The effect of oxygen in the photocatalytic oxidation pathways of perfluorooctanoic acid

The influence of oxygen in the photocatalytic oxidation of perfluorooctanoic acid (PFOA) promoted by a commercial nano-sized titanium dioxide was studied by testing the reaction in different conditions: static air, oxygen flux, nitrogen flux and pre-saturated nitrogen flux. The reaction was monitored by Total Organic Carbon (TOC) analysis and Ionic Chromatography (IC). Shorter chain perfluorocarboxylic acids (PFCAs; C-n, n = 1-7) intermediate degradation products were quantitatively determined by High-Performance Liquid Chromatography combined with Mass Spectrometry (HPLC-MS) analysis. The presence of shorter chain PFCAs in solution was also monitored by F-19 NMR. The experimental findings are in agreement with two major oxidative pathways: C-n -> Cn-1 photo-redox and beta-scissions routes mediated by COF2 elimination. Depending on the experimental conditions, the mutually operating mechanisms could be unbalanced up to the complete predominance of one pathway over the other. In particular, the existence of the beta-scissions route with COF2 elimination was corroborated by the isolation and characterization of carbonyl difluoride, a predicted fluorinated decomposition by-product

Flexible Perfluoropolyethers-Functionalized CNTs-Based UHMWPE Composites: A Study on Hydrogen Evolution, Conductivity and Thermal Stability

Flexible conductive composites based on ultra-high molecular weight polyethylene (UHMWPE) filled with multi-walled carbon nanotubes (CNTs) modified by perfluoropolyethers (PFPEs) were produced. The bonding of PFPE chains, added in 1:1 and 2:1 weight ratios, on CNTs influences the dispersion of nanotubes in the UHMWPE matrix due to the non-polar nature of the polymer, facilitating the formation of nanofillers-rich conductive pathways and improving composites' electrical conductivity (two to five orders of magnitude more) in comparison to UHMWPE-based nanocomposites obtained with pristine CNTs. Electrochemical atomic force microscopy (EC-AFM) was used to evaluate the morphological changes during cyclic voltammetry (CV). The decrease of the overpotential for hydrogen oxidation peaks in samples containing PFPE-functionalized CNTs and hydrogen production (approximately -1.0 V vs. SHE) suggests that these samples could find application in fuel cell technology as well as in hydrogen storage devices. Carbon black-containing composites were prepared for comparative study with CNTs containing nanocomposites

Perfluoropolyethers as superhydrophobizing agents for carbon-based surfaces of fuel cell gas diffusion layers

Perfluoropolyether (PFPE) peroxide confers superhydrophobic properties to carbon black (CB) and carbon cloth (CC) as Gas Diffusion Layer (GDL) materials by direct functionalization. The thermal decomposition of PFPE peroxide synthesizes PFPE radicals which covalently bond the unsaturated moieties on carbonaceous surfaces. PFPE-functionalized CB and CC were characterized by X-ray photoelectron spectroscopy (XPS), surface area analysis, resistivity measurements, scanning electron microscopy (SEM) and contact angle measurements. The PFPE-modified materials resulted superhydrophobic were employed for the fabrication of single and dual layer GDLs. GDLs were tested in a single fuel cell at the lab scale. The cell tests were run at two temperatures (60°C and 80°C) with a relative humidity (RH) of hydrogen and air feeding gases equal to 80/100% and 60/100%, respectively

Flexible Perfluoropolyethers-Functionalized CNTs-Based UHMWPE Composites: A Study on Hydrogen Evolution, Conductivity and Thermal Stability

