Comparative evaluation of polymer surface functionalization techniques before iron oxide deposition. Activity of the iron oxide-coated polymer films in the photo-assisted degradation of organic pollutants and inactivation of bacteria

The preparation of iron oxide-coated polymer films and their photocatalytic activity in organic pollutants degradation and bacterial inactivation is described. Polyvinyl fluoride (PVF), polyethylene (PE) and polyethylene terephtalate (PET) films were used as catalyst supports. Polymer surfaces were functionalized by vacuum-UV radiation (V-UV) and radio-frequency plasma (RF-P); and also by photo-Fenton oxidation (P-FO) and TiO2 photocatalysis (Ti-PC) in solution. These pre-treatments were performed to improve iron oxide adhesion on the commercial polymer surface. The functionalized polymers films (P-f) were afterward immersed in an aqueous solution for the deposition of iron oxide layer by hydrolysis of FeCl3. The photocatalytic activities of iron oxide-coated functionalized polymers films (P-f-Fe oxide) prepared by different methods were compared during hydroquinone degradation in presence of H2O2. RF-P and Ti-PC pre-treated polymers showed significantly higher photocatalytic activity and long-term stability during processes leading to pollutant abatement, if compared with not treated ones (NT), although similar leaching of iron was observed for all the materials. PET bottles (PETb) were used as reactor and catalyst supports. The produced PETbf-Fe oxide surfaces were efficient in photo-assisted bacterial inactivation in the presence of H2O2, and no dissolved iron species were detected in solution. (C) 2010 Elsevier B.V. All rights reserved.

Development of a Photo-Fenton Catalyst Supported on Modified Polymer Films

Félicien Mazille

The work presented in this thesis is a part of the European project INNOWATECH. The global objective of this project was to provide effective technological solutions for the treatment of industrial wastewater, to propose new concepts in wastewater treatment with potential benefits for the protection of the environment. In particular photo-assisted Fenton oxidation was investigated. It is a promising technology to decontaminate industrial wastewater as it makes use of the natural energy that provides the sun, abundant chemicals (iron ions and hydrogen peroxide) and does not produce toxic waste. Apart from short detour about homogenous photo-Fenton reaction (chapter 2) where the influence of pollutant physico-chemical properties on reactivity is studied, this thesis focuses on photo-Fenton treatment using a new solid catalysis. The immobilization of iron oxide on a suitable support is a strategy proposed to overcome the practical limitation related to homogeneous photo-Fenton treatment (i.e. the limited operational pH range and the problems caused by the separation of catalyst from the effluent). The preparation and the surface characterization of new photo-Fenton catalysts based on iron oxide supported on modified polymer films is described in chapters 3 and 4. The photocatalytic activities of prepared materials were evaluated mainly toward organic pollutant degradation both at laboratory (chapter 3-5) and at pilot (chapter 6) scales. In detail, chapter 2 focuses on the effect of contaminant physico-chemical properties on the reactivity via photo-assisted Fenton catalysis. Several para-substituted phenols were used in order to cover a wide range of electronics effects. Many physico-chemical descriptors were correlated with the initial Fenton and photo-Fenton degradation rates (r0). Electronic descriptors such as calculated zero point energy (Ezero) and energy of the highest occupied orbital were found to be the most adequate to predict Fenton and photo-assisted Fenton reactivity. The preparation of iron oxide-coated polymer films is described in chapter 3. Polyvinyl fluoride (PVF) film surface was functionalized by different methods, either by Vacuum-UV radiation, radio-frequency plasma, photo-Fenton oxidation or TiO2 photocatalysis. These pre-treatments were performed to increase iron oxide adhesion to polymer surface. Afterward the functionalized polymers films were immersed in an aqueous solution for the deposition of iron oxide layer by hydrolysis of FeCl3. The catalytic activities of resulting materials were compared during hydroquinone degradation in presence of H2O2 and under simulated solar light illumination. The most efficient and stable catalyst obtained was prepared by means of TiO2 photocatalytic functionalization of polymers followed by iron oxide coating (leading to so called Pf-TiO2-Fe oxide), therefore this preparation procedure was selected in chapters 4-6. Chapter 4 focuses on the study of the mechanisms involved during the preparation and use of Pf-TiO2-Fe oxide. In particular, the modifications induced by TiO2 photocatalysis on polymer surface such as oxygen group formation and deposition of TiO2 particles were characterized by x-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and UV-visible spectrophotometry. The photocatalytic activity of Pf-TiO2-Fe oxide in presence of H2O2 and under simulated solar light radiation was evaluated toward HQ degradation. The occurrence of important synergistic effects between TiO2 and iron oxide was discussed. Finally, the effect of preparation parameters on photocatalytic activity of Pf-TiO2-Fe oxide/H2O2/light system was determined allowing the optimization of preparation procedure. Hence highly efficient photocatalysts for hydroquinone degradation and E. Coli inactivation were obtained. The degradation of hydroquinone and nalidixic acid (NA) mediated the system Pf-TiO2-Fe oxide/H2O2/light was examined (chapter 5). The contribution of homogeneous photo-Fenton oxidation in the degradation process was determined and the mechanisms involved in iron leaching are discussed. Besides, the effect of operational parameters on degradation rates was assessed. The rates are independent on initial pH and NaCl presence but were enhanced by increasing temperature. Long-term stability of Pf-TiO2-Fe oxide was evaluated by repetitive nalidixic acid degradation runs. The adaptation of Pf-TiO2-Fe oxide to pilot scale in a compound parabolic collector (CPC) solar photoreactor is described in chapter 6: solar photocatalytic degradation of phenol, nalidixic acid, mixture of pesticides, and another of emerging contaminants, in water was investigated. The influences of operational pH and pollutant structure on the degradation rates were evaluated. It was found that compounds with chelating moieties (or carboxylic acids) were the most quickly removed by Pf-TiO2-Fe oxide/H2O2/light and allowed the photo-Fenton catalyst to be efficient at higher pH values.

