Design and analysis of an electronically switchable ion exchange system

Metal contamination is a considerable environmental problem because metals are persistent contaminants. Ion exchange is one of the most commonly used treatment options for trace metal removal. This research develops and evaluates a redox active modified ion exchange system that has the potential to reduce the ionic strength of ion exchange regeneration streams. Poly-L-cysteine (PLC) was selected as the redox active, adsorbing functional group on the surface of a reticulated vitreous carbon (RVC) electrode. PLC is an excellent soft acid metal chelator and is unique in that its thiol groups can form disulfide bonds with each other. The reduction of available thiols changes the metal binding capacity of the peptide since the thiol is the primary binding group. RVC provides a macroporous conductive monolithic resin to support the peptide. An experimental apparatus was designed to study the properties of this system and estimate performance. Distinct oxidized and reduced states of PLC on the surface of the RVC were confirmed by changes in metal binding characteristics. Adsorption edges showed a sharper pH dependence for the reduced electrode compared to the oxidized electrode from pH 3-7. Adsorption isotherms performed at pH 7 showed increased capacity for the reduced electrode. The change was reversible by chemical and electrical reduction. This difference was confirmed at the molecular level with Cd- EXAFS of oxidized and reduced electrodes. A greater degree of cadmium-sulfur coordination was observed on the reduced electrode and a greater cadmium-oxygen coordination was apparant on an oxidized electrode. A multidentate adsorption model was developed to model the pH dependent behavior of cadmium adsorption on the PLC-RVC surface. Nickel adsorption showed increased adsorption in the oxidized state. The most likely explanation is increased carboxylate complexation. The electronically switchable ion exchange system (ESIE) provides a framework for modifying traditional ion exchange processes. The system has 5 to 10 times less specifc capacity than current ion exchange systems, but uses solutions 10-100 times lower in ionic strength for regeneration. Further studies on the effect of ionic strength on adsorption and current usage are necessary to compare the cost of the ESIE process to traditional ion exchange.