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Irreversible xenon insertion into a small-pore zeolite at moderate pressures and temperatures

Nature Chemistry volume 6, pages 835–839 (2014)Cite this article

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Abstract

Pressure drastically alters the chemical and physical properties of materials and allows structural phase transitions and chemical reactions to occur that defy much of our understanding gained under ambient conditions. Particularly exciting is the high-pressure chemistry of xenon, which is known to react with hydrogen and ice at high pressures and form stable compounds. Here, we show that Ag16Al16Si24O8·16H2O (Ag-natrolite) irreversibly inserts xenon into its micropores at 1.7 GPa and 250 °C, while Ag+ is reduced to metallic Ag and possibly oxidized to Ag2+. In contrast to krypton, xenon is retained within the pores of this zeolite after pressure release and requires heat to desorb. This irreversible insertion and trapping of xenon in Ag-natrolite under moderate conditions sheds new light on chemical reactions that could account for the xenon deficiency relative to argon observed in terrestrial and Martian atmospheres.

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Figure 1: Pressure- and heat-induced changes in the synchrotron XRD patterns measured for Ag-NAT using Xe as a pressure-transmitting medium.
Figure 2: Heat-induced changes observed in XRD patterns and XRF spectra of recovered Ag-NAT·Xe.
Figure 3: Graphical representations to illustrate the pressure- and temperature-induced sequential conversions of Ag-NAT to Ag-NAT·Xe and to the Xe-desorbed and rehydrated Ag-NAT.
Figure 4: HAADF-STEM image of Ag-NAT·Xe after pressure release and comparison of the derivatives of the EPR absorption spectra from Ag-NAT, Ag-NAT·Xe and Xe-desorbed Ag-NAT.

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Acknowledgements

This work was supported by the Global Research Laboratory Program of the Korean Ministry of Science, ICT and Planning (MSIP) and was performed under the auspices of the US Department of Energy (contracts W-7405-Eng-48 and DE-AC52-07NA27344). Experiments using the synchrotron were supported by MSIP's PAL-XFEL project. A portion of this work was performed at HPCAT (Sector 16), the Advanced Photon Source (APS), Argonne National Laboratory. HPCAT operations were supported by the DOE-NNSA (under award no. DE-NA0001974) and the DOE-BES (under award no. DE-FG02-99ER45775), with partial instrumentation funding by the National Science Foundation. The APS is supported by the DOE-BES (under contract no. DE-AC02-06CH11357). K.C. acknowledges financial support from the National Research Foundation of Korea (NRF, grant no. 2009-0093817).

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Authors and Affiliations

  1. Department of Earth System Sciences, Yonsei University, Seoul, 120749, Korea

    Donghoon Seoung, Yongmoon Lee & Yongjae Lee

  2. High-Pressure Physics Group, Physics and Life Sciences, Lawrence Livermore National Laboratory, Livermore, 94550, California, USA

    Hyunchae Cynn & William J. Evans

  3. HPCAT, Geophysical Laboratory, Carnegie Institution of Washington, Argonne, 60439-4803, Illinois, USA

    Changyong Park

  4. Department of Physics, Chung-Ang University, Seoul, 156-756, Korea

    Kwang-Yong Choi

  5. NanoCenter & Department of Chemistry and Biochemistry, University of South Carolina, Columbia, 29208, South Carolina, USA

    Douglas A. Blom & Thomas Vogt

  6. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, 94025, California, USA

    Chi-Chang Kao

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Contributions

Y.L. and T.V. designed the research and edited and wrote the paper. D.S. and Y.L. performed the HPXRD experiments and structure analyses. H.C. and C.P. engineered the experiments at APS. D.B. and K.C. carried out the HAADF-STEM and EPR measurements, respectively. W.E. and C.K. discussed the results with Y.L.

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Correspondence to Yongjae Lee.

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Supplementary information

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Supplementary information (PDF 893 kb)

Supplementary information

Crystallographic data for compound Ag-NAT (CIF 80 kb)

Supplementary information

Crystallographic data for compound Ag-Nat.Xe (CIF 43 kb)

Supplementary information

Crystallographic data for compound Ag-NAT (recovered by heating Ag-NAT.Xe to 95°C) (CIF 117 kb)

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Seoung, D., Lee, Y., Cynn, H. et al. Irreversible xenon insertion into a small-pore zeolite at moderate pressures and temperatures. Nature Chem 6, 835–839 (2014). https://doi.org/10.1038/nchem.1997

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