Preparation of novel composites based on hydrophilized and functionalized polyacrylonitrile membrane-immobilized NZVI for reductive transformation of metronidazole

For the first time, hydrophilized and functionalized polyacrylonitrile (PAN) membrane was synthesized via two-stage process, addition of polyvinyl alcohol and in situ polymerization of acrylic acid (AA), and nano zero-valent iron (NZVI) was incorporated within modified membrane. The as-prepared PAA/PAN-NZVI (PPN) composites possessed superior reactivity for metronidazole (MNZ) with transformation ratio 2.03 and reaction rate 4.77 times higher than that by bare NZVI. Meanwhile, the enhanced stability and recyclability of PPN composites were maintained over repeated cycles. The major advantages of synthetic method lie in the remarkably increased loading and decreased agglomeration of NZVI. Moreover, with hydrophilized and functionalized synthesis processes of membrane, the potential risk of released iron ions was not a concern due to strong chelation of grafted carboxyl groups. Analyses of morphological characteristics (FE-SEM), chemical structure (FTIR), element valence and groups (XPS) of samples confirmed the successful graft of carboxylic acid groups and formation of a uniform iron nanoparticles coating onto PAN matrix. The reaction kinetics of MNZ with PPN composites were well-described by a two-parameter pseudo-first-order decay model with activation energy of 29.5 kJ/mol. The co-solutes except humic acid had a negligible effect on MNZ transformation. Determination of intermediates revealed that nitro reduction, N-denitration and hydroxyethyl cleavage were the main pathways for transformation of MNZ. The findings suggest that the novel composites possess huge potential for antibiotics wastewater treatment. (C) 2016 Elsevier B.V. All rights reserved.