By closing and opening ion channels, electric eels are able to convert ion concentration gradients into electricity. Inspired by electric eels, considerable artificial sub-nanoscale ion channels with high ion selectivity and transportation efficiency have been designed for harvesting the osmotic energy between ionic solutions of different salinities, but constructing smart ion-gated sub-nanochannels for effective ion transport is still a huge challenge. Herein, photo-controllable sub-nanochannels of metal–organic framework (MOF) NH2-MIL-53 encapsulated with spiropyrans (SP-MIL-53) were fabricated by a facile in situ growth strategy. Interestingly, the highly ordered sub-nanochannels of SP-MIL-53 were switched on and off to efficiently regulate the ion flux by the light-driven isomerization of SP, which made it a smart ionic gate with a high on–off ratio of 16.2 in 10 mM KCl aqueous solution via UV irradiation. Moreover, the ion-gated sub-nanochannel membrane yielded a high power density of 8.3 W m–2 under a 50-fold KCl concentration gradient in the open state. Density functional theory calculations revealed that K+ ions in SP-MIL-53 sub-nanochannels had a higher mobility constant (3.61 × 10–2) with UV irradiation than without UV illumination (2.33 × 10–22). This work provides an effective way to develop smart ion-gating sub-nanochannels for capturing salinity gradient power.
The waste organic solvents containing inorganic salts have been considered sustainable resources, which can effectively capture salinity gradient energy using ion-selective membranes. However, it still remains a great challenge to fabricate the ion-selective membranes with high conversion efficiency and stability in an organic system. Here, the bioinspired nacre-like layered MXene/poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonate) (PEDOT:PSS) (MP) composite membranes for capturing salinity gradient energy from an organic solvent are fabricated via filtration method, in which PEDOT:PSS molecules are introduced into MXene interlayers. Accordingly, the MP membrane exhibits high mechanical property and wonderful stability in common organic solvents. As expected, the power generation of the MP membrane reaches up to 3216 ± 603 nW in a 2/0.001 M methanol (Met)–LiCl solution and a record high power generation of 6926 ± 959 nW after adding NaOH into the Met–LiCl solution, which is superior to the previous report. Both experimental and theoretical studies confirm that the MP membrane has excellent cation selectivity and fast ion transport performance. The results are attributable to an increased interlayer spacing between MXene layers and an improved cation selectivity due to the insertion of PEDOT:PSS chains and the enhanced dissociation of negative charges by NaOH. The ultrastable two-dimensional (2D) nanochannel membrane provides practical application for harvesting energy from waste organic solvents.
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