Abstract
Ammonia is a critical chemical in agriculture and industry that is produced on a massive scale via the Haber–Bosch process1. The environmental impact of this process, which uses methane as a fuel and feedstock for hydrogen, has motivated the need for more sustainable ammonia production2,3,4,5. However, many strategies that use renewable hydrogen are not compatible with existing methods for ammonia separation6,7,8,9. Given their high surface areas and structural and chemical versatility, metal–organic frameworks (MOFs) hold promise for ammonia separations, but most MOFs bind ammonia irreversibly or degrade on exposure to this corrosive gas10,11. Here we report a tunable three-dimensional framework that reversibly binds ammonia by cooperative insertion into its metal–carboxylate bonds to form a dense, one-dimensional coordination polymer. This unusual adsorption mechanism provides considerable intrinsic thermal management12, and, at high pressures and temperatures, cooperative ammonia uptake gives rise to large working capacities. The threshold pressure for ammonia adsorption can further be tuned by almost five orders of magnitude through simple synthetic modifications, pointing to a broader strategy for the development of energy-efficient ammonia adsorbents.
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Acknowledgements
This research was supported by the US Department of Energy, Office of Basic Energy Sciences, Separation Science in the Chemical Sciences, Geosciences, and Biosciences Division, under Award Number DE-SC0019992. We are grateful for the support of BERS through an Arnold O. Beckman Postdoctoral Fellowship in Chemical Sciences and of ABT and EOV through NSF Graduate Research Fellowships (DGE 1752814). DFT calculations were performed using infrastructure from the UC Berkeley Molecular Graphics and Computation Facility, which is supported by the NIH (NIH S10OD023532). Use of the APS at Argonne National Laboratory was supported by US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract no. DE-AC02-06CH11357. We acknowledge K. R. Meihaus for editorial assistance.
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B.E.R.S. and J.R.L. designed the research. B.E.R.S., A.B.T., H.F., E.O.V., M.V.P. and M.N.D. performed the experiments. B.E.R.S. and J.R.L. analysed the data. B.E.R.S. wrote the manuscript. B.E.R.S. and J.R.L. edited the manuscript.
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Snyder, B.E.R., Turkiewicz, A.B., Furukawa, H. et al. A ligand insertion mechanism for cooperative NH3 capture in metal–organic frameworks. Nature 613, 287–291 (2023). https://doi.org/10.1038/s41586-022-05409-2
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DOI: https://doi.org/10.1038/s41586-022-05409-2
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