Enhanced sieving from exfoliated MoS2 membranes via covalent functionalization

Abstract

Nanolaminate membranes made of two-dimensional materials such as graphene oxide are promising candidates for molecular sieving via size-limited diffusion in the two-dimensional capillaries, but high hydrophilicity makes these membranes unstable in water. Here, we report a nanolaminate membrane based on covalently functionalized molybdenum disulfide (MoS2) nanosheets. The functionalized MoS2 membranes demonstrate >90% and ~87% rejection for micropollutants and NaCl, respectively, when operating under reverse osmotic conditions. The sieving performance and water flux of the functionalized MoS2 membranes are attributed both to control of the capillary widths of the nanolaminates and to control of the surface chemistry of the nanosheets. We identify small hydrophobic functional groups, such as the methyl group, as the most promising for water purification. Methyl- functionalized nanosheets show high water permeation rates as confirmed by our molecular dynamic simulations, while maintaining high NaCl rejection. Control of the surface chemistry and the interlayer spacing therefore offers opportunities to tune the selectivity of the membranes while enhancing their stability.

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Fig. 1: Nanolaminate membranes made of covalently functionalized MoS2 nanosheets.
Fig. 2: Characterization of the functionalized MoS2 membranes.
Fig. 3: Performance of the functionalized MoS2 membranes towards water purification and desalination.
Fig. 4: MD simulations of water transport in 2D nanochannels.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding authors upon reasonable request.

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Acknowledgements

L.R. acknowledges scholarship from the Graduate School ‘Ecole doctorale des Sciences Chimiques Balard, ED 459’. D.V. acknowledges financial supports from ‘Project Axe Transverse Santé’ and CNRS Cellule Energie exploratory project ‘NANOSMO’. This project has also received partial funding from the European Research Council under the European Union’s Horizon 2020 research and innovation programme (grant no. 804320). The French Région Ile de France – SESAME programme is acknowledged for financial support (700 MHz NMR spectrometer). We thank The Hong Kong Polytechnic University and the Department of Applied Physics for the computational resources. D. Cot and E. Oliviero are acknowledged for support with the electron microscopy. We thank V. Flaud and L. Causse for the X-ray photoelectron spectroscopy and the inductively coupled plasma optical emission spectrometry measurements.

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D.V. conceived the idea, designed the experiments and wrote the manuscript. L.R. designed the experiments with D.V., fabricated the membranes and performed membrane characterizations and analysed the results. L.R. and D.V. analysed the data and wrote the manuscript. E.P. carried out high-performance liquid chromatography and liquid NMR spectroscopy measurements. T.M. performed Raman spectroscopy measurements with L.R. and discussed the results with D.V. and L.R.. C.C.D. and C.G. performed 13C CAS NMR spectroscopy measurements and C.S. discussed the results with D.V. and L.R.. S.B. and M.B. assisted L.R. on ionic permeation experiments and discussed the water permeation results. N.O. performed the MD simulations and wrote the manuscript with D.V. and L.R. P.M. discussed the results with D.V. and L.R. All of the authors edited the manuscript before submission.

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Correspondence to Nicolas Onofrio or Damien Voiry.

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Supplementary materials and methods, Supplementary Figs. 1–43, Supplementary Tables 1–10 and Supplementary refs. 1–57

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Ries, L., Petit, E., Michel, T. et al. Enhanced sieving from exfoliated MoS2 membranes via covalent functionalization. Nat. Mater. 18, 1112–1117 (2019). https://doi.org/10.1038/s41563-019-0464-7

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