Year of Publication


Document Type





Materials Science and Engineering

First Advisor

Bruce J. Hinds


Molecular transport through hollow cores of crystalline carbon nanotubes (CNTs) are of considerable interest from the fundamental and application point of view. This dissertation focuses on understanding molecular transport through a membrane platform consisting of open ended CNTs with ~ 7 nm core diameter and ~ 1010 CNTs/cm2 encapsulated in an inert polymer matrix. While ionic diffusion through the membrane is close to bulk diffusion expectations, gases and liquids were respectively observed to be transported ~ 10 times faster than Knudsen diffusion and ~ 10000-100000 times faster than hydrodynamic flow predictions. This phenomenon has been attributed to the non-interactive and frictionless graphitic interface. Functionalization of the CNT tips was observed to change selectivity and flux through the CNT membranes with analogy to gate-keeper functionality in biological membranes. An electro-chemical diazonium grafting chemistry was utilized for enhancing the functional density on the CNT membranes. A strategy to confine the reactions at the CNT tips by a fast flowing liquid column was also designed. Characterization using electrochemical impedance spectroscopy and dye assay indicated ~ 5-6 times increase in functional density. Electrochemical impedance spectroscopy experiments on CNT membrane/electrode functionalized with charged macro-molecules showed voltage-controlled conformational change. Similar chemistry has been applied for realizing voltage-gated transport channels with potential application in trans-dermal drug delivery. Electrically-facilitated transport ( a geometry in which an electric field gradient acts across the membrane) through the CNT and functionalized CNT membranes was observed to be electrosmotically controlled. Finally, a simulation framework based on continuum electrostatics and finite elements has been developed to further the understanding of transport through the CNT membranes.