An array of aligned carbon nanotubes (CNTs) was incorporated across a polymer film to form a well-ordered nanoporous membrane structure. This membrane structure was confirmed by electron microscopy, anisotropic electrical conductivity, gas flow, and ionic transport studies. The measured nitrogen permeance was consistent with the flux calculated by Knudsen diffusion through nanometer-scale tubes of the observed microstructure. Data on Ru(NH 3 ) 63+ transport across the membrane in aqueous solution also indicated transport through aligned CNT cores of the observed microstructure. The lengths of the nanotubes within the polymer film were reduced by selective electrochemical oxidation, allowing for tunable pore lengths. Oxidative trimming processes resulted in carboxylate end groups that were readily functionalized at the entrance to each CNT inner core. Membranes with CNT tips that were functionalized with biotin showed a reduction in Ru(NH 3 ) 63+ flux by a factor of 15 when bound with streptavidin, thereby demonstrating the ability to gate molecular transport through CNT cores for potential applications in chemical separations and sensing.
Many current treatments for the reclamation of contaminated water sources are chemical-intensive, energy-intensive, and/or require posttreatment due to unwanted by-product formation. We demonstrate that through the integration of nanostructured materials, enzymatic catalysis, and iron-catalyzed free radical reactions within pore-functionalized synthetic membrane platforms, we are able to conduct environmentally important oxidative reactions for toxic organic degradation and detoxification from water without the addition of expensive or harmful chemicals. In contrast to conventional, passive membrane technologies, our approach utilizes two independently controlled, nanostructured membranes in a stacked configuration for the generation of the necessary oxidants. These include biocatalytic and organic/inorganic (polymer/iron) nanocomposite membranes. The bioactive (top) membrane contains an electrostatically immobilized enzyme for the catalytic production of one of the main reactants, hydrogen peroxide (H 2 O 2 ), from glucose. The bottom membrane contains either immobilized iron ions or ferrihydrite/iron oxide nanoparticles for the decomposition of hydrogen peroxide to form powerful free radical oxidants. By permeating (at low pressure) a solution containing a model organic contaminant, such as trichlorophenol, with glucose in oxygen-saturated water through the membrane stack, significant contaminant degradation was realized. To illustrate the effectiveness of this membrane platform in real-world applications, membrane-immobilized ferrihydrite/iron oxide nanoparticles were reacted with hydrogen peroxide to form free radicals for the degradation of a chlorinated organic contaminant in actual groundwater. Although we establish the development of these nanostructured materials for environmental applications, the practical and methodological advances demonstrated here permit the extension of their use to applications including disinfection and/or virus inactivation.