Year of Publication


Degree Name

Doctor of Philosophy (PhD)

Document Type

Doctoral Dissertation




Chemical and Materials Engineering

First Advisor

Dr. Dibakar Bhattacharyya


The development of functionalized membranes with tunable pores and catalytic properties provides us an opportunity to manipulate the membrane pore structure, selectivity and reactivity. By introducing the functional groups into membrane pores, dissolved metal ions and reactive particles can be effectively immobilized within the polymer matrix for toxic chloro-organic and heavy metal remediation in water.

A polyelectrolyte functionalized membrane platform with tunable pore size and ion exchange capacity has been developed for iron/iron oxide nano-catalyst synthesis and chlorinated organic compound (trichloroethylene, TCE and polychlorinated biphenyls, PCBs) degradation. Highly robust polyvinylidene fluoride (PVDF) microfiltration membranes are used as the support with cross-linked polyacrylic acid (PAA) filled in the pores. By varying the environmental pH, PAA hydrogels have either swelling or collapsing behavior, resulting in different effective membrane pore sizes for different separation purposes. Cation exchange groups (i.e. carboxyl groups) in PAA chains prevent the aggregation and leaching of nanoparticles (NPs) during in-situ synthesis and reaction. Depending on the catalyst loading and residence time, TCE and PCBs can be completely degraded by reduction of zero-valent iron and bimetallic iron/palladium NPs, or iron oxide catalyzed free radical oxidation at near-neutral pH. Biphenyl from PCB dechlorination can be further oxidized by hydroxyl radicals (OH•) generated from hydrogen peroxide (H2O2) decomposition. Hydroxybiphenyls and benzoic acid are identified as oxidation products. Line scan and elemental mapping in transmission electron microscopy (TEM) and X-ray photo electron spectroscopy (XPS) characterizations are conducted to understand the effect of iron surface transformation on NP reactivity, and to optimize the membrane functionalization.

The same platform can also be used to remove toxic metal selenium in the scrubber water of coal-fired power plants. By reducing the salt concentration in water or increasing the residence time and temperature, the concentration of selenium oxyanions in functionalized membrane permeate can be reduced to less than 10 µg/L. Selenium is captured in membranes by both iron reduction to metallic selenium and iron oxide adsorption. The full-scale flat sheet functionalized membrane and spiral wound modules have also been developed. Iron NPs with alterable loadings are successfully synthesized inside the membrane module for real water applications.