Many current treatments for the reclamation of contaminated water sources are chemical-intensive, energy-intensive, and/or require posttreatment due to unwanted by-product formation. We demonstrate that through the integration of nanostructured materials, enzymatic catalysis, and iron-catalyzed free radical reactions within pore-functionalized synthetic membrane platforms, we are able to conduct environmentally important oxidative reactions for toxic organic degradation and detoxification from water without the addition of expensive or harmful chemicals. In contrast to conventional, passive membrane technologies, our approach utilizes two independently controlled, nanostructured membranes in a stacked configuration for the generation of the necessary oxidants. These include biocatalytic and organic/inorganic (polymer/ iron) nanocomposite membranes. The bioactive (top) membrane contains an electrostatically immobilized enzyme for the catalytic production of one of the main reactants, hydrogen peroxide (H 2 O 2 ), from glucose. The bottom membrane contains either immobilized iron ions or ferrihydrite/iron oxide nanoparticles for the decomposition of hydrogen peroxide to form powerful free radical oxidants. By permeating (at low pressure) a solution containing a model organic contaminant, such as trichlorophenol, with glucose in oxygen-saturated water through the membrane stack, significant contaminant degradation was realized. To illustrate the effectiveness of this membrane platform in real-world applications, membrane-immobilized ferrihydrite/iron oxide nanoparticles were reacted with hydrogen peroxide to form free radicals for the degradation of a chlorinated organic contaminant in actual groundwater. Although we establish the development of these nanostructured materials for environmental applications, the practical and methodological advances demonstrated here permit the extension of their use to applications including disinfection and/or virus inactivation.enzyme catalysis | functionalized membranes | pollutant | microfiltration | responsive materials

The potential for using hydroxyl radical (OH•) reactions catalyzed by iron oxide nanoparticles (NPs) to remediate toxic organic compounds was investigated. Iron oxide NPs were synthesized by controlled oxidation of iron NPs prior to their use for contaminant oxidation (by H2O2 addition) at near-neutral pH values. Cross-linked polyacrylic acid (PAA) functionalized polyvinylidene fluoride (PVDF) microfiltration membranes were prepared by in situ polymerization of acrylic acid inside the membrane pores. Iron and iron oxide NPs (80–100 nm) were directly synthesized in the polymer matrix of PAA/PVDF membranes, which prevented the agglomeration of particles and controlled the particle size. The conversion of iron to iron oxide in aqueous solution with air oxidation was studied based on X-ray diffraction, Mössbauer spectroscopy and BET surface area test methods. Trichloroethylene (TCE) was selected as the model contaminant because of its environmental importance. Degradations of TCE and H2O2 by NP surface generated OH• were investigated. Depending on the ratio of iron and H2O2, TCE conversions as high as 100 % (with about 91 % dechlorination) were obtained. TCE dechlorination was also achieved in real groundwater samples with the reactive membranes.

The remediation of toxic metals from water with high concentrations of salt has been an emerging area for membrane separation. Cost-effective nanomaterials such as iron and iron oxide nanoparticles have been widely used in reductive and oxidative degradation of toxic organics. Similar procedures can be used for redox transformations of metal species (e.g. metal oxyanions to elemental metal), and/or adsorption of species on iron oxide surface. In this study, iron-functionalized membranes were developed for reduction and adsorption of selenium from coal-fired power plant scrubber water. Iron-functionalized membranes have advantages over iron suspension as the membrane prevents particle aggregation and dissolution. Both lab-scale and full-scale membranes were prepared first by coating polyvinylidene fluoride (PVDF) membranes with polyacrylic acid (PAA), followed by ion exchange of ferrous ions and subsequent reduction to zero-valent iron nanoparticles. Water permeability of membrane decreased as the percent PAA functionalization increased, and the highest ion exchange capacity (IEC) was obtained at 20% PAA with highly pH responsive pores. Although high concentrations of sulfate and chloride in scrubber water decreased the reaction rate of selenium reduction, this was shown to be overcome by integration of nanofiltration (NF) and iron-functionalized membranes, and selenium concentration below 10 μg/L was achieved.

Membranes have been widely used in water remediation (e.g. desalination and heavy metal removal) because of the ability to control membrane pore size and surface charge. The incorporation of nanomaterials into the membranes provides added benefits through increased reactivity with different functionality. In this study, we report the dechlorination of 2-chlorobiphenyl in the aqueous phase by a reactive membrane system. Fe/Pd bimetallic nanoparticles (NPs) were synthesized (in-situ) within polyacrylic acid (PAA) functionalized polyvinylidene fluoride (PVDF) membranes for degradation of polychlorinated biphenyls (PCBs). Biphenyl formed in the reduction was further oxidized into hydroxylated biphenyls and benzoic acid by an iron-catalyzed hydroxyl radical (OH•) reaction. The formation of magnetite on Fe surface was observed. This combined pathway (reductive/oxidative) could reduce the toxicity of PCBs effectively while eliminating the formation of chlorinated degradation byproducts. The successful manufacturing of full-scale functionalized membranes demonstrates the possibility of applying reactive membranes in practical water treatment.

Abstract:Membranes are finding wide applications in various fields spanning biological, water, and energy areas. Synthesis of membranes to provide tunable flux, metal sorption, and catalysis has been done through pore functionalization of microfiltration (MF) type membranes with responsive behavior. This methodology provides an opportunity to improve synthetic membrane performance via polymer fabrication and surface modification. By optimizing the polymer coagulation conditions in phase inversion fabrication, spongy polyvinylidene fluoride (PVDF) membranes with high porosity and large internal pore volume were created in lab and full scale. This robust membrane shows a promising mechanical strength as well as high capacity for loading of adsorptive and catalytic materials. By applying surface modification techniques, synthetic membranes with different functionality (carboxyl, amine, and nanoparticle-based) were obtained. These functionalities provide an opportunity to fine-tune the membrane surface properties such as charge and reactivity. The incorporation of stimuli-responsive acrylic polymers (polyacrylic acid or sodium polyacrylate) in membrane pores also results in tunable pore size and ion-exchange capacity. This provides the added benefits of adjustable membrane permeability and metal capture efficiency. The equilibrium and dynamic binding capacity of these functionalized spongy membranes were studied via calcium ion-exchange. Iron/palladium catalytic nanoparticles were immobilized in the polymer matrix in order to perform the challenging degradation of the environmental pollutant trichloroethylene (TCE).