Precise Cation Recognition in Two-Dimensional Nanofluidic Channels of Clay Membranes Imparted from Intrinsic Selectivity of Clays

Various kinds of clays occur naturally and are accompanied by particular cations in their interlayer domains. Here we report the reassembled membranes with nanofluidic channel arrays by using the natural clays montmorillonite, mica, and vermiculite, which were imparted with the natural selectivity for realizing precise recognition and directional regulation of the naturally occurring interlayer cations. A typical surface-governed ionic transport behavior was observed in the clay nanofluidic channels. Through asymmetric structural modification, cationic current rectification was realized in montmorillonite channels that performed as a nanofluidic diode. Interestingly, in the mica nanofluidic channel, the K+ that was naturally occurring in the interlayer domain of mica showed a reciprocating motion and resulted in a periodically fluctuating current. Electrodialysis demonstrated that such a fluctuating current reflects a directional selectivity for K+, achieving at least a 6000 times permeation rate difference with Li+ ions. The specific selectivity for Li+/Mg2+ on vermiculite reached up to 856 times with similar cations by the current technique. As-obtained clay membranes possess application prospects in energy conversion, brine resource development, etc. Such a strategy can achieve the designed selectivity through systematic screening of the building blocks, thus imparting them with the inherent characteristics of natural clays, which provides an alternative solution to the present manufacture of selective membranes.