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.

The ability to fabricate a charge-driven water pump is a crucial step toward mimicking the catalytic ability of natural enzyme systems. The first step towards making this water pump a reality is the ability to make a carbon nanotube (CNT) membrane with uniform, 0.8 nm pore diameter. Proposed in this work is a method for synthesizing these carbon nanotubes via VPI-5 zeolite templated, transition metal catalyzed pyrolysis. Using a membrane composed of these CNTs, it is possible to get water molecules to flow single file at a high flow rate, and to orient them in such a way that would maximize their ability to be catalyzed. Additionally, using the ability to plate a monolayer of precious metal catalyst molecules around the exit to the membrane, catalyst efficiency can be maximized by making every catalyst atom come into contact with a substrate molecule. In this work, we also demonstrate the ability to plate a monolayer of precious metal catalyst atoms onto an insulating, mesoporous, support material. By combining these two chemical processes, it is possible to mimic the catalytic efficiency of natural enzyme systems.