Capacitive deionization for selective separation of ions is rarely reported since it relies on the electrostatic attraction of oppositely charged ions with no capability to distinguish ions of different valent states. Using molecular dynamic simulation, a screening process identified a hybrid material known as AC/PTh, which consists of activated carbon with a thin layer of polythiophene (PTh) coating. By utilizing AC/PTh as electrode material implementing the short-circuit cycle (SCC) mode in flow-electrode capacitive deionization (FCDI), selective separation of mono-/divalent ions can be realized via precise control of dynamic adsorption and desorption of mono-/divalent ions at a particular surface. Specifically, AC/PTh shows strong interaction with divalent ions but weak interaction with monovalent ions, the distribution of divalent ions can be enriched in the electric double layer after a couple of adsorption-desorption cycles. At Cu2+/Na+ molar ratio of 1:40, selectivity toward divalent ions can reach up to 110.3 in FCDI SCC mode at 1.0 V. This work presents a promising strategy for separating ions of different valence states in a continuously operated FCDI device. Switching from different interfacial behavior on cathode and anode, dynamic adsorption and desorption of mono-/divalent ions can be achieved via flow-electrode capacitive deionization. Owing to strong interaction with electrode surface, divalent ions get enriched in the Helmhotlz layer, thus realizing high selectivity towards divalent ions. image
