Selectivity toward heavier monovalent cations of carbon ultramicropores used for capacitive deionization

Electrolyte confinement inside carbon nanopores strongly affects ion electrosorption in capacitive deionization. A thorough understanding of the intricate pore size influence enables enhanced charge storage performance and desalination in addition to ion separation. In subnanometer pores, where the pore size is smaller than hydrated ion size, a dehydration energy barrier must be overcome before the ions can be electrosorbed into the pores. Ion sieving is observed when the dehydration energy is larger than the applied energy. However, when a high electrochemical potential is used, the ions can desolvate and enter the pores. Capitalizing on the difference in size and dehydration energy barriers, this work applies the subnanometer porous carbon material, and a high electrochemical ion selectivity for Cs + and K + over Na + , Li + , Mg 2+ , and Ca 2+ is observed. This establishes a possible way for selective heavy metal removal by varying pore and solvated ion sizes. Our work also shows the transition from double-layer capacitance to diffusion-limited electrochemical features in narrow ultramicropores. • Selective monovalent heavy metal removal • Chemical online monitoring of ion uptake • Ion transport in subnanometer confinement