Breathable Vapor Toxicant Barriers Based on Multilayer Graphene Oxide.

There is tremendous interest in graphene-based membranes as protective molecular barriers or molecular sieves for separation technologies. Graphene oxide (GO) films in the dry state are known to be effective barriers for molecular transport and to expand in the presence of moisture to create enlarged intersheet gallery spaces that allow rapid water permeation. Here we explore an application for GO membranes as water-breathable barrier layers for personal protective equipment, which are designed to allow outward perspiration while protecting the wearer from chemical toxicants or biochemical agents in the local environment. A device was developed to measure permeation rates of small-molecular toxicants in the presence of counter-current water flow simulating active perspiration. The technique was applied to trichloroethylene (TCE) and benzene, which are important environmental toxicants, and ethanol as a limiting case to model very small, highly water-soluble organic molecules. Submicron GO membranes are shown to be effective TCE barriers, both in the presence and absence of simulated perspiration flux, and to outperform current barrier technologies. A molecular transport model is developed, which suggests the limited toxicant back-permeation observed occurs not by diffusion against the convective perspiration flow in hydrophobic channels, but rather through oxidized domains where hydrogen-bonding produces a near-stagnant water phase. Benzene and ethanol permeation fluxes are higher than those for TCE, likely reflecting the effects of higher water solubility and smaller minimum molecular dimension. Overall, GO films have high water breathability relative to competing technologies and are known to exclude most classes of target toxicants, including particles, bacteria, viruses, and macromolecules. The present results show good barrier performance for some very small-molecule species, but not others, with permeation being favored by high water solubility and small minimum molecular dimension.

Hierarchical Metal Oxide Topographies Replicated from Highly Textured Graphene Oxide by Intercalation Templating.

Confined assembly in the intersheet gallery spaces of two-dimensional (2D) materials is an emerging templating route for creation of ultrathin material architectures. Here, we demonstrate a general synthetic route for transcribing complex wrinkled and crumpled topographies in graphene oxide (GO) films into textured metal oxides. Intercalation of hydrated metal ions into textured GO multilayer films followed by dehydration, thermal decomposition, and air oxidation produces Zn, Al, Mn, and Cu oxide films with high-fidelity replication of the original GO textures, including "multi-generational", multiscale textures that have been recently achieved through extreme graphene compression. The textured metal oxides are shown to consist of nanosheet-like aggregates of interconnected particles, whose mobility, attachment, and sintering are guided by the 2D template. This intercalation templating approach has broad applicability for the creation of complex, textured films and provides a bridging technology that can transcribe the wide variety of textures already realized in graphene into insulating and semiconducting materials. These textured metal oxide films exhibit enhanced electrochemical and photocatalytic performance over planar films and show potential as high-activity electrodes for energy storage, catalysis, and biosensing.

Electrosorption/Electrodesorption of Arsenic on a Granular Activated Carbon in the Presence of Other Heavy Metals.

The adsorption, electrosorption, and electrodesorption of aqueous, inorganic arsenic on the granular activated carbon (GAC), DARCO((R)) 12x20 GAC was investigated in solutions containing arsenic as the only contaminant, as well as with chromium, nickel and iron. Darco 1220 was selected for these investigations primarily because it is relatively ineffective as a normal (unassisted) arsenic adsorbent in the chosen electrolytes at the low loadings used. It is shown that the application of anodic potentials in the 1.0 - 1.5V range, however, result in enhanced uptake, most probably due to charging of the electrochemical double-layer at the electrode surface. 100% regeneration of electrosorbed arsenic was achieved via electrodesorption at a cathodic potential of 1.50V. The presence of ad-metal ions was observed to have a significant and complex effect on arsenic adsorption, electrosorption, and electrodesorption. In particular, the Cr:As ratio was shown to have complex effects, decreasing adsorption uptake when present as 3:2, but enhancing adsorption when present as 5:1. Nickel was found to have less of an effect than chromium except at the highest anodic potential used of 1.50V, where it exhibited better performance than chromium. The presence of iron significantly enhanced uptake. With a 1.50V anodic potential, the bulk arsenic concentration was reduced to less than detectable limits, well below the USEPA MCL for drinking water. Regeneration efficiency by electrodesorption for the As-Fe system was greater than about 90%.