Dechlorination of 3, 3’, 4, 4’ – tetrachlorobiphenyl (PCB77) in water, by nickel/iron nanoparticles immobilized on L-lysine/PAA/PVDF membrane

M.Sc. (Chemistry)Zero-valent nanoscale metal, especially iron nanoparticles have attracted significant attention with regards to remediation of organochlorinated compounds in drinking water. For a more rapid and complete dechlorination, a second and usually electronegative element is often added, resulting in the formationof bimetallic nanoparticles. However, in the absence of surfactants,the bimetallic nanoparticles easily aggregate into large particles (if they are not anchored on solid supports) with wide size distributions, thus losing their reactivity. This work reports an in-situ synthesis method of bimetallic nanoparticles immobilized on L-lysine functionalized microfiltration membranes by chemical reduction of metal ions chelated by amine and hydroxyl functional groups of L-lysine on the composite. The immobilization of the nanoparticles on membranes offers many advantages: reduction of particle loss, prevention of particle agglomeration and application under convective flow. The objective of this research wasto produce catalytic filtration membranes for dechlorination of organic compound, PCB-77. This was achieved first by (i) the modification of commercial PVDF to introduce functional groups that render the membrane more hydrophilic and have the ability to capture metal ions through chelation, and secondly (ii) the controlled introduction of catalytic nanoparticles onto the composite membrane surface, anchored through chelation to the surface functional groups. This approach was selected with aview to produce uniform surface distribution of monodispersed bimetallic nanoparticles that are resistant to leaching during the reduction reactions. The modification of the PVDF membrane was achieved by firstly performing an in situ polymerization of acrylic acid followed by covalently bonded L-lysine to the polymerized acrylic acid chains using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC). The Fe ions were introduced to the composite by L-lysine chelation and subsequently reduced to Fe0 with NaBH4, and finally deposition of Ni2+ which later were also reduced to Ni0 with NaBH4. The Fe/Ni bimetallic NPs system was chosen based on its proven ability for the total dechlorination of chlorinated organic compounds. Systematic characterization of the composite was performed using ATR-FTIR, FESEM, EDS, HRTEM, XRD, AFM and Contact Angle measurements. A relatively uniform distribution of Fe/Ni nanoparticles was found in L-lysine/PAA/PVDF membrane. The diameter of Fe/Ni nanoparticles was predominantly within the range 20-30 nm. Furthermore, the mechanism of the catalytic dechlorination of the model compound, PCB 77, was investigated by careful analysis of the reaction products. It is generally known that zero-valent iron undergoes corrosion to provide hydrogen atoms and electrons for the reductive catalytic hydrodechlorination reaction. The second metal in the bimetallic system on the other hand, acts as..