Slow Proton Transfer in Nanoconfined Water

The transport of protons in nanoconfined environments, such as in nanochannels of biological or artificial proton conductive membranes, is essential to chemistry, biology, and nanotechnology. In water, proton diffusion occurs by hopping of protons between water molecules. This process involves the rearrangement of many hydrogen bonds and as such can be strongly affected by nanoconfinement. We study the vibrational and structural dynamics of hydrated protons in water nanodroplets stabilized by a cationic surfactant using polarization-resolved femtosecond infrared transient absorption spectroscopy. We determine the time scale of proton hopping in the center of the water nanodroplets from the dynamics of the anisotropy of the transient absorption signals. We find that in small nanodroplets with a diameter <4 nm, proton hopping is more than 10 times slower than in bulk water. Even in relatively large nanodroplets with a diameter of ∼7 nm, we find that the rate of proton hopping is slowed by ∼4 times compared with bulk water.