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

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Nature Energy (2024 )Cite this article magnesium chloride white flake

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

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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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.

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

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

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

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

Liping Zhong & Andreas Züttel

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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.

Correspondence to Kumar Varoon Agrawal.

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

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

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

The supplementary data for calculating average and standard deviation.

The source data for Fig. 5.

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

DOI: https://doi.org/10.1038/s41560-024-01556-0

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