We present a facile approach to encapsulate functional porous organic cages (POCs) into a robust MOF by an incipient‐wetness impregnation method. Porous cucurbit[6]uril (CB6) cages with high CO2 affinity were successfully encapsulated into the nanospace of Cr‐based MIL‐101 while retaining the crystal framework, morphology, and high stability of MIL‐101. The encapsulated CB6 amount is controllable. Importantly, as the CB6 molecule with intrinsic micropores is smaller than the inner mesopores of MIL‐101, more affinity sites for CO2 are created in the resulting CB6@MIL‐101 composites, leading to enhanced CO2 uptake capacity and CO2/N2, CO2/CH4 separation performance at low pressures. This POC@MOF encapsulation strategy provides a facile route to introduce functional POCs into stable MOFs for various potential applications.

Metal-organic frameworks (MOFs) and inorganic fillers are frequently incorporated into mixed-matrix membranes (MMMs) to overcome the traditional trade-off in permeability ( P) and selectivity for pure organic polymer membranes. Therefore, it is of great interest to examine the influence of porous and nonporous fillers in MMMs with respect to the possible role of the polymer-filler interface, that is, the void volume. In this work, we compare the same MOF filler in a porous and nonporous state, so that artifacts from a different polymer-filler interface are excluded. MMMs with the porous MOF aluminum fumarate (Al-fum) and with a nonporous dimethyl sulfoxide solvent-filled aluminum fumarate (Al-fum(DMSO)), both with Matrimid as polymer, were prepared. Filler contents ranged from 4 to 24 wt %. Gas separation performances of both MMMs were studied by mixed gas measurements using a binary mixture of CO/CH with gas permeation following the theoretical prediction by the Maxwell model for both porous and nonporous dispersed phase (filler). MMMs with the porous Al-fum filler showed increased CO and CH permeability with a moderate rise in selectivity upon increasing filler fraction. The MMMs with the nonporous Al-fum(DMSO) filler displayed a reduction in permeability while maintaining the selectivity of the neat polymer. A linear dependence of log P versus the reciprocal specific free fractional volume (sFFV) rules out a significant contribution from a void volume. The sFFV includes the free volume of the polymer and the MOF, but not the polymer-filler interface volume (so-called void volume). The sFFV for the MMM was calculated between 0.23 cm/g for a 24 wt % Al-fum/Matrimid MMM and 0.12 cm/g for a 24 wt % Al-fum(DMSO)/Matrimid MMM. The negligible effect of an interface volume is supported by a good matching of theoretical and experimental density of the Al-fum and Al-fum/(DMSO) MMMs which gave a specific void volume below 0.02 cm/g, often even below 0.01 cm/g.

Surface halogenation is an important means to tune or improve functionalities of solid-state materials. However, this concept has been hardly explored and exploited in the engineering of metal-organic frameworks (MOFs). Here, a facile approach to obtain halo-functionalized derivatives of zirconium fumarate (MOF-801) is developed by reacting zirconium halides (ZrX4; X = Cl, Br, I) in water with acetylenedicarboxylic acid. The latter quantitatively undergoes an unusual in situ linker transformation into halofumarate via trans addition of HX to the −CC– triple bond. This HX addition and MOF formation happen in a one-pot reaction, that is, the in situ generated halogenated linker reacts with zirconium ions in solution to yield three microporous HHU-2-X MOFs (X = Cl, Br, I) with an fcu topology, containing UiO-type [Zr6O4(OH)4] secondary building units 12-fold connected by halofumarate linkers. The halogen (Cl) groups in HHU-2-Cl result in increased hydrophilicity for water vapor sorption as well as increased gas uptakes of 21% SO2, 24% CH4, 44% CO2, and 154% N2 when compared to the non-halogenated MOF-801. The tuning of the inner surface chemistry is realized to yield multipurpose adsorbent materials for enhanced gas and vapor uptakes over their non-halogenated analogues. The gas sorption properties of the chlorinated HHU-2-Cl material indicate its suitability for CO2, N2, and SO2 capture and separation, while its water sorption profile yields a high heat storage capacity of 500 kJ kg–1, making it promising for adsorption-based thermal batteries and dehumidification applications.

The report is the first broader evaluation of the gas sorption properties of CAU-23 for the adsorptives CO 2 , H 2 , CH 4 , and SO 2 . CAU-23 is of intermediate porosity among Al-MOFs with specific BET surface areas of the order of MIL-100 > MIL-53 > CAU-23 > MIL-160 > MIL-53-TDC > Alfum > CAU-10-H and total pore volumes of the order of MIL-100 > MIL-53 > CAU-23 > Alfum = MIL-160 > MIL-53-TDC > CAU-10-H. CO 2 uptake (3.97 mmol g À 1 , 293 K) and H 2 uptake (10.25 mmol g À 1 , 77 K) of CAU-23 are second in the series and only slightly smaller than for MIL-160. The CH 4 uptake of CAU-23 (0.89 mmol g À 1 , 293 K) is unremarkable in comparison with the other Al-MOFs. The SO 2 uptake (8.4 mmol g À 1 , 293 K) follows the porosity and higher SO 2 uptakes were only observed for MIL-53 and MIL-100. CAU-23 is one of the best Al-MOFs for high-pressure sorption of CO 2 , with an uptake of 33 wt.-% at 20 bar, 293 K. Gas sorption measurements at two different temperatures gave near zero-coverage enthalpy of adsorptions, ~Hads 0 for CO 2 of À 22 kJ mol À 1 and of SO 2 for À 38 kJ mol À 1 which is at the low end of the other Al-MOFs (À 22 to À 39 kJ mol À 1 for CO 2 ; À 41 to À 51 kJ mol À 1 for SO 2 ), yet ~Hads increases for CAU-23 with CO 2 and SO 2 to À 25 and À 57 kJ mol À 1 , respectively. For CO 2 /CH 4 and SO 2 /CO 2 separation, ideal adsorbed solution theory (IAST) predicted gas selectivities of 5 and 27-50 (depending on molar ratio and model), respectively, in line with 4.5-6.3 and 17-50, respectively, with most of the other Al-MOFs, where only MIL-53-TDC with 83 and MIL-160 with 126 gave a higher SO 2 /CO 2 selectivity at a molar ratio of 0.5.

The flexible, activated MOF rtl-[Cu(HIsa-az-dmpz)] undergoes a reversible phase change into a closed form with gate opening at cryogenic temperatures for N2 and CO2.