFU mL(-1)). Not only the high titania surface area of this configuration is responsible for the bacteria inactivation but the important contribution of the mechanical stress has to be considered. The main advantage of the fixed-bed TiO(2) catalyst is the outstanding stability, without deactivation effects after ten reaction cycles, being readily applicable for continuous water treatment systems.

Kinetic modelling of the photocatalytic inactivation of bacteria.

This work analyzes the kinetic modelling of the photocatalytic inactivation of E. coli in water using different types of kinetic models; from an empirical equation to an intrinsic kinetic model including explicit radiation absorption effects. Simple empirical equations lead to lower fitting errors, but require a total of 12 parameters to reproduce the results of four inactivation curves when the catalyst concentration was increased. Moreover, these parameters have no physical meaning and cannot be extrapolated to different experimental conditions. The use of a pseudo-mechanistic model based on a simplified reaction mechanism reduces the number of required kinetic parameters to 6, being the kinetic constant the only parameter that depends on the catalyst concentration. Finally, a simple modification of a kinetic model based on the intrinsic mechanism of photocatalytic reactions including explicit radiation absorption effects achieved the fitting of all the experiments with only three parameters. The main advantage of this approach is that the kinetic parameters estimated for the model become independent of the irradiation form, as well as the reactor size and its geometrical configuration, providing the necessary information for scaling-up and design of commercial-scale photoreactors for water disinfection.

Kinetics and influence of water composition on photocatalytic disinfection and photocatalytic oxidation of pollutants.

This work is focused on the comparison between the photocatalytic inactivation of Escherichia coli and the photocatalytic oxidation of methylene blue, regarding the reaction kinetics and the influence of water composition. Disinfection profiles show an initial delay, in contrast with the exponential decay shown by the decolorization of methylene blue solutions. A serial-event mechanism is proposed for both disinfection and mineralization processes, the number of intermediate species being the main difference between them. Concerning the influence of water composition, inactivation of bacteria is more sensitive to the presence of inorganic ions and/or organic matter in the solution. In some cases opposite behaviours are observed, such as in the presence of chloride ions, which enhance the disinfection rate but decrease degradation activity for methylene blue. Consequently, the results obtained in the evaluation of photocatalytic processes for the degradation of chemical pollutants cannot be always extrapolated to the inactivation of microorganisms.

Emerging micropollutant oxidation during disinfection processes using UV-C, UV-C/H2O2, UV-A/TiO2 and UV-A/TiO2/H2O2.

Regeneration of wastewater treatment plant effluents constitutes a solution to increase the availability of water resources in arid regions. Water reuse legislation imposes an exhaustive control of the microbiological quality of water in the operation of disinfection tertiary treatments. Additionally, recent reports have paid increasing attention to emerging micropollutants with potential biological effects even at trace level concentration. This work focuses on the evaluation of several photochemical technologies as disinfection processes with the aim of simultaneously achieving bacterial inactivation and oxidation of pharmaceuticals as examples of emerging micropollutants typically present in water and widely studied in the literature. UV-C-based processes show a high efficiency to inactivate bacteria. However, the bacterial damages are reversible and only when using H(2)O(2), bacterial reproduction is affected. Moreover, a complete elimination of pharmaceutical compounds was not achieved at the end of the inactivation process. In contrast, UV-A/TiO(2) required a longer irradiation time to inactivate bacteria but pharmaceuticals were completely removed along the process. In addition, its oxidation mechanism, based on hydroxyl radicals (OH), leads to irreversible bacterial damages, not requiring of chemicals to avoid bacterial regrowth. For UV-A/TiO(2)/H(2)O(2) process, the addition of H(2)O(2) improved Escherichia coli inactivation since the cell wall weakening, due to OH attacks, allowed H(2)O(2) to diffuse into the bacteria. However, a total elimination of the pharmaceuticals was not achieved during the inactivation process.

Analogies and differences between photocatalytic oxidation of chemicals and photocatalytic inactivation of microorganisms.

This study reports the analogies and differences found when comparing TiO(2) photocatalytic treatment for chemical oxidation and microorganisms inactivation, using methylene blue and Escherichia coli as references, respectively. In both processes the activation is based on the same physicochemical phenomena and consequently a good correlation between them is observed when analyzing the effect of operational variables such as catalyst concentration or incident radiation flux, both factors influencing common stages such radiation absorption and generation of reactive oxygen species. However, different microbiological aspects (osmotic stress, repairing mechanism, regrowth, bacterial adhesion to the titania surface, etc) makes disinfection kinetics significantly more complex than the first-order profiles usually observed for the oxidation of chemical pollutants. Moreover, bacterial inactivation reactions are found to be extremely sensitive to the composition of water and modifications of the catalysts in comparison with the decolorization of the dye solutions, showing opposite behaviors to the presence of chlorides, incorporation of silver to the catalysts or the use of different types of immobilized TiO(2) systems. Therefore, the activity observed for the photocatalytic oxidation of organics can not be always extrapolated to photocatalytic disinfection processes.

Mechanism of CIT-6 and VPI-8 crystallization from zincosilicate gels.

The crystallisation of CIT-6, a large-pore zincosilicate with the framework topology of zeolite Beta and synthesised from clear hydrogels that contain, tetraethylammonium (TEA+), Li+ and Zn2+ cations, proceeds initially through the formation of an amorphous solid that incorporates all the initial Zn species. Nucleation of the *BEA phase is effected by reorganisation of the amorphous phase, whereas crystal growth involves the incorporation of soluble species also. A highly crystalline CIT-6 material is obtained after 164 h of synthesis at 140 degrees C. Scanning electron microscopy (SEM) shows that this sample exhibits two different types of crystals: well-defined pseudo-cubic crystals and rounded crystals. The latter has a broad crystal-size distribution. If crystallisation is continued with longer synthesis times, the VPI-8 crystalline phase appears, and a new population of needle-shaped crystals is detected in the SEM images. This new crystalline phase is nucleated on the surface of the rounded CIT-6 crystals, which disappear as the crystallisation progresses, while no changes are observed in the population of pseudo-cubic CIT-6 crystals. At higher crystallisation temperatures these phase transformations are accelerated, and the formation of VPI-8 is favoured over that of CIT-6.