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Nature Nanotechnology volume 12, pages 546–550 (2017)
Tunable sieving of ions using graphene oxide membranes
Jijo Abraham, Kalangi S. Vasu, Christopher D. Williams, Kalon Gopinadhan, Yang Su, Christie T. Cherian, James Dix, Eric Prestat, Sarah J. Haigh, Irina V. Grigorieva, Paola Carbone, Andre K. Geim & Rahul R. Nair
Abstract
Graphene oxide membranes show exceptional molecular permeation properties, with promise for many applications1,2,3,4,5. However, their use in ion sieving and desalination technologies is limited by a permeation cutoff of ~9 Å (ref. 4), which is larger than the diameters of hydrated ions of common salts4,6. The cutoff is determined by the interlayer spacing (d) of ~13.5 Å, typical for graphene oxide laminates that swell in water2,4. Achieving smaller d for the laminates immersed in water has proved to be a challenge. Here, we describe how to control d by physical confinement and achieve accurate and tunable ion sieving. Membranes with d from ~9.8 Å to 6.4 Å are demonstrated, providing a sieve size smaller than the diameters of hydrated ions. In this regime, ion permeation is found to be thermally activated with energy barriers of ~10–100 kJ mol–1 depending on d. Importantly, permeation rates decrease exponentially with decreasing sieve size but water transport is weakly affected (by a factor of <2). The latter is attributed to a low barrier for the entry of water molecules and large slip lengths inside graphene capillaries. Building on these findings, we demonstrate a simple scalable method to obtain graphene-based membranes with limited swelling, which exhibit 97% rejection for NaCl.
Precise and ultrafast molecular sieving through graphene oxide membranes.
Joshi, R. K. et al.
Abstract
Graphene-based materials can have well-defined nanometer pores and can exhibit low frictional water flow inside them, making their properties of interest for filtration and separation. We investigate permeation through micrometer-thick laminates prepared by means of vacuum filtration of graphene oxide suspensions. The laminates are vacuum-tight in the dry state but, if immersed in water, act as molecular sieves, blocking all solutes with hydrated radii larger than 4.5 angstroms. Smaller ions permeate through the membranes at rates thousands of times faster than what is expected for simple diffusion. We believe that this behavior is caused by a network of nanocapillaries that open up in the hydrated state and accept only species that fit in. The anomalously fast permeation is attributed to a capillary-like high pressure acting on ions inside graphene capillaries.
Membranes based on graphene can simultaneously block the passage of very small molecules while allowing the rapid permeation of water. Joshi et al. (p. 752; see the Perspective by Mi) investigated the permeation of ions and neutral molecules through a graphene oxide (GO) membrane in an aqueous solution. Small ions, with hydrated radii smaller than 0.45 nanometers, permeated through the GO membrane several orders of magnitude faster than predicted, based on diffusion theory. Molecular dynamics simulations revealed that the GO membrane can attract a high concentration of small ions into the membrane, which may explain the fast ion transport.
Selective removal of technetium from water using graphene oxide membranes
Williams, C. D. & Carbone, P.
The effective removal of radioactive technetium (99Tc) from contaminated water is of enormous importance from an environmental and public health perspective, yet many current methodologies are highly ineffective. In this work, however, we demonstrate that graphene oxide membranes may remove 99Tc, present in the form of pertechnetate (TcO4–), from water with a high degree of selectivity, suggesting they provide a cost-effective and efficient means of achieving 99Tc decontamination. The results were obtained by quantifying and comparing the free energy changes associated with the entry of the ions into the membrane capillaries (?Fperm), using molecular dynamics simulations. Initially, three capillary widths were investigated (0.35, 0.68, and 1.02 nm). In each case, the entry of TcO4– from aqueous solution into the capillary is associated with a decrease in free energy, unlike the other anions (SO42–, I–, and Cl–) investigated. For example, in the model with a capillary width of 0.68 nm, ?Fperm(TcO4–) = -6.3 kJ mol–1, compared to ?Fperm(SO42–) = +22.4 kJ mol–1. We suggest an optimum capillary width (0.48 nm) and show that a capillary with this width results in a difference between ?Fperm(TcO4–) and ?Fperm(SO42–) of 89 kJ mol–1. The observed preference for TcO4– is due to its weakly hydrating nature, reflected in its low experimental hydration free energy.
The chemistry of graphene oxide.
Dreyer, D. R., Park, S., Bielawski, C. W. & Ruoff, R. S.
Abstract
The chemistry of graphene oxide is discussed in this critical review. Particular emphasis is directed toward the synthesis of graphene oxide, as well as its structure. Graphene oxide as a substrate for a variety of chemical transformations, including its reduction to graphene-like materials, is also discussed. This review will be of value to synthetic chemists interested in this emerging field of materials science, as well as those investigating applications of graphene who would find a more thorough treatment of the chemistry of graphene oxide useful in understanding the scope and limitations of current approaches which utilize this material (91 references).
