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The preparation of stable large pore aluminophosphate (AlPO) zeotypes offers materials for applications in adsorption and catalysis. Here we report the synthesis of the pure AlPO with the SAO topology type (AlPO STA-1) using N,N′-diethylbicyclo[2.2.2]oct-7-ene-2,3:5,6-dipyrrolidine (DEBOP) as the organic structure directing agent in the presence of fluoride. The AlPO STA-1 can be rendered microporous (pore volume 0.36 cm3 g−1) via calcination and the calcined form remains stable in the presence of moisture. The structure of the dehydrated form has been established by Rietveld refinement (tetragonal P4¯n2, a = 13.74317(10) Å, c = 21.8131(5) Å, V = 4119.94(16) Å3). Multinuclear 27Al and 31P MAS NMR, together with 2D COSY and CASTEP NMR calculations, enables resolution and assignment of the signals from all crystallographically distinct Al and P framework sites. Structural elucidation of the as-prepared aluminophosphate-fluoride is more challenging, because of the presence of partially protonated OSDA molecules in the 3D-connected channel system and in particular because the fluoride ions coordinate with positional disorder to some of the Al atoms to give 5-fold as well as tetrahedrally-coordinated framework Al species. These are postulated to occupy Al–F–Al bridging sites, where they are responsible for distortion of the framework [P4¯n2, a = 13.3148(9) Å, c = 22.0655(20) Å, V = 3911.9(7) Å3]. Calcination and removal of fluoride ions and OSDAs allows the framework to expand to its relaxed configuration. The SAO topology type aluminophosphate can also be synthesised with small amounts of Si and Ge in the framework, and these SAPO and GeAPO STA-1 materials are also stable to template removal. IR spectroscopy with CO as a probe at 123 K indicates all have weak-to-mild acidity, increasing in the order AlPO < GeAPO < SAPO. These STA-1 materials have been investigated for their activity in the Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam at 598 K: while all are active, the AlPO form is favoured due to its high selectivity and slow deactivation, both of which are a consequence of its very weak acid strength, which is nevertheless sufficient to catalyse the reaction. [ABSTRACT FROM AUTHOR]

The flexibility of the zeolite Rho framework offers great potential for tunable molecular sieving. The fully copper‐exchanged form of Rho and mixed Cu,H‐ and Cu,Na‐forms have been prepared. EPR spectroscopy reveals that Cu2+ ions are present in the dehydrated forms and Rietveld refinement shows these prefer S6R sites, away from the d8r windows that control diffusion. Fully exchanged Cu‐Rho remains in an open form upon dehydration, the d8r windows remain nearly circular and the occupancy of window sites is low, so that it adsorbs CO2 rapidly at room temperature. Breakthrough tests with 10 % CO2/40 % CH4 mixtures show that Cu4.9‐Rho is able to produce pure methane, albeit with a relatively low capacity at this pCO2 due to the weak interaction of CO2 with Cu cations. This is in strong contrast to Na‐Rho, where cations in narrow elliptical window sites enable CO2 to be adsorbed with high selectivity and uptake but too slowly to enable the production of pure methane in similar breakthrough experiments. A series of Cu,Na‐Rho materials was prepared to improve uptake and selectivity compared to Cu‐Rho, and kinetics compared to Na‐Rho. Remarkably, Cu,Na‐Rho with >2 Cu cations per unit cell exhibited exsolution, due to the preference of Na cations for narrow S8R sites in distorted Rho and of Cu cations for S6R sites in the centric, open form of Rho. The exsolved Cu,Na‐Rho showed improved performance in CO2/CH4 breakthrough tests, producing pure CH4 with improved uptake and CO2/CH4 selectivity compared to that of Cu4.9‐Rho. [ABSTRACT FROM AUTHOR]

