The Peculiar Size and Temperature Dependence of Water Diffusion in Carbon Nanotubes studied with 2D NMR Diffusion-Relaxation D-T2eff Spectroscopy

Abstract: It is well known that water inside hydrophobic nano-channels diffuses faster than bulk water. Recent theoretical studies have shown that this enhancement depends on the size of the hydrophobic nanochannels. However, experimental evidence of this dependence is lacking. Here, by combining two-dimensional Nuclear Magnetic Resonance (NMR) diffusion-relaxation D-T2eff spectroscopy in the stray field of a superconducting magnet, and Molecular Dynamics (MD) simulations, we analyze the size dependence of water dynamics inside carbon nanotubes (CNTs) of different diameters (1.1 nm to 6.0 nm), in the temperature range of 265K to 305K. Depending on the CNTs diameter, the nanotube water is shown to resolve in two or more tubular components acquiring different self-diffusion coefficients. Most notable, a favourable CNTs diameter range 3.0-4.5 nm is experimentally verified for the first time, in which water molecule dynamics at the centre of the CNTs exhibit distinctly non-Arrhenius behaviour, characterized by ultrafast diffusion and extraordinary fragility, a result of significant importance in the efforts to understand water behaviour in hydrophobic nanochannels.