One-Step Synthesis of CuxOy/TiO2 Photocatalysts by Laser Pyrolysis for Selective Ethylene Production from Propionic Acid Degradation.

In an effort to produce alkenes in an energy-saving way, this study presents for the first time a photocatalytic process that allows for the obtention of ethylene with high selectivity from propionic acid (PA) degradation. To this end, TiO2 nanoparticles (NPs) modified with copper oxides (CuxOy/TiO2) were synthetised via laser pyrolysis. The atmosphere of synthesis (He or Ar) strongly affects the morphology of photocatalysts and therefore their selectivity towards hydrocarbons (C2H4, C2H6, C4H10) and H2 products. Specifically, CuxOy/TiO2 elaborated under He environment presents highly dispersed copper species and favours the production of C2H6 and H2. On the contrary, CuxOy/TiO2 synthetised under Ar involves copper oxides organised into distinct NPs of ~2 nm diameter and promotes C2H4 as the major hydrocarbon product, with selectivity, i.e., C2H4/CO2 as high as 85% versus 1% obtained with pure TiO2.

TiO2 Catalyzed Dihydroxyacetone (DHA) Conversion in Water: Evidence That This Model Reaction Probes Basicity in Addition to Acidity.

In this paper, evidence is provided that the model reaction of aqueous dihydroxyacetone (DHA) conversion is as sensitive to the TiO2 catalysts' basicity as to their acidity. Two parallel pathways transformed DHA: while the pathway catalyzed by Lewis acid sites gave pyruvaldehyde (PA) and lactic acid (LA), the base-catalyzed route afforded fructose. This is demonstrated on a series of six commercial TiO2 samples and further confirmed by using two reference catalysts: niobic acid (NbOH), an acid catalyst, and a hydrotalcite (MgAlO), a basic catalyst. The original acid-base properties of the six commercial TiO2 with variable structure and texture were investigated first by conventional methods in gas phase (FTIR or microcalorimetry of pyridine, NH3 and CO2 adsorption). A linear relationship between the initial rates of DHA condensation into hexoses and the total basic sites densities is highlighted accounting for the water tolerance of the TiO2 basic sites whatever their strength. Rutile TiO2 samples were the most basic ones. Besides, only the strongest TiO2 Lewis acid sites were shown to be water tolerant and efficient for PA and LA formation.

Influence of the Micro-Nanostructuring of Titanium Dioxide Films on the Photocatalytic Degradation of Formic Acid under UV Illumination.

Surface micro-nanostructuring can provide new functionalities and properties to coatings. For example, it can improve the absorption efficiency, hydrophobicity and/or tribology properties. In this context, we studied the influence of micro-nanostructuring on the photocatalytic efficiency of sol-gel TiO2 coatings during formic acid degradation under UV illumination. The micro-nanostructuring was performed using the UV illumination of microspheres deposited on a photopatternable sol-gel layer, leading to a hexagonal arrangement of micropillars after development. The structures and coatings were characterized using Raman spectroscopy, ellipsometry, atomic force microscopy and scanning electron microscopy. When the sol-gel TiO2 films were unstructured and untreated at 500 °C, their effect on formic acid's degradation under UV light was negligible. However, when the films were annealed at 500 °C, they crystallized in the anatase phase and affected the degradation of formic acid under UV light, also depending on the thickness of the layer. Finally, we demonstrated that surface micro-nanostructuring in the form of nanopillars can significantly increase the photocatalytic efficiency of a coating during the degradation of formic acid under UV light.

Pickering Emulsions of Fluorinated TiO2: A New Route for Intensification of Photocatalytic Degradation of Nitrobenzene.

