Coordinated Cation Transport in Ti₃C₂T_x MXene Membranes

Membrane nanofiltration is an attractive strategy for the selective recovery of high-demand metals from wastewater and brine. Effective sieving of ions in aqueous environments will require precise control over membranes' nanochannel size and chemistry. Ti₃C₂T_x MXene is an environmentally stable 2D material that can be processed into laminar membranes containing nanoscale interlayer spaces. The MXene interlayer environment depends on the ion species and amount of water intercalated between MXene sheets, and it is the major factor governing permeation and selectivity through MXene membranes. Coordinated ion-ion and ion-interlayer dynamics in the presence of complex mixtures can impact ion permeability and selectivity. Herein, we observe strong competitive effects between different cations (Li⁺, Na⁺, and Ca²⁺) in binary mixtures, resulting in reduced selectivity when compared with single-salt permeability ratios. X-ray diffraction, molecular dynamics, and density functional theory simulations support the conclusion that cations with stronger attraction to MXene flakes can preferentially occupy the MXene nanochannels and hinder other ions via charge or size exclusion. Elucidation of ion transport behavior in MXene under complex conditions will allow for more rational design of efficient ion-sieving membranes.