Abstract
Structural transitions of host systems in response to guest binding dominate many chemical processes. We report an unprecedented type of structural flexibility within a meta-rigid material, MFM-520, which exhibits a reversible periodic-to-aperiodic structural transition resulting from a drastic distortion of a [ZnO4N] node controlled by the specific host-guest interactions. The aperiodic crystal structure of MFM-520 has no three-dimensional (3D) lattice periodicity but shows translational symmetry in higher-dimensional (3 + 2)D space. We have directly visualized the aperiodic state which is induced by incommensurate modulation of the periodic framework of MFM-520·H2O upon dehydration to give MFM-520. Filling MFM-520 with CO2 and SO2 reveals that, while CO2 has a minimal structural influence, SO2 can further modulate the structure incommensurately. MFM-520 shows exceptional selectivity for SO2 under flue-gas desulfurization conditions, and the facile release of captured SO2 from MFM-520 enabled the conversion to valuable sulfonamide products. MFM-520 can thus be used as a highly efficient capture and delivery system for SO2.
Original language | English |
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Pages (from-to) | 19189-19197 |
Number of pages | 9 |
Journal | Journal of the American Chemical Society |
Volume | 142 |
Issue number | 45 |
DOIs | |
State | Published - Nov 11 2020 |
Funding
We thank the EPSRC (EP/I011870), the Royal Society and University of Manchester, the National Basic Research Program (nos. 2013CB933402 and 2016YFA0301004), and the National Natural Science Foundation of China (nos. 21527803, 21471009, 21621061, and 21871009) for funding. This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (grant agreement no. 742401, NANOCHEM). We are grateful to the Diamond Light Source and the STFC/ISIS Facility for access to beamlines B22 and TOSCA, respectively. This research used the resources of beamlines 11.3.1 and 12.2.1 at the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. The computing resources were made available through the VirtuES and ICEMAN projects, funded by the Laboratory Directed Research and Development Program and the Compute and Data Environment for Science (CADES) at ORNL. J.L., X.Z., and Z.Z. thank the China Scholarship Council (CSC) for funding. We thank the EPSRC (EP/I011870), the Royal Society and University of Manchester, the National Basic Research Program (nos. 2013CB933402 and 2016YFA0301004), and the National Natural Science Foundation of China (nos. 21527803, 21471009, 21621061, and 21871009) for funding. This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 Research and Innovation Programme (grant agreement no. 742401, NANOCHEM). We are grateful to the Diamond Light Source and the STFC/ISIS Facility for access to beamlines B22 and TOSCA, respectively. This research used the resources of beamlines 11.3.1 and 12.2.1 at the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. The computing resources were made available through the VirtuES and ICE-MAN projects, funded by the Laboratory Directed Research and Development Program and the Compute and Data Environment for Science (CADES) at ORNL. J.L., X.Z., and Z.Z. thank the China Scholarship Council (CSC) for funding.