Self-coagulating polyelectrolyte complexes for target-tunable adsorption and separation of metal ions

Metal-containing wastes in aquatic environments lead to public health hazards and valuable resource lose. Metal-bearing wastewater must be treated to remove heavy metals or recover precious metals. To achieve these, target-tunable adsorbents that bind cationic and anionic metal species were developed through facile polyelectrolyte complexation using polyethylenimine (PEI) and polyacrylic acid (PAA). Utilizing the properties of the two polyelectrolytes and pK_a variabilities, stable tunable adsorbents were fabricated in water without additional solvents. The homogenous complex adsorbents were strategically synthesized via dissolution in 0.1 M NaOH and drop-wise addition of 1 M HCl, followed by crosslinking with glutaraldehyde. Consequently, the adsorbents in alternating weight ratios of 4:1 and 1:4 (PEI:PAA) exhibited good tunability and adsorption properties. The maximum single metal adsorption capacities were 1609.7 ± 49.6 and 558.6 ± 9.67 mg/g for gold and cadmium, respectively. The pseudo-second-order model fitted the kinetics data more appropriately and was recognized as the rate controlling step. In a binary mixture, gold selectivity was observed to be influenced by adsorption-reduction mechanism, which was elucidated by XRD and XPS. Moreover, the adsorbents demonstrated NO₃- sequestration properties, a feat deemed important for environmental remediation of nitrate ions. Finally, sequential separation was achieved with ethylenediaminetetraacetic acid (EDTA) and acidified thiourea.