The efficient separation of xenon (Xe) and krypton (Kr) is one of the industrially important processes. While adsorptive separation of these two species is considered to be an energy efficient process, developing highly selective adsorbent remains challenging. Herein, a rigid squarate-based metal− organic framework (MOF), having a perfect pore size (4.1 Å × 4.3 Å) comparable with the kinetic diameter of Xe (4.047 Å) as well as pore surface decorated with very polar hydroxyl groups, is able to effectively discriminate Xe atoms, affording a record-high Xe/Kr selectivity. An exceptionally high Xe uptake capacity of 58.4 cm 3 /cm 3 and selectivity of 60.6 at low pressure (0.2 bar) are achieved at ambient temperature. The MOF exhibits the highest Xe Henry coefficient (192.1 mmol/g/bar) and Xe/Kr Henry selectivity (54.1) among all state-of-the-art adsorbents reported so far. Direct breakthrough experiments further confirm the excellent separation performance. The density functional theory calculations reveal that the strong interaction between Xe and the framework is a result of the synergy between optimal pore size and polar porosity.

Research on hydrogen-bonded organic frameworks (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 metal-organic frameworks and hydrogen bonds, we have realized a microporous hydrogen-bonded metal-complex or metallotecton framework HOF-21, which not only shows permanent porosity, but also exhibits highly selective separation performance of CH/CH 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 CH and SiF 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 were observed for the first time in HOFs, underlying the bright perspective of such new HOF materials for their industrial usage.

The demand for CO 2 /C 2 H 2 separation, especially the removal of CO 2 impurity, continues to grow because of the high-purity C 2 H 2 required for various industrial applications. The adsorption separation of C 2 H 2 and CO 2 via porous materials is gaining a considerable attention as it is more energy-efficient compared with cryogenic distillation. The ideal porous materials are those that preferentially adsorb CO 2 over C 2 H 2 ; however, very few adsorbents meet such requirement. Herein, two isostructural cyclodextrin-based CD-MOFs (CD-MOF-1 and CD-MOF-2) were demonstrated to have an inverse ability to selectively capture CO 2 from C 2 H 2 by single-component adsorption isotherms and dynamic breakthrough experiments. These two MOFs showed excellent adsorption capacity and benchmark selectivity (118.7) for CO 2 /C 2 H 2 mixture at room temperature, enabling the pure C 2 H 2 to be obtained in only one step. This work revealed that these materials were promising adsorbents for obtaining high-purity C 2 H 2 via selectively capturing CO 2 from C 2 H 2 .

The separation and purification of xylene isomers is an industrially important but challenging process. Developing highly efficient adsorbents is crucial for the implementation of simulated moving bed technology for industrial separation of these isomers. Herein, we report a stacked one-dimensional coordination polymer {[Mn(dhbq)(H 2 O) 2 ], H 2 dhbq = 2,5-dihydroxy-1,4-benzoquinone} that exhibits an ideal molecular recognition and sieving of xylene isomers. Its distinct temperature-adsorbate–dependent adsorption behavior enables full separation of p -, m -, and o -xylene isomers in both vapor and liquid phases. The delicate stimuli-responsive swelling of the structure imparts this porous material with exceptionally high flexibility and stability, well-balanced adsorption capacity, high selectivity, and fast kinetics at conditions mimicking industrial settings. This study may offer an alternative approach for energy-efficient and adsorption-based industrial xylene separation and purification processes.