Abstract
Metal–organic microporous materials1,2,3,4 (MOMs) have attracted wide scientific attention owing to their unusual structure and properties, as well as commercial interest due to their potential applications in storage5,6,7,8,9, separation10,11 and heterogeneous catalysis12,13. One of the advantages of MOMs compared to other microporous materials, such as activated carbons, is their ability to exhibit a variety of pore surface properties such as hydrophilicity and chirality, as a result of the controlled incorporation of organic functional groups into the pore walls11,13,14,15. This capability means that the pore surfaces of MOMs could be designed to adsorb specific molecules; but few design strategies for the adsorption of small molecules have been established so far. Here we report high levels of selective sorption of acetylene molecules as compared to a very similar molecule, carbon dioxide, onto the functionalized surface of a MOM. The acetylene molecules are held at a periodic distance from one another by hydrogen bonding between two non-coordinated oxygen atoms in the nanoscale pore wall of the MOM and the two hydrogen atoms of the acetylene molecule. This permits the stable storage of acetylene at a density 200 times the safe compression limit of free acetylene at room temperature.
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Acknowledgements
We thank H. Tanaka, K. Kato and the staff of the Center for Computational Materials Science at the Institute for Materials Research, Tohoku University. The synchrotron radiation experiments were performed at the BL02B2 in SPring-8. This work was supported by a Grant-In-Aid for Science Research in a Priority Area ‘Chemistry of Coordination Space’ from the Ministry of Education, Science, Sports and Culture, Japan.
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Supplementary information
Supplementary Discussion
Extra discussions of the results: acetylene desorption process and binding energy estimations of various configuration of acetylene molecule in the pore. (DOC 29 kb)
Supplementary Data
The crystal information details for 1 with C2H2 at 170 K and 1 without guest molecule at 390 K, which are written by CIF format. (DOC 52 kb)
Supplementary Methods
Additional details of methods for X-ray powder diffraction (XRPD) experiment, structure determinations by MEM/Rietveld analysis and in situ Raman spectroscopic analysis. (DOC 19 kb)
Supplementary Table S1
Crystallographic data and Rietveld refinement summary for 1 with C2H2 at 170 K and 1 without guest at 390 K. (DOC 24 kb)
Supplementary Figures S1-S3
Supplementary Figure S1 details molecular size and thermodynamic properties of C2H2 and CO2. Supplementary Figure S2 details the channel structure of as-synthesized 1. Supplementary Figure S3 details MEM electron densities of C2H2 adsorbed 1 at 170 K. (PDF 619 kb)
Supplementary Figures S4-S6
Supplementary Figure S4 details in situ synchrotron XRPD patterns of 1 with desorption of acetylene. Supplementary Figure S5 details adsorption and desorption isotherms of C2H2. Supplementary Figure S6 details relative energy diagrams accompanying the rotation of the acetylene molecule. (PDF 109 kb)
Supplementary Figures S7-S12
This file contains six Supplementary Figures for supporting this study, such as DFT calculated electron density maps, XRPD patterns in the desorption process, nitrogen adsorption isotherms, Raman spectra of acetylene in the pore, and so on. (PDF 965 kb)
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Matsuda, R., Kitaura, R., Kitagawa, S. et al. Highly controlled acetylene accommodation in a metal–organic microporous material. Nature 436, 238–241 (2005). https://doi.org/10.1038/nature03852
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DOI: https://doi.org/10.1038/nature03852
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