A spin transition mechanism for cooperative adsorption in metal–organic frameworks

Abstract

Cooperative binding, whereby an initial binding event facilitates the uptake of additional substrate molecules, is common in biological systems such as haemoglobin1,2. It was recently shown that porous solids that exhibit cooperative binding have substantial energetic benefits over traditional adsorbents3, but few guidelines currently exist for the design of such materials. In principle, metal–organic frameworks that contain coordinatively unsaturated metal centres could act as both selective4,5,6,7 and cooperative adsorbents if guest binding at one site were to trigger an electronic transformation that subsequently altered the binding properties at neighbouring metal sites8,9,10. Here we illustrate this concept through the selective adsorption of carbon monoxide (CO) in a series of metal–organic frameworks featuring coordinatively unsaturated iron(ii) sites. Functioning via a mechanism by which neighbouring iron(ii) sites undergo a spin-state transition above a threshold CO pressure, these materials exhibit large CO separation capacities with only small changes in temperature. The very low regeneration energies that result may enable more efficient Fischer–Tropsch conversions and extraction of CO from industrial waste feeds, which currently underutilize this versatile carbon synthon11. The electronic basis for the cooperative adsorption demonstrated here could provide a general strategy for designing efficient and selective adsorbents suitable for various separations.

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Figure 1: Idealized adsorption isotherms and the cooperative spin transition mechanism.
Figure 2: Solid state structures.
Figure 3: Characterization of the spin transition mechanism.
Figure 4: Gas adsorption isotherms, working capacities, and molar selectivity values.

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Acknowledgements

This research was supported through the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under award DE-SC0001015. Powder X-ray diffraction data were collected at Beamline 11-BM and Beamline 17-BM at the Advanced Photon Source, a DOE Office of Science User Facility, operated by Argonne National Laboratory under contract DE-AC02-06CH11357. We thank P. C. Bunting, R. L. Siegelman and J. E. Bachman for discussions, and H. Z. H. Jiang for experimental assistance. D.A.R., J.O., J.A.M., D.J.X. and L.E.D. thank the National Science Foundation for graduate fellowship support.

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D.A.R., B.K.K. and J.R.L. formulated the project. D.A.R. and B.K.K. synthesized the compounds. D.A.R. and B.K.K. collected and analysed the gas adsorption data. J.O., J.A.M. and T.R. collected and analysed the X-ray diffraction data. D.J.X. collected and analysed the Mössbauer spectra. L.E.D. collected and analysed the magnetic susceptibility data. V.C. and S.B. collected and analysed the infrared spectra. D.A.R., B.K.K. and J.R.L. wrote the paper, and all authors contributed to revising it.

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Correspondence to Jeffrey R. Long.

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J.R.L., D.A.R., B.K.K. and the University of California, Berkeley have filed for a patent on some of the results contained herein.

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Reed, D., Keitz, B., Oktawiec, J. et al. A spin transition mechanism for cooperative adsorption in metal–organic frameworks. Nature 550, 96–100 (2017). https://doi.org/10.1038/nature23674

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