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© 2020, The Author(s). Three-dimensional metal−organic frameworks (MOFs) are cutting-edge materials in the adsorptive removal of trace gases due to the availability of abundant pores with specific chemistry. However, the development of ideal adsorbents combining high adsorption capacity with high selectivity and stability remains challenging. Here we demonstrate a strategy to design adsorbents that utilizes the tunability of interlayer and intralayer space of two-dimensional fluorinated MOFs for capturing acetylene from ethylene. Validated by X-ray diffraction and modeling, a systematic variation of linker atom oxidation state enables fine regulation of layer stacking pattern and linker conformation, which affords a strong interlayer trapping of molecules along with cooperative intralayer binding. The resultant robust materials (ZUL-100 and ZUL-200) exhibit benchmark capacity in the pressure range of 0.001–0.05 bar with high selectivity. Their efficiency in acetylene/ethylene separation is confirmed by breakthrough experiments, giving excellent ethylene productivities (121 mmol/g from 1/99 mixture, 99.9999%), even when cycled under moist conditions.

peer-reviewed, Research on HOFs has been developed for quite a long time; however, those with both established permanent porosities and functional properties are extremely rare due to weak hydrogen-bonding interactions among molecular organic linkers which are much more fragile and difficult to stabilize. Herein, through judiciously combining the superiority of both the moderately stable coordination bonds in MOFs and hydrogen bonds, we have realized a microporous hydrogenbonded metal-complex or metallotecton framework HOF-21, which not only shows permanent porosity but also exhibits highly selective separation performance of C2H2/C2H4 at room temperature. The outstanding separation performance can be ascribed to sieving effect confined by the fine-tuning pores and the superimposed hydrogen-bonding interaction between C2H2 and SiF62- on both ends as validated by both modeling and neutron powder diffraction experiments. More importantly, the collapsed HOF-21 can be restored by simply immersing it into water or salt solution. To the best of our knowledge, such extraordinary water stability and restorability of HOF-21 was observed for the first time in HOFs, underlying the bright perspective of such new HOF materials for their industrial usage.