The fully La-exchanged form of the large pore zeolite L, La3.0Al9.0Si27.0O72, has been prepared by repeated aqueous ion exchange and internal cation exchange resulting from calcination to give a low silica zeolite (Si/Al = 3) with all cations hidden from available porosity. This results from the migration of La3+ from sites in the large 12-membered ring (12R) channel (exchangeable via aqueous solution) to 'closed' sites in the structure. The mechanism for this internal cation exchange, which has been elucidated by Rietveld analysis of powder X-ray diffraction data, comprises sequential La3+ migration, first to ste cages between cancrinite (can) cages in the framework and then into the can cages. In each case K+ cations must first leave the closed cages, in the first case through 8Rs, in the second via puckered 6Rs. The first migration step is achieved by 573 K, the second by 1073 K. Decrease of the K+ occupation in accessible main channel sites of zeolites K9.0–, K5.7La1.1–, K2.7La2.1– and La3.0–L strongly changes the shape of the CO2 adsorption isotherms, as the strength of interaction decreases. The Henry law constant for K9.0–L zeolite is 36.60(2) mol (kg bar)−1, whereas for La3.0–L it is 1.80(3) mol (kg bar)−1, if an initial uptake of 0.1 mmol g−1 is neglected. The isosteric heat of adsorption is correspondingly strongly reduced. A CO2 isotherm shape similar to that observed for La–L is also shown by a fully-exchanged La–Y, La18.7Al56.0Si136.0O384, prepared from Na–Y by repeated aqueous and internal ion exchange. In this case the internal exchange requires the egress of Na+ cations from sodalite cages via planar 6R windows and so is possible at lower temperatures (<673 K). The ability to modify CO2 isotherm shape in low silica zeolites by hiding cations in inaccessible cages can be of interest to tailor pressure swing adsorbents for a range of CO2-containing gas streams. [ABSTRACT FROM AUTHOR]

Abstract: To gain insight into the influence of metal–organic framework (MOF) fillers and polymers on membrane performance, eight different composites were studied by combining four MOFs and two polymers. MOF materials (NH2‐MIL‐53(Al), MIL‐69(Al), MIL‐96(Al) and ZIF‐94) with various chemical functionalities, topologies, and dimensionalities of porosity were employed as fillers, and two typical polymers with different permeability‐selectivity properties (6FDA‐DAM and Pebax) were selected as matrices. The best‐performing MOF–polymer composites were prepared by loading 25 wt % of MIL‐96(Al) as filler, which improved the permeability and selectivity of 6FDA‐DAM to 32 and 10 %, while for Pebax they were enhanced to 25 and 18 %, respectively. The observed differences in membrane performance in the separation of CO2 from N2 are explained on the basis of gas solubility, diffusivity properties, and compatibility between the filler and polymer phases. [ABSTRACT FROM AUTHOR]

Adsorption of CO2andCH4has been measuredon the Na-, K-, and Cs-forms of zeolite Rho (0–9 bar; 283–333K). Although CH4is excluded, CO2is readilytaken up, although the uptake at low pressures decreases strongly,in the order Na+> K+> Cs+. Structuralstudies by powder X-ray diffraction (PXRD) suggest that cations inintercage window sites block CH4adsorption; however, inthe presence of CO2, the cations can move enough to permitadsorption (several angstroms). Determination of time-averaged cationpositions during CO2adsorption at 298 K by Rietveld refinementagainst PXRD data shows that (i) in Na-Rho, there is a small relaxationof Na+cations within single eight-ring (S8R) sites, (ii)in Cs-Rho, D8R cations move to S8R sites (remaining within windows)and two phases of Cs-Rho (I4̅3m, Im3̅m) are present overa wide pressure range, and (iii) in K-Rho, there is relocation ofsome K+cations from window sites to cage sites and twophases coexist, each with I4̅3msymmetry, over the pressure range of 0–1 bar. The final cationdistributions at high PCO2aresimilar for Na-, K-, and Cs-Rho, and adsorption in each case is onlypossible by “trapdoor”-type cation gating. Complementarystudies on K-chabazite (Si/Al = 3) also show changes in time-averagedcation location during CO2adsorption. [ABSTRACT FROM AUTHOR]

Mixed-linker zeolitic imidazolate frameworks (ZIFs) with the sodalite ( sod ) topology type and based on ZIF-7 have been prepared by direct synthesis from the mixtures of benzimidazole (BzIm) and 4,5-dichloroimidazole (dcIm). Incorporation of dcIm into the ZIF-7 structure gives ZIF-7/COK-17 hybrids with rhombohedral symmetry that do not show the "open-to-closed form" structural transition upon solvent removal exhibited by ZIF-7. They show Type I isotherms for low molecular weight gases and high affinity for CO 2 even at low partial pressures. Synthesis under mild conditions gives ZIF nanoparticles (250-400 nm) suitable for incorporation into mixed matrix membranes (MMMs): these were prepared with both glassy (Matrimid) and rubbery (PEBAX 1657) polymers. Permeation tests at 298 K and 1.2 bar reveal that the incorporation of Zn(BzIm 0.55 dcIm 0.45 ) 2 nanoparticles at up to ca. 12 wt % gives defect-free membranes with enhanced CO 2 permeability in both polymer matrices, with retention of selectivity (Matrimid) or with an enhancement in selectivity that is most pronounced for the smaller nanoparticles (PEBAX). The membrane with the best performance exhibits a selectivity of ca. 200 for CO 2 /N 2 (a 4-fold increase compared to the pure polymer) and a CO 2 permeability of 64 Barrer. At the relatively low loadings investigated, the MMMs' performance obeys the Maxwell model, and the intrinsic property of diffusivity of the ZIFs can be extracted as a result.

