Competitive water adsorption can have a significant impact on metal–organic framework performance properties, ranging from occupying active sites in catalytic reactions to co-adsorbing at the most favourable adsorption sites in gas separation and storage applications. In this study, we investigate, for a metal–organic framework that is stable after moisture exposure, what are the reversible, loading-dependent structural changes that occur during water adsorption. Herein, a combination of in situ synchrotron powder and single-crystal diffraction, infrared spectroscopy and molecular modelling analysis was used to understand the important role of loading-dependent water effects in a water stable metal–organic framework. Through this analysis, insights into changes in crystallographic lattice parameters, water siting information and water-induced defect structure as a response to water loading were obtained. This work shows that, even in stable metal–organic frameworks that maintain their porosity and crystallinity after moisture exposure, important molecular-level structural changes can still occur during water adsorption due to guest–host interactions such as water-induced bond rearrangements.
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Data supporting the claims and findings of this paper are available within the Supplementary Information or are available upon request from the corresponding author. Crystallographic data for all structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre (CCDC), CCDC numbers 1864840 (DMOF-TM_crystal 09_Flow_01), 1864836 (DMOF-TM_crystal 09_Flow_02), 1864833 (DMOF-TM_crystal 09_Flow_03), 1864842 (DMOF-TM_crystal 09_Flow_04), 1864834 (DMOF-TM_crystal 09_Flow_05), 1864835 (DMOF-TM_crystal 09_Flow_06), 1864838 (DMOF-TM_crystal 09_Flow_07), 1864837 (DMOF-TM_crystal 09_Flow_08), 1864839 (DMOF-TM_crystal 09, static) and 1864841 (DMOF-1, crystal 15, static; where crystal 09 and crystal 15 were both selected from the same batch). Copies of the crystallographic data can be obtained at https://www.ccdc.cam.ac.uk/structures/ free of charge. A SCXRD structure of the ‘activated’ DMOF-TM structure could not be obtained; unit cell parameters and atomic positions were obtained by Rietveld refinement, refined to the SCXRD data from this study (P4/nbm) and also to the structure previously reported for this material (P4/mmm).
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This work was supported as a part of the Center for Understanding and Control of Acid Gas-Induced Evolution of Materials for Energy, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences under award no. DE-SC0012577. Use of the Advanced Photon Source was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. N.C.B. acknowledges support from the National Science Foundation Graduate Research Fellowship and the Graduate Research Opportunities Worldwide (GROW) award under grant no. DGE-1148903. D.D. acknowledges support from the Netherlands Research Council for Chemical Sciences through a VIDI grant and the Dutch Research Council (NWO) Exacte Wetenschappen (Physical Sciences) for the use of supercomputer facilities with financial support from the NWO. NSF’s ChemMatCARS Sector 15 is supported by the Divisions of Chemistry (CHE) and Materials Research (DMR), National Science Foundation, under grant no. NSF/CHE- 1834750. Use of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy Office of Science by Argonne National Laboratory, was supported by the US Department of Energy under contract no. DE-AC02-06CH11357.
The authors declare no competing interests.
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Sample synthesis and preparation; characterization; molecular dynamics simulations; theoretical defects calculations; Supplementary Figures 1–46; references 1–33.
CIF for DMOF-TM, crystal 09, Flow 1; CCDC reference 1864840
Structure factors for DMOF-TM, crystal 09, Flow 1; CCDC reference 1864840
CIF for DMOF-TM, crystal 09, Flow 2; CCDC reference 1864836
Structure factors for DMOF-TM, crystal 09, Flow 2; CCDC reference 1864836
CIF for DMOF-TM, crystal 09, Flow 3; CCDC reference 1864833
Structure factors for DMOF-TM, crystal 09, Flow 3; CCDC reference 1864833
CIF for DMOF-TM, crystal 09, Flow 4; CCDC reference 1864842
Structure factors for DMOF-TM, crystal 09, Flow 4; CCDC reference 1864842
CIF for DMOF-TM, crystal 09, Flow 5; CCDC reference 1864834
Structure factors for DMOF-TM, crystal 09, Flow 5; CCDC reference 1864834
CIF for DMOF-TM, crystal 09, Flow 6; CCDC reference 1864835
Structure factors for DMOF-TM, crystal 09, Flow 6; CCDC reference 1864835
CIF for DMOF-TM, crystal 09, Flow 7; CCDC reference 1864838
Structure factors for DMOF-TM, crystal 09, Flow 7; CCDC reference 1864838
CIF for DMOF-TM, crystal 09, Flow 8; CCDC reference 1864837
Structure factors for DMOF-TM, crystal 09, Flow 8; CCDC reference 1864837
CIF for DMOF-TM, crystal 09, Static; CCDC reference 1864839
Structure factors for DMOF-TM, crystal 09, Static; CCDC reference 1864839
CIF for DMOF-TM, crystal 15, Static; CCDC reference 1864841
Structure factors for DMOF-TM, crystal 15, Static; CCDC reference 1864841
CIF for the activated DMOF-TM, refined to P4/nbm
CIF for the activated DMOF-TM, refined to P4/mmm
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Burtch, N.C., Walton, I.M., Hungerford, J.T. et al. In situ visualization of loading-dependent water effects in a stable metal–organic framework. Nat. Chem. 12, 186–192 (2020). https://doi.org/10.1038/s41557-019-0374-y