EPFL2010

Degradation of Eight Relevant Micropollutants in Different Water Matrices by Neutral Photo-Fenton Process under UV254 and Simulated Solar Light Irradiation – a comparative study

Luiz Felippe De Alencastro, Dominique Grandjean, César Pulgarin, Andrzej Sienkiewicz

This is a comparative study of photolytic degradation under exposure to UV254 nm and solar-simulator irradiation of a mixture of eight equally concentrated relevant micropollutants in the presence of H2O2 and Fe(II) in ultrapure water, Lake Geneva water, and effluent from a wastewater treatment plant (WWTP). The electron-spin resonance (ESR) experiments point to a low efficiency of singlet oxygen formation by the mixture of micropollutants. This finding corroborates with the chemical stability of the micropollutants under UVC irradiation (in decreasing order: gabapentin, metformin, metoprolol, atenolol, clarithromycin, primidone, methylbenzotriazole, and benzotriazole). The oxidation rate increased in the presence of low-concentration H2O2 and Fe(II), except for metformin and gabapentin. Gabapentin and metformin were the most persistent compounds, less than 24% were removed after 60 minutes of UV254/H2O2/Fe(II) treatment. The low micropollutant removal rates were observed in WWTP effluent and lake water, and using sunlight simulation. Guanylurea, phenol, oxalic acid, tartronic acid, glycolic acid, oxamic acid, and maleic acid, could also be detected as fragmental oxidation products. Furthermore, up to 300 µg/L of nitrate and ammonia were identified as final degradation products. Ecotoxicological tests showed that the degradation products are more toxic for algae Chlamydomonas reinhardtii than the parent compounds themselves.

Elsevier Science Bv2014

Development of a Photo-Fenton Catalyst Supported on Modified Polymer Films

Félicien Mazille

EPFL2010