Alginate fibers as photocatalyst immobilizing agents applied in hybrid photocatalytic/ultrafiltration water treatment processes.

Ca alginate polymer fibers were developed to effectively disperse and stabilize an efficient photocatalyst such as AEROXIDE(®) TiO(2) P25 in their matrix. The biopolymer/TiO(2) fibers were prepared and tested either in the hydrogel non-porous form or in the highly porous aerogel form prepared by sc-CO(2) drying. Batch photocatalytic experiments showed that the porous, Ca alginate/TiO(2) fibers, exhibited high efficiency for the removal of methyl orange (MO) from polluted water. In addition, their high porosity and surface area led to high MO degradation rate which was faster than that observed not only for their non-porous analogs but also of the bulk P25 TiO(2) powder. Specifically, 90% removal for 20 µM MO was achieved within 220 min for the porous sc-CO(2) dried fibers while for their non-porous analogs at 325 min. The corresponding value (at 60 µM MO) for the porous sc-CO(2) dried fibers was 140 min over 240 min for the AEROXIDE(®) TiO(2) P25 as documented in the literature. Furthermore the composite alginate/photocatalyst porous fibers were combined with TiO(2) membranes in a continuous flow, hybrid photocatalytic/ultrafiltration water treatment process that led to a three fold enhancement of the MO removal efficiency at 400 ml of 20 µM MO total treated volume and to dilution rather than condensation in the membrane retentate as commonly observed in filtration processes. Furthermore the permeability of the photocatalytic membrane was enhanced in the presence of the fibers by almost 20%. This performance is achieved with 26 cm(2) and 31 cm(2) of membrane and stabilized photocatalyst surfaces respectively and in this context there is plenty of room for the up-scaling of both membranes and fibers and the achievement of much higher water yields since the methods applied for the development of the involved materials (CVD and dry-wet phase inversion in a spinning set-up) are easily up-scalable and are not expected to add significant cost to the proposed water treatment process.

Double-side active TiO2-modified nanofiltration membranes in continuous flow photocatalytic reactors for effective water purification.

A chemical vapour deposition (CVD) based innovative approach was applied with the purpose to develop composite TiO(2) photocatalytic nanofiltration (NF) membranes. The method involved pyrolytic decomposition of titanium tetraisopropoxide (TTIP) vapor and formation of TiO(2) nanoparticles through homogeneous gas phase reactions and aggregation of the produced intermediate species. The grown nanoparticles diffused and deposited on the surface of γ-alumina NF membrane tubes. The CVD reactor allowed for online monitoring of the carrier gas permeability during the treatment, providing a first insight on the pore efficiency and thickness of the formed photocatalytic layers. In addition, the thin TiO(2) deposits were developed on both membrane sides without sacrificing the high yield rates. Important innovation was also introduced in what concerns the photocatalytic performance evaluation. The membrane efficiency to photo degrade typical water pollutants, was evaluated in a continuous flow water purification device, applying UV irradiation on both membrane sides. The developed composite NF membranes were highly efficient in the decomposition of methyl orange exhibiting low adsorption-fouling tendency and high water permeability.

Photocatalytic degradation and mineralization of microcystin-LR under UV-A, solar and visible light using nanostructured nitrogen doped TiO2.

In an attempt to face serious environmental hazards, the degradation of microcystin-LR (MC-LR), one of the most common and more toxic water soluble cyanotoxin compounds released by cyanobacteria blooms, was investigated using nitrogen doped TiO(2) (N-TiO(2)) photocatalyst, under UV-A, solar and visible light. Commercial Degussa P25 TiO(2), Kronos and reference TiO(2) nanopowders were used for comparison. It was found that under UV-A irradiation, all photocatalysts were effective in toxin elimination. The higher MC-LR degradation (99%) was observed with Degussa P25 TiO(2) followed by N-TiO(2) with 96% toxin destruction after 20 min of illumination. Under solar light illumination, N-TiO(2) nanocatalyst exhibits similar photocatalytic activity with that of commercially available materials such as Degussa P25 and Kronos TiO(2) for the destruction of MC-LR. Upon irradiation with visible light Degussa P25 practically did not show any response, while the N-TiO(2) displayed remarkable photocatalytic efficiency. In addition, it has been shown that photodegradation products did not present any significant protein phosphatase inhibition activity, proving that toxicity is proportional only to the remaining MC-LR in solution. Finally, total organic carbon (TOC) and inorganic ions (NO(2)(-), NO(3)(-) and NH(4)(+)) determinations confirmed that complete photocatalytic mineralization of MC-LR was achieved under both UV-A and solar light.

