October 08, 2012

Graphene membranes may lead to enhanced natural gas production, less CO2 pollution

Engineering faculty and students at the University of Colorado Boulder have produced the first experimental results showing that atomically thin graphene membranes with tiny pores can effectively and efficiently separate gas molecules through size-selective sieving.

The findings are a significant step toward the realization of more energy-efficient membranes for natural gas production and for reducing carbon dioxide emissions from power plant exhaust pipes.

The research team introduced nanoscale pores into graphene sheets through ultraviolet light-induced oxidative “etching,” and then measured the permeability of various gases across the porous graphene membranes. Experiments were done with a range of gases including hydrogen, carbon dioxide, argon, nitrogen, methane and sulphur hexaflouride -- which range in size from 0.29 to 0.49 nanometers -- to demonstrate the potential for separation based on molecular size. One nanometer is one billionth of a meter.

“These atomically thin, porous graphene membranes represent a new class of ideal molecular sieves, where gas transport occurs through pores which have a thickness and diameter on the atomic scale,” said Bunch.

Nature Nanotechnology - Selective molecular sieving through porous graphene

Graphene is an ideal material for creating a separation membrane because it is durable and yet doesn’t require a lot of energy to push molecules through it, he said.

Other technical challenges will need to be overcome before the technology can be fully realized. For example, creating large enough sheets of graphene to perform separations on an industrial scale, and developing a process for producing precisely defined nanopores of the required sizes are areas that need further development. The CU-Boulder experiments were done on a relatively small scale.

18 pages of Supplemental material

ABSTRACT - 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 would have to be introduced into the material. Here, we show that ultraviolet-induced oxidative etching can create pores in micrometre-sized graphene membranes, and the resulting membranes can be used as molecular sieves. A pressurized blister test and mechanical resonance are used to measure the transport of a range of gases (H2, CO2, Ar, N2, CH4 and SF6) through the pores. The experimentally measured leak rate, separation factors and Raman spectrum agree well with models based on effusion through a small number of ångstrom-sized pores.

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