Molecular Valves for Controlling Gas Phase Transport Made from Discrete Angstrom-Sized Pores in Graphene

An ability to precisely regulate the quantity and location of molecular flux is of value in applications such as nanoscale 3D printing, catalysis, and sensor design. Barrier materials containing pores with molecular dimensions have previously been used to manipulate molecular compositions in the gas phase, but have so far been unable to offer controlled gas transport through individual pores. Here, we show that gas flux through discrete angstrom-sized pores in monolayer graphene can be detected and then controlled using nanometer-sized gold clusters, which are formed on the surface of the graphene and can migrate and partially block a pore. In samples without gold clusters, we observe stochastic switching of the magnitude of the gas permeance, which we attribute to molecular rearrangements of the pore. Our molecular valves could be used, for example, to develop unique approaches to molecular synthesis that are based on the controllable switching of a molecular gas flux, reminiscent of ion channels in biological cell membranes and solid state nanopores.

Selective Molecular Sieving through Porous Graphene

Membranes act as selective barriers and play an important role in processes such as cellular compartmentalization and industrial-scale chemical and gas purification. The ideal membrane should be as thin as possible to maximize flux, mechanically robust to prevent fracture, and have well-defined pore sizes to increase selectivity. Graphene is an excellent starting point for developing size selective membranes because of its atomic thickness, high mechanical strength, relative inertness, and impermeability to all standard gases. However, pores that can exclude larger molecules, but allow smaller molecules to pass through have to be introduced into the material. Here we show UV-induced oxidative etching can create pores in micrometre-sized graphene membranes and the resulting membranes used as molecular sieves. A pressurized blister test and mechanical resonance is used to measure the transport of a variety of gases (H2, CO2, Ar, N2, CH4, and SF6) through the pores. The experimentally measured leak rates, separation factors, and Raman spectrum agree well with models based on effusion through a small number of angstrom-sized pores.

Ultrathin Oxide Films by Atomic Layer Deposition on Graphene

In this paper, a method is presented to create and characterize mechanically robust, free standing, ultrathin, oxide films with controlled, nanometer-scale thickness using Atomic Layer Deposition (ALD) on graphene. Aluminum oxide films were deposited onto suspended graphene membranes using ALD. Subsequent etching of the graphene left pure aluminum oxide films only a few atoms in thickness. A pressurized blister test was used to determine that these ultrathin films have a Youngs modulus of 154 pm 13 GPa. This Youngs modulus is comparable to much thicker alumina ALD films. This behavior indicates that these ultrathin two-dimensional films have excellent mechanical integrity. The films are also impermeable to standard gases suggesting they are pinhole-free. These continuous ultrathin films are expected to enable new applications in fields such as thin film coatings, membranes and flexible electronics.