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Graphene membranes with pyridinic nitrogen at pore edges for high-performance CO2 capture

Nature Energy (2024)Cite this article

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Abstract

Membranes based on a porous two-dimensional selective layer offer the potential to achieve exceptional performance to improve energy efficiency and reduce the cost for carbon capture. So far, separation from two-dimensional pores has exploited differences in molecular mass or size. However, competitive sorption of CO2 with the potential to yield high permeance and selectivity has remained elusive. Here we show that a simple exposure of ammonia to oxidized single-layer graphene at room temperature incorporates pyridinic nitrogen at the pore edges. This leads to a highly competitive but quantitatively reversible binding of CO2 with the pore. An attractive combination of CO2/N2 separation factor (average of 53) and CO2 permeance (average of 10,420) from a stream containing 20 vol% CO2 is obtained. Separation factors above 1,000 are achieved for dilute (~1 vol%) CO2 stream, making the membrane promising for carbon capture from diverse point emission sources. Thanks to the uniform and scalable chemistry, high-performance centimetre-scale membranes are demonstrated. The scalable preparation of high-performance two-dimensional membranes opens new directions in membrane science.

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Fig. 1: Uptake of CO2 on pyridinic-N-substituted graphene.
Fig. 2: Uptake of CO2 on pyridinic-N-substituted graphene.
Fig. 3: Quantitatively reversible CO2 sorption on pyridinic-N-substituted graphene.
Fig. 4: Confirmation of N functional groups in pyridinic-N-substituted graphene by EDS and Raman.
Fig. 5: CO2 adsorption and gas transport properties of pyridinic-N-substituted graphene.
Fig. 6: Competitive CO2 adsorption led to attractive carbon capture performance from pyridinic-N-substituted graphene.

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The datasets are available in the article, Supplementary Information and the Source Data file. Source data are provided with this paper.

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Acknowledgements

We acknowledge the host institution École Polytechnique Fédérale de Lausanne (EPFL) for generous support. K.V.A. is thankful to Gaznat AG for funding the project. K.V.A. would also like to thank Swiss National Science Foundation Assistant Professor Energy Grant (PYAPP2_173645), European Research Council Starting Grant (805437-UltimateMembranes) and Swiss National Science Foundation Project (200021_192005) for funding parts of this project. K.-J.H. would like to thank the joint EPFL-Taiwan Scholarship programme for the PhD grant.

Author information

Author notes

  1. Luis Francisco Villalobos

    Present address: Mork Family Department of Chemical Engineering and Materials Science, University of Southern California, Los Angeles, CA, USA

  2. Shiqi Huang

    Present address: Department of Chemical Engineering, University of Bath, Bath, UK

Authors and Affiliations

  1. Laboratory of Advanced Separations (LAS), École Polytechnique Fédérale de Lausanne (EPFL), Sion, Switzerland

    Kuang-Jung Hsu, Shaoxian Li, Marina Micari, Heng-Yu Chi, Luis Francisco Villalobos, Shiqi Huang, Shuqing Song, Xuekui Duan & Kumar Varoon Agrawal

  2. Laboratory of Materials for Renewable Energy (LMER), École Polytechnique Fédérale de Lausanne (EPFL), Sion, Switzerland

    Liping Zhong & Andreas Züttel

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Contributions

K.V.A. and K.-J.H. conceived the project and wrote the manuscript. K.-J.H. prepared the samples for the membrane testing, XPS, Raman, SEM, HRTEM and STM. K.-J.H. and L.Z. performed the XPS measurement. K.-J.H., H.-Y.C. and X.D. collected SEM data. H.-Y.C. and L.F.V. collected the AC-HRTEM images. K.-J.H. carried out the modelling of the transport. S.L. collected the STM data. K.-J.H., S.H. and S.S. developed support layers. M.M. performed the techno-economic analysis. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Kumar Varoon Agrawal.

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A patent application (European patent application EP22206687 (2022)) based on the findings of the work has been filed.

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Nature Energy thanks Simon Smart and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–39, Notes 1–7 and Tables 1–13.

Supplementary Video 1

The movie of pyridinic-N-substituted graphene exposed under electron beams.

Supplementary Video 2

The movie of pyridinic-N-substituted graphene exposed under electron beams.

Supplementary Data 1

The supplementary data for calculating average and standard deviation.

Source data

Source Data Fig. 5

The source data for Fig. 5.

Source Data Fig. 6

The source data for Fig. 6.

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Hsu, KJ., Li, S., Micari, M. et al. Graphene membranes with pyridinic nitrogen at pore edges for high-performance CO2 capture. Nat Energy (2024). https://doi.org/10.1038/s41560-024-01556-0

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