Visible light induced wetting of nanostructured N-F co-doped titania films.

Nitrogen and fluorine co-doped TiO(2) films have been prepared by dip coating of a modified titania sol-gel based on a nitrogen precursor and a nonionic fluorosurfactant as pore template and fluorine source. The modified NF-TiO(2) films absorb in the visible spectral range, between 400-510 nm and undergo reversible hydrophilic conversion under visible light to a final contact angle of 8°, in contrast to the UV limited optical response of their undoped anatase TiO(2) analogues. The phenomenon takes place at a rate slower than the corresponding one observed for the UV stimulated superhydrophilic effect. The wetting response of the N-F doped TiO(2) films correlates well with the variation of their optical properties and surface morphological characteristics and most importantly with their photocatalytic activity, rendering these materials very promising for self-cleaning applications under visible light.

Use of titanium dioxide (TiO2) photocatalysts as alternative means for Listeria monocytogenes biofilm disinfection in food processing.

The aim of this work was to study the photocatalytic activity of titanium dioxide (TiO(2)) against Listeria monocytogenes bacterial biofilm. Different TiO(2) nanostructured thin films were deposited on surfaces such as stainless steel and glass using the doctor-blade technique. All the surfaces were placed in test tubes containing Brain Heart (BH) broth and inoculated with L. monocytogenes. Test tubes were then incubated for 10 days at 16°C in order to allow biofilm development. After biofilm formation, the surfaces were illuminated by ultraviolet A light (UVA; wavelength of 315-400 nm). The quantification of biofilms was performed using the bead vortexing method, followed by agar plating and/or by conductance measurements (via the metabolic activity of biofilm cells). The presence of the TiO(2) nanoparticles resulted in a fastest log-reduction of bacterial biofilm compared to the control test. The biofilm of L. monocytogenes for the glass nanoparticle 1 (glass surface modified by 16% w/v TiO(2)) was found to have decreased by 3 log CFU/cm(2) after 90 min irradiation by UVA. The use of TiO(2) nanostructured photocatalysts as alternative means of disinfecting contaminated surfaces presents an intriguing case, which by further development may provide potent disinfecting solutions. Surface modification using nanostructured titania and UV irradiation is an innovative combination to enhance food safety and economizing time and money.

Dye-sensitization of self-assembled titania nanotubes prepared by galvanostatic anodization of Ti sputtered on conductive glass.

Self-organized porous TiO(2) nanotubes (NTs) were prepared on conductive glass by galvanostatic anodizing of sputtered titanium in an NH(4)F /glycerol electrolyte. DC magnetron sputtering at an elevated substrate temperature (500 degrees C) was used to deposit 650 nm thick titanium films. After anodizing, NTs, 830 nm long, with an average external diameter of 92 nm, were grown; this gave a high conversion rate of oxide from titanium (1.9), with a 220 nm thick layer of titanium, which was not oxidized, located at the base of the tubes. The NTs revealed a mainly amorphous structure, which transformed mostly to anatase upon thermal treatment in air at 450 degrees C. The tubes were sensitized by the N719 complex and the resultant photoelectrodes were incorporated into liquid dye solar cells (DSCs) and further tested under back-side illumination. High values of V(oc) (714 mV) were obtained under 1 sun (AM 1.5), assigned to low dark current magnitude and large recombination resistance and electron lifetime. In addition, typical values of fill factors (of the order of 0.62) were attained, in agreement with the estimated ohmic resistance of the cells in combination with low electron transfer resistance at the platinum/electrolyte interface. The overall moderate power conversion efficiency (of the order of 0.3%) was mainly due to the low short-circuit photocurrents (J(sc) = 0.68 mA cm(-2)), which was confirmed further by the corresponding IPCE values (5.2% at 510 nm). The magnitude of J(sc) was attributed to absorbed light losses due to back-side illumination of the cells, the low dye loading (due to the limited thickness of anodic titania) and the high charge transfer resistance at the TiO(2)/conductive substrate due to the presence of barrier layer(s) underneath the tubes. These preliminary results encourage the DSC community to explore further the galvanostatic anodizing of titanium in order to produce highly efficient porous TiO(2) NTs directly on conductive glass. Current work is focusing on achieving complete anodizing of the metal substrate and full transparency for the photoelectrode in order to increase and optimize the resultant cell efficiencies.

