Iron-Based Nanoparticles for Toxic Organic Degradation: Silica Platform and Green Synthesis.

Iron and iron oxide nanoparticles (NPs) are finding wide applications for the remediation of various toxic chloro-organic compounds (such as trichloroethylene, TCE), via reductive and oxidative processes. In this study, Fe NPs (30-50 nm) are synthesized by reduction from ferric ions immobilized (by ion exchange) on a platform (two types of sulfonated silica particles), in order to prevent the NP agglomeration. Next, the Fe NPs are oxidized and their effectiveness for the oxidative dechlorination of TCE via the heterogeneous decomposition of hydrogen peroxide to OH• on the surface of the iron oxide NPs was demonstrated. For the reductive approach, the use of ascorbic acid as a "green" reducing agent in conjunction with a secondary metal (Pd) inhibits NP oxidation and agglomeration through surface adsorbed species. The Fe/Pd NPs have been successfully applied for the dechlorination of TCE (k(SA), surface-area normalized reaction rate, = 8.1 ×10(-4) L/m(2)h).

Iron oxide nanoparticle synthesis in aqueous and membrane systems for oxidative degradation of trichloroethylene from water.

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.

Nanostructured membranes for enzyme catalysis and green synthesis of nanoparticles.

Macroporous membranes functionalized with ionizable macromolecules provide promising applications in high capacity toxic metal capture, nanoparticle syntheses, and catalysis. Our low-pressure membrane approach has good reaction and separation selectivities, which are tunable by varying pH, ionic strength, or pressure. The sustainable green chemistry approach under ambient conditions and the evaluation of a reactive poly(acrylic acid) (PAA)-modified polyvinylidene fluoride (PVDF) membrane is described. Two distinct membrane types were obtained through different methods: 1) a stacked membrane through layer-by-layer assembly for the incorporation of enzymes (catalase and glucose oxidase), providing tunable product yields and 2) Fe/Pd nanoparticles for degradation of pollutants, obtained through an in situ green synthesis. Bioreactor-nanodomain interactions and mixed matrix nanocomposite membranes provide remarkable versatility compared to conventional membranes.

Iron-Functionalized Membranes for Nanoparticle Synthesis and Reactions.

Membrane-based separation processes have been used extensively for drinking water purification, wastewater treatment, and numerous other applications. More recent developments in membrane functionalization have made the use of membrane science important in diverse fields, from tunable separations to catalysis. The focus of this work is to create a common membrane platform for the incorporation of technologies capable of degrading target pollutants. Functionalized membranes capable of metal capture were created using water-based and solvent-based acrylic acid polymerization to synthesize poly (acrylic acid) (PAA) within poly(vinylidene fluoride) (PVDF) membrane pores. The COO(-) groups of PAA were used to capture Fe(II), which was then either reduced and doped with Pd to form Fe/Pd nanoparticles or used as-is for free radical generation with hydrogen peroxide. Fe/Pd nanoparticles were synthesized within the pores of a PAA/PVDF membrane functionalized via aqueous (green) chemistry and used to dechlorinate trichloroethylene (TCE) and 2,2'-dichlorobiphenyl (DiCB). A PAA/PVDF membrane containing immobilized Fe(III) was used to obtain controlled free radical generation and target organic (pentachlorophenol) degradation within the membrane pore under convective flow conditions.