The Effect of Bulk Modification of the MF-4SK Membrane with Phosphorylated Hyper-Branched Dendrimer Bolthorn H20 on the Mechanisms of Electroconvection/Dissociation of Water and Specific Selectivity to Divalent Ions

This study focuses on the modification of ion-exchange membranes by incorporating a phosphorylated dendrimer into sulfonated polytetrafluoroethylene membranes to enhance the specific selectivity between mono-/divalent ions, using the Ca²⁺/Na⁺ pair as an example. This research employs mechanical, physicochemical, and electrochemical analyses to explore the effects of P-H20 incorporation on membrane properties. Bulk modification significantly increases membrane selectivity towards calcium ions (the specific permselectivity coefficient rises from 1.5 to 7.2), while maintaining the same level of the limiting current density. Other findings indicate that bulk modification significantly changes the transport-channel structure of the membrane and alters the mechanism of over-limiting mass transfer. The over-limiting current for the pristine membrane is mainly due to non-equilibrium electroconvection, while modified membranes actively participate in the water-splitting reaction, leading to the suppression of the electroconvection. Despite this drawback, the decrease of the over-limiting potential drop results in a decrease in specific energy consumption from 0.11 to 0.07 kWh/mol. In the underlimiting current mode, the specific energy consumption for all studied membranes remains within the same limits of 0.02–0.03 kWh/mol.