Photo-induced effects on self-organized TiO2 nanotube arrays: the influence of surface morphology.

Self-organized TiO(2) nanotubes with packed, vertically aligned morphology and different lateral characteristics were grown on Ti metal substrates by controlled electrochemical anodization in phosphate/HF and ethylene glycol/HF electrolytes. The wetting, photo-induced superhydrophilicity, and photocatalytic activity of the nanotubular materials were investigated under ultraviolet irradiation. The photoactivity of the TiO(2) nanotube arrays was analysed in terms of their morphological characteristics that were determined by means of scanning electron microscopy and atomic force microscopy in conjunction with geometrical modelling. The wetting and the UV-induced superhydrophilicity could be accordingly modelled by the Cassie-Baxter mode arising from the large scale roughness of the nanotubular arrays in combination with the Wenzel mode due to the small scale roughness induced by ridges at the outer tube surface. The photocatalytic activity of the TiO(2) nanotube arrays was further found to correlate quantitatively with the variation of the geometric roughness factor, verifying the strong impact of morphology on the photo-induced properties of the vertically oriented TiO(2) tubular architecture.

Dye-sensitized solar cells based on thick highly ordered TiO(2) nanotubes produced by controlled anodic oxidation in non-aqueous electrolytic media.

Dye-sensitized solar cells (DSSCs) were prepared using TiO(2) nanotubes, grown by controlled Ti anodic oxidation in non-aqueous media. Smooth, vertically oriented TiO(2) nanotube arrays, presenting a high degree of self-organization and a length of 20 µm, have been grown using ethylene glycol electrolyte containing HF. As-grown nanotubes exhibit an amorphous structure, which transforms to the anatase TiO(2) crystalline phase upon post-annealing in air at 450 °C. Atomic force microscopy (AFM) revealed the porous morphology together with high roughness and fractality of the surface. The annealed tubes were sensitized by the standard N719 ruthenium dye and the adsorption was characterized using resonance micro-Raman spectroscopy and adsorption-desorption measurements. The sensitized tubes were further used as active photoelectrodes after incorporation in sandwich-type DSSCs using both liquid and solidified electrolytes. The efficiencies obtained under air mass (AM) 1.5 conditions, using a back-side illumination geometry, were very promising: 0.85% using a composite polymer redox electrolyte, while the efficiency was further increased up to 1.65% using a liquid electrolyte.

Morphology, ionic diffusion and applicability of novel polymer gel electrolytes with LiI/I2.

Novel polymer gel electrolytes have been prepared by incorporating LiI-I(2) solutions into a polyethylene oxide matrix supported by a TiO(2) filler. The gel electrolytes, based on either acetonitrile or propylene carbonate solvents are compared with liquid standard ones and are examined by (7)Li solid state nuclear magnetic resonance relaxometry and diffusion measurements. In parallel, the triiodide apparent diffusion coefficient has been determined by linear sweep voltammetry. The results are correlated with atomic force microscopic images of the electrolytes and give insight of the dynamic properties of the ions in the constrained polymer medium. Furthermore, the dissociation of the ions is estimated by relating the ionic conductivity to the ionic diffusion. As a prime application, the polymer gel electrolytes were incorporated in dye sensitized solar cells and the measured energy conversion efficiencies were successfully correlated with their morphological, diffusive and conducting properties.