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On the origin of the stability of graphene oxide membranes in water

Abstract

Graphene oxide (GO) films are known to be highly stable in water and this property has made their use in membrane applications in solution possible. However, this state of affairs is somewhat counterintuitive because GO sheets become negatively charged on hydration and the membrane should disintegrate owing to electrostatic repulsion. We have now discovered a long-overlooked reason behind this apparent contradiction. Our findings show that neat GO membranes do, indeed, readily disintegrate in water, but the films become stable if they are crosslinked by multivalent cationic metal contaminants. Such metal contaminants can be introduced unintentionally during the synthesis and processing of GO, most notably on filtration with anodized aluminium oxide filter discs that corrode to release significant amounts of aluminium ions. This finding has wide implications in interpreting the processing–structure–property relationships of GO and other lamellar membranes. We also discuss strategies to avoid and mitigate metal contamination and demonstrate that this effect can be exploited to synthesize new membrane materials.

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Figure 1: GO membranes obtained from AAO and Teflon filters have similar microstructures but drastically different mechanical properties and stability in water.
Figure 2: GO membrane obtained from the AAO filter is contaminated with Al.
Figure 3: Effect of pH on the corrosion of AAO and the stability of the corresponding GO membranes in water.
Figure 4: Cation-stabilized GO films can swell in water and function as a structural template for chemical reactions.

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Acknowledgements

This work was primarily funded by the National Science Foundation (DMR-CAREER 0955612) and the Office of Naval Research (ONRN000141310556). C-N.Y. acknowledges 3M for a graduate fellowship, and the International Institute for Nanotechnology at Northwestern University for a Ryan Fellowship. J.S. acknowledges the China Scholarship Council for an exchange student fellowship. J.H. acknowledges the John Simon Guggenheim Memorial Foundation for a Guggenheim Fellowship. Q-H.Y. thanks the National Basic Research Program of China (2014CB932403) and National Natural Science Foundation of China (No. 51372167) for support. The work made use of experimental facilities at the Quantitative Bioelemental Imaging Center (QBIC) supported by the National Aeronautics and Space Administration Ames Research Center (NNA06CB93G), the Northwestern University Atomic and Nanoscale Characterization Experimental Center (NUANCE, Keck-II) and the J.B. Cohen X-Ray Diffraction Facility supported by the National Science Foundation Materials Research Science and Engineering Centers program (DMR-1121262). We thank C. L. Brinson for letting us use her mechanical analyser.

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All authors contributed to the design of the experiments. C-N.Y. performed all the experiments, identified critical prior results in the literature and wrote the paper with J.H., who conceived the idea and oversaw the project.

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Correspondence to Jiaxing Huang.

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The authors declare no competing financial interests.

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Yeh, CN., Raidongia, K., Shao, J. et al. On the origin of the stability of graphene oxide membranes in water. Nature Chem 7, 166–170 (2015). https://doi.org/10.1038/nchem.2145

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