Flexible conductive composites based on ultra-high molecular weight polyethylene (UHMWPE) filled with multi-walled carbon nanotubes (CNTs) modified by perfluoropolyethers (PFPEs) were produced. The bonding of PFPE chains, added in 1:1 and 2:1 weight ratios, on CNTs influences the dispersion of nanotubes in the UHMWPE matrix due to the non-polar nature of the polymer, facilitating the formation of nanofillers-rich conductive pathways and improving composites’ electrical conductivity (two to five orders of magnitude more) in comparison to UHMWPE-based nanocomposites obtained with pristine CNTs. Electrochemical atomic force microscopy (EC-AFM) was used to evaluate the morphological changes during cyclic voltammetry (CV). The decrease of the overpotential for hydrogen oxidation peaks in samples containing PFPE-functionalized CNTs and hydrogen production (approximately −1.0 V vs. SHE) suggests that these samples could find application in fuel cell technology as well as in hydrogen storage devices. Carbon black-containing composites were prepared for comparative study with CNTs containing nanocomposites

Comparison of Branched and Linear Perfluoropolyether Chains Functionalization on Hydrophobic, Morphological and Conductive Properties of Multi-Walled Carbon Nanotubes

The functionalization of multi-walled carbon nanotubes (MW-CNTs) was obtained by generating reactive perfluoropolyether (PFPE) radicals that can covalently bond to MW-CNTs\u2019 surface. Branched and linear PFPE peroxides with equivalent molecular weights of 1275 and 1200 amu, respectively, have been thermally decomposed for the production of PFPE radicals. The functionalization with PFPE chains has changed the wettability of MW-CNTs, which switched their behavior from hydrophilic to super-hydrophobic. The low surface energy properties of PFPEs have been transferred to MW-CNTs surface and branched units with trifluoromethyl groups, CF3, have conferred higher hydrophobicity than linear units. Porosimetry discriminated the effects of PFPE functionalization on meso-porosity and macro-porosity. It has been observed that reactive sites located in MW-CNTs mesopores have been intensively functionalized by branched PFPE peroxide due to its low average molecular weight. Conductivity measurements at different applied pressures have showed that the covalent linkage of PFPE chains, branched as well as linear, weakly modified the electrical conductivity of MW-CNTs. The decomposed portions of PFPE residues, the PFPE chains bonded on carbon nanotubes, and the PFPE fluids obtained by homo-coupling side-reactions were evaluated by mass balances. PFPE-modified MW-CNTs have been characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), static contact angle (SCA), surface area, and porosity measurements

Immobilization of TiO2 nanopowders in multilayer fluorinated coatings for highly efficient clear and turbid wastewater remediation

The use of nanosized photocatalytic TiO2 in suspension or slurry type reactors is well reported. However, the industrial feasibility of such systems is limited, on account of the low quantum efficiency reported for slurry processes and of the need for a post-treatment catalyst recovery stage, which may present poor efficiency, with the double drawback of dispersing nanoparticles in the environment and losing precious photocatalyst. In this work, the photodegradative activity of titanium dioxide immobilized into a multilayered transparent fluoropolymeric matrix has been studied. Several TiO2 nanostructured powders featuring different primary particle size, crystalline phase and specific surface area have been produced by the flame spray pyrolysis (FSP) of organic solutions containing titanium (IV) isopropoxide. The activity of such powders has been tested and compared to that of TiO2 P25 by Evonik Degussa, which is the reference nanopowder commonly employed in the evaluation of the photocatalytic activity of non-commercial TiO2. A multilayer ionomeric-perfiuorinated matrix has been used to immobilize the powders, having high chemical resistance and transparency towards UV light, good permeability to oxygen and good wettability to favor interactions with the polluted aqueous solutions

The environmental issue on CFCs in the optimization of the Italian system for WEEE recycling

The fast innovation cycle of electrical and electronic equipments (EEEs) pose the problem of a large waste production. The correct disposal of WEEE is strictly needed because of their content in hazardous materials, like heavy metals and environmentally dangerous chemicals, which substances can be very dangerous both for the human health and the environment in which they are released. Chlorofl uorocarbons (CFCs) are largely present in a particular class of WEEE, cooling and freezing equipment. CFCs are well recognized as ozone-depleting gases and can have an impact on the global warming higher than CO2. Being Northern Italy the primary source of CFC in Europe, the Italian WEEE Management System development has been investigated, with a focus on cooling and freezing equipment and related CFCs disposal