Hybrid Photoelectrocatalytic TiO2-Co3O4/Co(OH)2 Materials Prepared from Bio-Based Surfactants for Water Splitting.

The development of new photoanode materials for hydrogen production and water treatment is in full progress. In this context, hybrid TiO2-Co3O4/Co(OH)2 photoanodes prepared using the sol-gel method using biosurfactants are currently being developed by our group. The combination of TiO2 with a cobalt-based compound significantly enhances the visible absorption and electrochemical performance of thin films, which is mainly due to an increase in the specific surface area and a decrease in the charge transfer resistance on the surface of the thin films. The formation of these composites allows for a 30-fold increase in the current density when compared to cobalt-free materials, with the best TiO2-CoN0.5 sample achieving a current of 1.570 mA.cm-2 and a theoretical H2 production rate of 0.3 µmol.min-1.cm-2 under xenon illumination.

Electro-oxidation of secondary effluents from various wastewater plants for the removal of acetaminophen and dissolved organic matter.

Electro-oxidation of acetaminophen (ACT) in three different doped secondary effluents collected from a conventional Municipal Waste Water Treatment Plant (MWWTP), a MWWTP using a membrane bioreactor (WWTP MBR) and a lab-scale MBR treating source-separated urine (Urine MBR) was investigated by electro-Fenton (EF) coupled with anodic oxidation (AO) using sub-stoichiometric titanium oxide anode (Ti4O7). After 8 h of treatment, 90 ± 15%, 76 ± 3.8% and 46 ± 1.3% of total organic carbon removal was obtained for MWWTP, MWWTP-MBR and Urine-MBR respectively, at a current intensity of 250 mA, pH of 3 and [Fe2+] = 0.2 mM. Faster degradation of ACT was observed in the WWTP MBR because of the lower amount of competitive organic matter, however, >99% degradation of ACT was obtained after 20 min for all effluents. The acute toxicity of the treated effluent was measured using Microtox® tests. Results showed an initial increase in toxicity, which could be assigned to formation of more toxic by-products than parent compounds. From 3D excitation and emission matrix fluorescence (3DEEM), different reactivity was observed according to the nature of the organic matter. Particularly, an increase of low molecular weight organic compounds fluorescence was observed during Urine MBR treatment. This could be linked to the slow decrease of the acute toxicity during Urine MBR treatment and ascribed to the formation and recalcitrance of toxic organic nitrogen and chlorinated organic by-products. By comparison, the acute toxicity of other effluents decreased much more rapidly. Finally, energy consumption was calculated according to the objective to achieve (degradation, absence of toxicity, mineralization).

Electrochemical advanced oxidation processes using novel electrode materials for mineralization and biodegradability enhancement of nanofiltration concentrate of landfill leachates.

The objective of this study was to implement electrochemical advanced oxidation processes (EAOPs) for mineralization and biodegradability enhancement of nanofiltration (NF) concentrate from landfill leachate initially pre-treated in a membrane bioreactor (MBR). Raw carbon felt (CF) or FeIIFeIII layered double hydroxides-modified CF were used for comparing the efficiency of homogeneous and heterogeneous electro-Fenton (EF), respectively. The highest mineralization rate was obtained by heterogeneous EF: 96% removal of dissolved organic carbon (DOC) was achieved after 8 h of electrolysis at circumneutral initial pH (pH0 = 7.9) and at 8.3 mA cm-2. However, the most efficient treatment strategy appeared to be heterogeneous EF at 4.2 mA cm-2 combined with anodic oxidation using Ti4O7 anode (energy consumption = 0.11 kWh g-1 of DOC removed). Respirometric analyses under similar conditions than in the real MBR emphasized the possibility to recirculate the NF retentate towards the MBR after partial mineralization by EAOPs in order to remove the residual biodegradable by-products and improve the global cost effectiveness of the process. Further analyses were also performed in order to better understand the fate of organic and inorganic species during the treatment, including acute toxicity tests (Microtox®), characterization of dissolved organic matter by three-dimensional fluorescence spectroscopy, evolution of inorganic ions (ClO3-, NH4+ and NO3-) and identification/quantification of degradation by-products such as carboxylic acids. The obtained results emphasized the interdependence between the MBR process and EAOPs in a combined treatment strategy. Improving the retention in the MBR of colloidal proteins would improve the effectiveness of EAOPs because such compounds were identified as the most refractory. Enhanced nitrification would be also required in the MBR because of the release of NH4+ from mineralization of refractory organic nitrogen during EAOPs.

