A Sulfonated All-Aromatic Polyamide for Heavy Metal Capture: A Model Study with Pb(II).

Polyelectrolytes are widely used in heavy metal removal, finding applications as coagulants and flocculants. We compare the heavy metal removal capability of a water-soluble sulfonated semirigid polyamide, poly(2,2'-disulfonyl-4,4'-benzidine isophthalamide) (PBDI), with that of a well-known random-coil polymer, poly(sodium 4-styrenesulfonate) (PSS). Using lead (Pb(II)) as a model contaminant, both polymers precipitate out from solution at ~500 mg/L Pb(II) in water. The ability to remove Pb(II) from water was quantified using adsorption isotherms and fitted with Langmuir and Freundlich adsorption models. The sorption of Pb(II) by PSS fit the Langmuir model with a high degree of correlation (0.976 R2), but the sorption of Pb(II) by PBDI could not be accurately predicted using the Langmuir or Freundlich model. The sorption of Pb(II) by PBDI and PSS was compared by normalizing sorption by the number of sulfonate groups of each polymer and the ion exchange capacity (IEC), found by titration. We find that PBDI removes a greater amount of Pb(II) per gram of sorbent compared to PSS, 410 mg/g vs 260 mg/g, respectively, which cannot be accounted for by differences in IEC or number of sulfonate groups. Our findings confirm that the positioning of the sulfonate groups and the rigidity of the polymer backbone play an important role in how Pb(II) coordinates to the polymer prior to precipitating out from solution.

Linear versus Nonlinear Aromatic Polyamides: The Role of Backbone Geometry in Thin Film Salt Exclusion Membranes.

Two aromatic polyamides─poly(3,3'-dihydroxybenzidine terephthalamide) (DHTA) and poly(3,3'-dihydroxybenzidine isophthalamide) (DHIA)─are compared for their ability to remove salts from water. DHTA is linear and rigid whereas DHIA is nonlinear and semirigid. DHTA and DHIA were selected as they allow us to investigate the effect of polymer backbone geometry on salt exclusion in a non-crosslinked thin film membrane, independently of the backbone chemistry. Because of their differences in solution viscosity, spin coating parameters for DHTA and DHIA solutions were optimized separately to produce thin film composites (TFCs) with reproducible membrane properties. The resulting DHTA TFCs displayed salt rejections of 87.8% (NaCl), 97.0% (MgSO4), and 80.3% (CaCl2). In comparison, DHIA TFCs demonstrated poor salt rejections of 21.0% (NaCl), 29.3% (MgSO4), and 15.4% (CaCl2). Cross-sectional SEM images of DHTA and DHIA films reveal that DHTA has a stratified (layered) morphology whereas DHIA exhibits a dense, featureless morphology. Both DHTA and DHIA TFCs exhibit similar surface morphology, contact angle, surface charge, and water uptake. PEG rejection experiments indicate that the average pore size of DHTA TFCs is ∼2 nm while DHIA TFCs have an average pore size of ∼3 nm. Our findings illustrate that using a rigid, linear aromatic polyamide gives an active layer with a stratified morphology, uniplanar orientation, smaller pores, and higher salt rejection, whereas the nonlinear aromatic polyamide analogue results in an isotropic active layer with larger pores and lower salt rejection.