High silica zeolite ZK-5 (framework Si/Al=4.8) has been prepared by interzeolite conversion from ultrastable zeolite Y via a co-templating route using alkali metal cations and nitrate anions but without organic structure directing agents. The mechanism, which involves zeolite framework - alkali metal cation - nitrate anion ordering, has been established by a combination of chemical and thermal analyses, Raman spectroscopy, computational modelling, and X-ray powder diffraction. Ammonium exchange gives ZK-5 with occluded ammonium nitrate and subsequent heating gives microporous zeolite ZK-5., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The flexibility of the zeolite Rho framework offers great potential for tunable molecular sieving. The fully copper-exchanged form of Rho and mixed Cu,H- and Cu,Na-forms have been prepared. EPR spectroscopy reveals that Cu 2+ ions are present in the dehydrated forms and Rietveld refinement shows these prefer S6R sites, away from the d8r windows that control diffusion. Fully exchanged Cu-Rho remains in an open form upon dehydration, the d8r windows remain nearly circular and the occupancy of window sites is low, so that it adsorbs CO 2 rapidly at room temperature. Breakthrough tests with 10 % CO 2 /40 % CH 4 mixtures show that Cu 4.9 -Rho is able to produce pure methane, albeit with a relatively low capacity at this p CO2 due to the weak interaction of CO 2 with Cu cations. This is in strong contrast to Na-Rho, where cations in narrow elliptical window sites enable CO 2 to be adsorbed with high selectivity and uptake but too slowly to enable the production of pure methane in similar breakthrough experiments. A series of Cu,Na-Rho materials was prepared to improve uptake and selectivity compared to Cu-Rho, and kinetics compared to Na-Rho. Remarkably, Cu,Na-Rho with >2 Cu cations per unit cell exhibited exsolution, due to the preference of Na cations for narrow S8R sites in distorted Rho and of Cu cations for S6R sites in the centric, open form of Rho. The exsolved Cu,Na-Rho showed improved performance in CO 2 /CH 4 breakthrough tests, producing pure CH 4 with improved uptake and CO 2 /CH 4 selectivity compared to that of Cu 4.9 -Rho., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

An AlPO 4 zeotype has been prepared using the aromatic diamine 1,10-phenanthroline and some of its methylated analogues as templates. In each case the two template N atoms bind to a specific framework Al site to expand its coordination to the unusual octahedral AlO 4 N 2 environment. Furthermore, using this framework-bound template, Fe atoms can be included selectively at this site in the framework by direct synthesis, as confirmed by annular dark field scanning transmission electron microscopy and Rietveld refinement. Calcination removes the organic molecules to give large pore framework solids, with BET surface areas up to 540 m 2  g -1 and two perpendicular sets of channels that intersect to give pore space connected by 12-ring openings along all crystallographic directions., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Membrane separation for gas purification is an energy-efficient and environment-friendly technology. However, the development of high performance membranes is still a great challenge. In principle, mixed matrix membranes (MMMs) have the potential to overcome current materials limitations, but in practice there is no straightforward method to match the properties of fillers and polymers (the main components of MMMs) in such a way that the final membrane performance reflects the high performance of the microporous filler and the processability of the continuous polymer phase. This issue is especially important when high flux polymers are utilized. In this work, we demonstrate that the use of small amounts of a glassy polymer in combination with high performance PIM-1 allow for the preparation of metal-organic framework (MOF)-based MMMs with superior separation properties and low aging rates under humid conditions, meeting the commercial target for post-combustion CO 2 capture., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

To gain insight into the influence of metal-organic framework (MOF) fillers and polymers on membrane performance, eight different composites were studied by combining four MOFs and two polymers. MOF materials (NH 2 -MIL-53(Al), MIL-69(Al), MIL-96(Al) and ZIF-94) with various chemical functionalities, topologies, and dimensionalities of porosity were employed as fillers, and two typical polymers with different permeability-selectivity properties (6FDA-DAM and Pebax) were selected as matrices. The best-performing MOF-polymer composites were prepared by loading 25 wt % of MIL-96(Al) as filler, which improved the permeability and selectivity of 6FDA-DAM to 32 and 10 %, while for Pebax they were enhanced to 25 and 18 %, respectively. The observed differences in membrane performance in the separation of CO 2 from N 2 are explained on the basis of gas solubility, diffusivity properties, and compatibility between the filler and polymer phases., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)