Covalent Organic Framework Interlayer Spacings as Perfectly Selective Artificial Proton Channels

Biological proton channels have perfect selectivity in aqueous environment against almost all ions and molecules, a property that differs itself from other biological channels and a feature that remains challenging to realize for bulk artificial materials. The biological perfect selectivity originates from the fact that the channel has almost no free space for ion or water transport but generates a hydrogen bonded wire in the presence of protons to allow the proton hopping. Inspired by this, we used the interlayer spacings of covalent organic framework materials consisting of hydrophilic functional groups as perfectly selective artificial proton channels. The interlayer spacings are so narrow that no atoms or molecules can diffuse through. However, protons exhibit a diffusivity in the same order of magnitude as that in bulk water. Density functional theory calculations show that water molecules and the COF material form hydrogen bonded wires, allowing the proton hopping. We further demonstrate that the proton transport rate can be tuned by adjusting the acidity of the functional groups.