Small Pore Aluminosilicate EMM-37: Synthesis and Structure Determination Using Continuous Rotation Electron Diffraction.

A new aluminosilicate zeolite, denoted EMM-37, with a 3D small pore channel system, has been synthesized using a diquaternary ammonium molecule as the structure directing agent (SDA) and metakaolin as the aluminum source. The structures of both as-made and calcined forms of EMM-37 were solved and refined using continuous rotation electron diffraction (cRED) data. cRED is a powerful method for the collection of 3D electron diffraction data from submicron- and nanosized crystals, which allows for successful solution and refinement of complex structures in symmetry as low as P1̅.

New High- and Low-Temperature Phase Changes of ZIF-7: Elucidation and Prediction of the Thermodynamics of Transitions.

We have found that the 3D zeolitic imidazolate framework ZIF-7 exhibits far more complex behavior in response to the adsorption of guest molecules and changes in temperature than previously thought. We believe that this arises from the existence of different polymorphs and different types of adsorption sites. We report that ZIF-7 undergoes a displacive, nondestructive phase change upon heating to above ∼700 °C in vacuum, or to ∼500 °C in CO2 or N2. This is the first example of a temperature-driven phase change in 3D ZIF frameworks. We predicted the occurrence of the high-temperature transition on the basis of thermodynamic arguments and analyses of the solid free-energy differences obtained from CO2 and n-butane adsorption isotherms. In addition, we found that ZIF-7 exhibits complex behavior in response to the adsorption of CO2 manifesting in double transitions on adsorption isotherms and a doubling of the adsorption capacity. We report adsorption microcalorimetry, molecular simulations, and detailed XRD investigations of the changes in the crystal structure of ZIF-7. Our results highlight mechanistic details of the phase transitions in ZIF-7 that are driven by adsorption of guest molecules at low temperature and by entropic effects at high temperature. We derived a phase diagram of CO2 in ZIF-7, which exhibits surprisingly complex re-entrant behavior and agrees with our CO2 adsorption measurements over a wide range of temperatures and pressures. We predicted phase diagrams of CH4, C3H6, and C4H10. Finally, we modeled the temperature-induced transition in ZIF-7 using molecular dynamics simulations in the isobaric-isothermal ensemble, confirming our thermodynamic arguments.

First principles derived, transferable force fields for CO2 adsorption in Na-exchanged cationic zeolites.

The development of accurate force fields is vital for predicting adsorption in porous materials. Previously, we introduced a first principles-based transferable force field for CO2 adsorption in siliceous zeolites (Fang et al., J. Phys. Chem. C, 2012, 116, 10692). In this study, we extend our approach to CO2 adsorption in cationic zeolites which possess more complex structures. Na-exchanged zeolites are chosen for demonstrating the approach. These methods account for several structural complexities including Al distribution, cation positions and cation mobility, all of which are important for predicting adsorption. The simulation results are validated with high-resolution experimental measurements of isotherms and microcalorimetric heats of adsorption on well-characterized materials. The choice of first-principles method has a significant influence on the ability of force fields to accurately describe CO2-zeolite interactions. The PBE-D2 derived force field, which performed well for CO2 adsorption in siliceous zeolites, does not do so for Na-exchanged zeolites; the PBE-D2 method overestimates CO2 adsorption energies on multi-cation sites that are common in cationic zeolites with low Si/Al ratios. In contrast, a force field derived from the DFT/CC method performed well. Agreement was obtained between simulation and experiment not only for LTA-4A on which the force field fitting is based, but for other two common adsorbents, NaX and NaY.

Control of zeolite framework flexibility and pore topology for separation of ethane and ethylene.

The discovery of new materials for separating ethylene from ethane by adsorption, instead of using cryogenic distillation, is a key milestone for molecular separations because of the multiple and widely extended uses of these molecules in industry. This technique has the potential to provide tremendous energy savings when compared with the currently used cryogenic distillation process for ethylene produced through steam cracking. Here we describe the synthesis and structural determination of a flexible pure silica zeolite (ITQ-55). This material can kinetically separate ethylene from ethane with an unprecedented selectivity of ~100, owing to its distinctive pore topology with large heart-shaped cages and framework flexibility. Control of such properties extends the boundaries for applicability of zeolites to challenging separations.

Experimental and computational studies of pyridine-assisted post-synthesis modified air stable covalent-organic frameworks.

Pyridine-modified COF-10 exhibits enhanced stability in humid air relative to un-modified COF-10. Solid state NMR and computational studies were used to probe the nature of pyridine interactions with the framework. We propose two models for pyridine-framework interactions with different stabilities.