Manganese oxide is an effective active material in several electrochemical systems, including batteries, supercapacitors, and electrochemical deionization (ECDI). This work conducts a comprehensive study on the ion-selective behavior of MnOx to fulfill the emptiness in the energy and environmental science field. Furthermore, it broadens the promising application of MnOx in the ion-selective ECDI system. We propose a time-dependent multimechanism ion-selective behavior with the following guidelines by utilizing a microfluidic cell and the electrochemical quartz crystal microbalance (EQCM) analysis. (1) Hydrated radius is the most critical factor for ions with the same valence, and MnOx tends to capture cations with a small hydrated radius. (2) The importance of charge density rises when comparing cations with different valences, and MnOx prefers to capture divalent cations with a strong electrostatic attraction at prolonged times. Under this circumstance, ion swapping may occur where divalent cations replace monovalent cations. (3) NH4+ triggers MnOx dissolution, leading to performance and stability decay. The EQCM evidence has directly verified the proposed mechanisms, and these data provide a novel but simple method to judge ion selectivity preference. The overall ion selectivity sequence is Ca2+ > Mg2+ > K+ > NH4+> Na+ > Li+ with the highest selectivity values of βCa//Li and βCa//Na around 3 at the deionization time = 10 min.
Keywords: MnOx; cation selectivity; charge density; electrochemical deionization; hydrated radius; time-dependent.