Photo-controllable Ion-Gated Metal-Organic Framework MIL-53 Sub-nanochannels for Efficient Osmotic Energy Generation

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.