Fluorination of the TiO2 surface has been often reported as a tool to increase the photocatalytic efficiency due to the beneficial effects in terms of production of oxidizing radicals. Moreover, it is shown that the unique amphiphilic properties of the fluorinated TiO2 (TiO2-F) surface allow one to use this material as a stabilizer for the formulation of Pickering emulsions of poorly soluble pollutants such as nitrobenzene (NB) in water. The emulsions have been characterized in terms of size of the droplets, type of emulsion, possibility of phase inversion, contact angle measurements, and optical microscopy. The emulsified system presents micrometer-sized droplets of pollutant surrounded by the TiO2-F photocatalyst. Consequently, the system can be considered to be composed of microreactors for the degradation of the pollutant, which maximize the contact area between the photocatalyst and substrate. The enhanced photocatalytic activity of TiO2-F was confirmed in the present paper as the apparent rate constants of NB photodegradation were 16 × 10-3 and 12 × 10-3 min-1 for fluorinated and bare TiO2, respectively. At NB concentrations largely exceeding its solubility, the rate constant was 0.04 × 10-3 min-1 in the presence of both TiO2 and TiO2-F. However, unlike TiO2, TiO2-F stabilized NB/water emulsions and, under these conditions, the efficiency of NB photocatalytic degradation in the emulsified system was ca. 18 times higher than in the nonemulsified one. This result is relevant also in terms of practical applications because it opens the route to one-pot treatments of biphasic polluted streams without the need of preliminary physical separation treatments.

Room-temperature conversion of Cu2-xSe to CuAgSe nanoparticles to enhance the photocatalytic performance of their composites with TiO2.

Rational design and precise engineering are needed to optimize the structural and chemical parameters of functional materials. In this work, we demonstrate how pre-formed binary metal selenides can be an excellent synthetic choice for the synthesis of ternary coinage metal selenide nanoparticles (NPs) with controlled composition. The mild conditions required to obtain these ternary coinage metal selenide NPs offered an easy synthesis of n% CuAgSe-TiO2 (n = 0.01, 0.1, 0.3 and 1.0 mol%) nanocomposites for photocatalytic applications without compromising the structural and morphological characteristics of TiO2 and without having any organic ligands around the NPs. The use of ternary metal selenide nanocomposites CuAgSe-TiO2 results in a clear improvement in their photocatalytic activity for the photodegradation of formic acid as compared to the well-known benchmark for photocatalysis, TiO2 (P25), and its binary metal selenide nanocomposites Cu2-xSe-TiO2. DFT calculations establish semi-metallic behavior of CuAgSe NPs and show that CuAgSe-TiO2 forms a semimetallic-semiconductor heterojunction allowing a better charge separation to enhance its photocatalytic activity.

Photocatalytic Degradation Enhancement in Pickering Emulsions Stabilized by Solid Particles of Bare TiO2.

Pickering emulsions provide a new way to enhance the efficiency of photocatalytic degradation of water-insoluble pollutants. Indeed, the semiconductor solid particles dually act as the photocatalyst and stabilizer of the emulsion droplets whose size dramatically affects the photocatalytic reaction. The present work aims at the validation of this concept by using bare TiO2 without any surface modification. Nanostructured TiO2 has been prepared by a simple sol-gel process and characterized by X-ray diffraction, specific surface area analysis, scanning electron microscopy, and diffuse reflectance spectroscopy. The emulsions were prepared by using 1-methylnaphthalene (1-MN) as a model organic contaminant scarcely soluble in water and bare TiO2 as the photocatalyst/stabilizer. The emulsions have been characterized by electrical conductivity, optical microscopy, and light-scattering analyses. The photocatalytic degradation of 1-MN was 50 times faster in stable Pickering emulsions with respect to the case of biphasic liquid systems containing TiO2. This finding allows us to propose Pickering emulsions stabilized by TiO2 nanoparticles as an effective and novel way to intensify the photocatalytic degradation of water-insoluble organic pollutants.

Precursor-mediated synthesis of Cu2-xSe nanoparticles and their composites with TiO2 for improved photocatalysis.

The direct synthesis of copper selenide nanoparticles from the reaction of ditertiarybutyl selenide tBu2Se with copper(ii) trifluoroacetate Cu(TFA)2 under mild conditions is reported. The isolation of a molecular species during the course of this reaction, established as [Cu2(TFA)2(tBu2Se)3], by spectroscopic studies and single crystal X-ray structure analysis, confirmed that metal selenide NPs are formed via this intermediate species containing a reduced copper center. Extending this reaction in the presence of commercial TiO2 (P25) offered an easy synthesis of copper selenide-titania nanocomposites with different Cu/Ti ratios. These nanocomposites, well-characterized by powder XRD, STEM, TEM, BET, XPS, EDX and UV-Vis studies, were examined as photocatalysts for the degradation of formic acid (FA). The nCu2-xSe-TiO2 nanocomposites with low mol% of copper selenide, i.e. n = 0.1 and 0.3 mol%, displayed a superior catalytic activity over P25, which is an established benchmark for photocatalysis under UV light.

