New concept to remove heavy metals from liquid waste based on electrochemical pH-switchable immobilized ligands

Absorption on resins is often used as secondary step in the treatment of water-based effluents, in order to reach very low concentrations. The separation of the trapped effluents from the resins and the regeneration of the resins for further use create wide volumes of secondary effluents coming from the washings of the resins with chemical reagents. We propose an alternative solution based on a "surface strategy" through adsorption phenomena and electrical control of the expulsion stage. The final goal is to limit or ideally to avoid the use of chemical reagents at the expulsion (or regeneration) stage of the depolluting process. Heavy metal ions were captured on active filters composed by a conducting surface covered by poly-4-vinylpyridine (P4VP). Due to pyridine groups those polymer films have chelating properties for copper ions. Our strategy for electrical triggering of the copper expulsion in aqueous medium is based on pH sensitive chelating groups. Applying moderate electro-oxidizing conditions generates acidic conditions in the vicinity of the electrode, i.e. "inside" the polymer film. This allows a "switch-off" of the complexing properties of the film from the basic form of pyridine to pyridinium. Interestingly, no buffer washing is necessary to restore (or "switch-on") the complexing properties of the polymer film because the pH of the external medium is left unchanged by the electrochemical effect that affects only the vicinity of the electrode. Switch-on/switch-off cycles are followed and attested by IR spectroscopy and EQCM method.