Effect of polyacid dopants on the performance of polyaniline membranes in organic solvent nanofiltration

Abstract

Polyaniline (PANI) has been widely explored as a promising membrane material, but the trade-off between porosity and stability limits its widespread application in organic solvent nanofiltration (OSN). Here we present a simple approach to prepare PANI membranes with excellent chemical stability and rejection performance in OSN by employing polyacids as PANI dopants for the first time. The PANI membranes were doped with two polyacids with different molecular weights (MW) and acid dissociation constants (pKa): namely poly(4-styrenesulfonic acid) (PSSA, MW: 75000 g mol(-1), pKa: 0.94) and poly(2-acrylamido-2-methyl-l-propanesulfonic acid) (PAMPSA, MW: 800000 g mol(-1), pKa: 0.87), and were compared with a small acid (HCI) doped PANI membrane. The polyacid doped membranes, PANI-PSSA and PANI-PAMPSA, obtained dense structures with increased hydrophilicity due to strong intermolecular interactions between the PANI and the polyacids. Stability tests showed that the PANI-PSSA and PANI-PAMPSA were stable in a wide range of polar and nonpolar solvents, while the undoped PANI and PANI-HCI had poor stability in these solvents. The swelling degree and permeance of the doped membranes decreased with the increase of the dopant MW. The PANI-PAMPSA membrane exhibited a molecular weight cut-off (MWCO) in the nanofiltration (NF) range of 400 g mol(-1) in methanol and isopropanol, while the PANI-HCl and PANI-PSSA membranes were in the ultrafiltration (UF) range. This study demonstrates that polyacid doping can make stable and nanoporous PANI membranes for OSN applications without the need for crosslinking. This simple approach can be used to design new classes of OSN membranes for challenging separation processes in the future.