Mineralization of organic pollutants by anodic oxidation using reactive electrochemical membrane synthesized from carbothermal reduction of TiO2.

Reactive Electrochemical Membrane (REM) prepared from carbothermal reduction of TiO2 is used for the mineralization of biorefractory pollutants during filtration operation. The mixture of Ti4O7 and Ti5O9 Magnéli phases ensures the high reactivity of the membrane for organic compound oxidation through •OH mediated oxidation and direct electron transfer. In cross-flow filtration mode, convection-enhanced mass transport of pollutants can be achieved from the high membrane permeability (3300 LMH bar-1). Mineralization efficiency of oxalic acid, paracetamol and phenol was assessed as regards to current density, transmembrane pressure and feed concentration. Unprecedented high removal rates of total organic carbon and mineralization current efficiency were achieved after a single passage through the REM, e.g. 47 g m-2 h-1 - 72% and 6.7 g m-2 h-1 - 47% for oxalic acid and paracetamol, respectively, at 15 mA cm-2. However, two mechanisms have to be considered for optimization of the process. When the TOC flux is too high with respect to the current density, aromatic compounds polymerize in the REM layer where only direct electron transfer occurs. This phenomenon decreases the oxidation efficiency and/or increases REM fouling. Besides, O2 bubbles sweeping at high permeate flux promotes O2 gas generation, with adverse effect on oxidation efficiency.

The Reductive Dehydration of Cellulose by Solid/Gas Reaction with TiCl4 at Low Temperature: A Cheap, Simple, and Green Process for Preparing Anatase Nanoplates and TiO2 /C Composites.

Metal oxides and metal oxide/carbon composites are entering the development of new technologies and should therefore to be prepared by sustainable chemistry processes. Therefore, a new aspect of the reactivity of cellulose is presented through its solid/gas reaction with vapour of titanium(IV) chloride in anhydrous conditions at low temperature (80 °C). This reaction leads to two transformations both for cellulose and titanium(IV) chloride. A reductive dehydration of cellulose is seen at the lowest temperature ever reported and results in the formation of a carbonaceous fibrous solid as the only carbon-containing product. Simultaneously, the in situ generation of water leads to the formation of titanium dioxide with an unexpected nanoplate morphology (ca. 50 nm thickness) and a high photocatalytic activity. We present the evidence showing the evolution of the cellulose and the TiO2 nanostructure formation, along with its photocatalytic activity. This low-temperature process avoids any other reagents and is among the greenest processes for the preparation of anatase and also for TiO2 /carbon composites. The anisotropic morphology of TiO2 questions the role of the cellulose on the growing process of these nanoparticles.

Dynamic Mechanisms of the Bactericidal Action of an Al2O3-TiO2-Ag Granular Material on an Escherichia coli Strain.

The bactericidal activity of an Al2O3-TiO2-Ag granular material against an Escherichia coli strain was confirmed by a culture-based method. In particular, 100% of microorganisms were permanently inactivated in 30 to 45 min. The present work aimed to investigate the mechanisms of the bactericidal action of this material and their dynamics on Escherichia coli using different techniques. Observations by transmission electron microscopy (TEM) at different times of disinfection revealed morphological changes in the bacteria as soon as they were put in contact with the material. Notably highlighted were cell membrane damage; cytoplasm detachment; formation of vacuoles, possibly due to DNA condensation, in association with regions exhibiting different levels of electron density; and membrane lysis. PCR and flow cytometry analyses were used to confirm and quantify the observations of cell integrity. The direct exposure of cells to silver, combined with the oxidative stress induced by the reactive oxygen species (ROS) generated, was identified to be responsible for these morphological alterations. From the first 5 min of treatment with the Al2O3-TiO2-Ag material, 98% of E. coli isolates were lysed. From 30 min, cell viability decreased to reach total inactivation, although approximately 1% of permeable E. coli cells and 1% of intact cells (10(5) genomic units·ml(-1)) were evidenced. This study demonstrates that the bactericidal effect of the material results from a synergic action of desorbed and supported silver. Supported silver was shown to generate the ROS evidenced.