Intrinsic Pseudocapacitive Affinity in Manganese Spinel Ferrite Nanospheres for High-Performance Selective Capacitive Removal of Ca<sup>2+</sup> and Mg<sup>2+</sup>
Yingsheng Xu, Shuhong Xiang, Hongjian Zhou, Guozhong Wang, Haimin Zhang, Huijun Zhao
Abstract
Pseudocapacitor-type hybrid capacitive deionization (PHCDI) has been developed extensively for deionization, which enables to address the worldwide freshwater shortage. However, the exploitation of selective hardness ion removal in resourceful hard water via the intrinsic pseudocapacitive effect, rather than the ion-sieving or ion-swapping effect based on the electric double layer (EDL) of porous carbon, is basically blank and urgent. Herein, manganese spinel ferrite (MFO) nanospheres were successfully fabricated by one-step solvothermal synthesis and used as the cathode for PHCDI assembled with commercial activated carbon. The MFO electrode exhibited prominent capacities of 534.6 μmol g –1 (CaCl 2 ) and 980.4 μmol g –1 (MgCl 2 ), outperforming those of other materials ever reported in the literature. Fascinatingly, systematic investigation of binary and ternary ion solutions showed the high electro-affinity of hardness ions (Ca 2+ and Mg 2+ ) toward Na +, especially the leading affinity of Mg 2+, in which the superhigh hardness selectivity of 34.76 was achieved in the ternary solution with a molar ratio of Na–Ca–Mg as 20:1:1. Unexpectedly, the ion-swapping trace in a multi-ion environment was also first detected in our pseudocapacitive-based electrode. The electrochemical response in unary and multiple electrolytes disclosed that the unique pseudocapacitive affinity based on the cation (de)intercalation-redox mechanism was from the synergistic effect of the relative redox potential, ionic radius, and valence, in which the redox potential was the dominant factor.