The molecular origin of fast fluid transport in carbon nanotubes: theoretical and molecular dynamics study of liqui/solid friction in graphitic nanopores

Within the scope of this thesis, a theoretical study of liquid flow in graphitic nanopores was performed. More precisely, a combination of numerical simulations and analytic approach was used to establish the special properties of carbon nanotubes for fluid transport: Molecular dynamics flow simulations of different liquids in carbon nanotubes exhibited flow velocities that are 1-3 orders of magnitude higher than predicted from the continuum hydrodynamics framework and the no-slip boundary condition. These results support previous experiments performed by several groups reporting exceptionally high flow rates for water in carbon nanotube membranes. The reason for this important flow enhancement with respect to the expectation was so far unclear. In this work, a careful investigation of the water/graphite friction coefficient which we identified as the crucial parameter for fast liquid transport in the considered systems, was carried out. In simulations, the friction coefficient was found to be very sensitive to wall curvature: friction is independent of confinement for water between flat graphene walls with zero curvature, while it increases with increasing negative curvature (water at the outside of the tube), and it decreases with increasing positive curvature (water inside the tube), eventually leading to quasi frictionless flow for water in a single file configuration in the smallest tubes. A similar behavior was moreover found with several other liquids, such as alcohol, alcane and OMCTS. Furthermore, a theoretical approximate expression for the friction coefficient is presented which predicts qualitatively and semi-quantitatively its curvature dependent behavior. Moreover, a deeper analysis of the simulations according to the proposed theoretical description shed light on the physical mechanisms at the origin of the ultra low liquid/solid friction in carbon nanotubes. In fine, it is due to their perfectly ordered molecular structure and their atomically smooth surface that carbon nanotubes are quasi-perfect liquid conductors compared to other membrane pores like, for example, nanochannels in amorphous silica. The newly gained understanding constitutes an important validation that carbon nanotubes operate as fast transporters of various liquids which makes them a promising option for different applications like energy conversion or filtration on the molecular level