Influenza viruses production: Evaluation of a novel avian cell line DuckCelt®-T17.

The influenza vaccine manufacturing industry is looking for production cell lines that are easily scalable, highly permissive to multiple viruses, and more effective in term of viral productivity. One critical characteristic of such cell lines is their ability to grow in suspension, in serum free conditions and at high cell densities. Influenza virus causing severe epidemics both in human and animals is an important threat to world healthcare. The repetitive apparition of influenza pandemic outbreaks in the last 20years explains that manufacturing sector is still looking for more effective production processes to replace/supplement embryonated egg-based process. Cell-based production strategy, with a focus on avian cell lines, is one of the promising solutions. Three avian cell lines, namely duck EB66®cells (Valneva), duck AGE.CR® cells (Probiogen) and quail QOR/2E11 cells (Baxter), are now competing with traditional mammalian cell platforms (Vero and MDCK cells) used for influenza vaccine productions and are currently at advance stage of commercial development for the manufacture of influenza vaccines. The DuckCelt®-T17 cell line presented in this work is a novel avian cell line developed by Transgene. This cell line was generated from primary embryo duck cells with the constitutive expression of the duck telomerase reverse transcriptase (dTERT). The DuckCelt®-T17 cells were able to grow in batch suspension cultures and serum-free conditions up to 6.5×106cell/ml and were easily scaled from 10ml up to 3l bioreactor. In the present study, DuckCelt®-T17 cell line was tested for its abilities to produce various human, avian and porcine influenza strains. Most of the viral strains were produced at significant infectious titers (>5.8 log TCID50/ml) with optimization of the infection conditions. Human strains H1N1 and H3N2, as well as all the avian strains tested (H5N2, H7N1, H3N8, H11N9, H12N5) were the most efficiently produced with highest titre reached of 9.05 log TCID50/ml for A/Panama/2007/99 influenza H3N2. Porcine strains were also greatly rescued with titres from 4 to 7 log TCID50/ml depending of the subtypes. Interestingly, viral kinetics showed maximal titers reached at 24h post-infection for most of the strains, allowing early harvest time (Time Of Harvest: TOH). The B strains present specific production kinetics with a delay of 24h before reaching the maximal viral particle release. Process optimization on H1N1 2009 human pandemic strain allowed identifying best operating conditions for production (MOI, trypsin concentration, cell density at infection) allowing improving the production level by 2 log. Our results suggest that the DuckCelt®-T17 cell line is a very promising platform for industrial production of influenza viruses and particularly for avian viral strains.

A Facile Molecular Precursor-based Synthesis of Ag2 Se Nanoparticles and Its Composites with TiO2 for Enhanced Photocatalytic Activity.

The reactions of different silver(I) reagents AgX (X(-) =iodide, trifluoroacetate, triflate) with selenoethers R2 Se (R=Me, tBu) in a variety of solvents were investigated in relation with their use as precursors for Ag2 Se nanomaterials. Different reaction conditions led to different reactivities and afforded either molecular complexes or metal selenide nanoparticles. The reactions leading to in situ formation of the metal selenide nanoparticles were then extended in the presence of commercial TiO2 (P25) to prepare silver selenide-titania nanocomposites with different Ag/Ti ratios. These nanocomposites, well characterized by elemental analysis (Ag, Se), PXRD, TEM, BET, XPS and UV/Vis studies, were investigated as photocatalysts for the degradation of formic acid (FA) solution. The xAg2 Se-TiO2 nanocomposites (x=0.01, 0.13 and 0.25 mol %) exhibited a much higher catalytic activity as compared to P25, which is an established benchmark for the photocatalysis under UV light, and retained a good photocatalytic stability after recycling for several times.