Membrane process including microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) have provided numerous successful applications ranging from drinking water purification, wastewater treatment, to material recovery. The addition of functional moiety in the membranes pores allows such membranes to be used in challenging areas including tunable separations, toxic metal capture, and catalysis. In this work, polyvinylidene fluoride (PVDF) MF membrane was functionalized with temperature responsive (poly(N-isopropylacrylamide), PNIPAAm) and pH responsive (polyacrylic acid, PAA) polymers. It’s revealed that the permeation of various molecules (water, salt and dextran) through the membrane can be thermally or pH controlled. The introduction of PAA as a polyelectrolyte offers an excellent platform for the immobilization of metal nanoparticles (NPs) applied for degradation of toxic chlorinated organics with significantly increased longevity and stability. The advantage of using temperature and pH responsive polymers/hydrogels also includes the high reactivity and effectiveness in dechlorination. Further advancement on the PVDF functionalization involved the alkaline treatment to create partially defluorinated membrane (Def-PVDF) with conjugated double bounds allowing for the covalent attachment of different polymers. The PAA-Def-PVDF membrane shows pH responsive behavior on both the hydraulic permeability and solute retention. The sponge-like PVDF (SPVDF) membranes by phase inversion were developed through casting PVDF solution on polyester backing. The SPVDF membrane was demonstrated to have 4 times more surface area than commercial PVDF MF membrane, allowing for enhanced nanoparticles loading for chloro-organics degradation. The advanced functionalization method and process were also validated to be able to be scaled-up through the evaluation of full-scale functionalized membrane provided by Ultura Inc. California, USA. Nanofiltration (NF) between UF and RO presents selectivity controlled by both steric and electrostatic repulsions, which are widely used to reject charged species, particularly multivalent ions. In this work, selective permeation of CaCl2 and high sucrose retention are obtained through the modification of nanofiltration membranes with lower charge compared to commercial nanofiltration membrane. The membrane module also shows high stability with constant water permeability in a long-term (two months) test. Extended Nernst-Planck equation were further used to evaluate the experimental results and it fits well.

Membrane-based separation processes have been used extensively for drinking water purification, wastewater treatment, and numerous other applications. Reactive membranes synthesized through functionalization of the membrane pores offer enhanced reactivity due to increased surface area at the polymer-solution interface and low diffusion limitations. Oxidative techniques utilizing free radicals have proven effective for both the destruction of toxic organics and non-environmental applications. Most previous work focuses on reactions in the homogeneous phase; however, the immobilization of reactants in membrane pores offers several advantages. The use of polyanions immobilized in a membrane or chelates in solution prevents ferric hydroxide precipitation at near-neutral pH, a common limitation of iron(Fe(II/III))-catalyzed hydrogen peroxide (H2O2) decomposition. The objectives of this research are to develop a membrane-based platform for the generation of free radicals, degrade toxic organic compounds using this and similar solution-based reactions, degrade toxic organic compounds in droplet form, quantify hydroxyl radical production in these reactions, and develop kinetic models for both processes. In this study, a functionalized membrane containing poly(acrylic acid) (PAA) was used to immobilize iron ions and conduct free radical reactions by permeating H2O2 through the membrane. The membrane’s responsive behavior to pH and divalent cations was investigated and modeled. The conversion of Fe(II) to Fe(III) in the membrane and its effect on the decomposition of hydrogen peroxide were monitored and used to develop kinetic models for predicting H2O2 decomposition in these systems. The rate of hydroxyl radical production, and hence contaminant degradation can be varied by changing the residence time, H2O2 concentration, and/or iron loading. Using these membrane-immobilized systems, successful removal of toxic organic compounds, such as pentachlorophenol (PCP), from water was demonstrated. Another toxic organic compound of interest for water treatment applications is trichloroethylene (TCE). Due to its limited solubility in water, a majority of the TCE is often present in the form of droplets. In this study, effective TCE droplet degradation using chelate-modified, iron-catalyzed free radical reactions at near-neutral pH was demonstrated. In order to predict the degradation of aqueous and non-aqueous phase TCE for these reactions, a mathematical model was constructed through the use of droplet mass transfer correlations and free radical reaction kinetics.