No abstract

The theoretical extent of framework flexibility of Zeolite A (LTA) in response to the steric and geometric effects of different Si/Al compositions and extra-framework cation content has been explored using GASP software. Flexibility windows and compression mechanisms for siliceous LTA and aluminosilicate Na-LTA, Ca-LTA and K-LTA have been modelled. As expected, relatively small cations in the zeolite pores have little effect on the range of flexibility observed. Aluminosilicate LTA, Na-LTA and Ca-LTA frameworks exhibit identical flexibility windows and these frameworks also follow the same compression mechanisms. The introduction of larger K+ ions, however, results in greater steric hindrance. This restricts the flexibility of the framework and alters the compression mechanism to accommodate these larger cations. It is shown that the limits of the flexibility window of Zeolite A are dependent on framework aluminium content and extra-framework cation size.

Previous work has shown a strong correlation between zeolite framework flexibility and the nature of structural symmetry and phase transitions. However, there is little experimental data regarding this relationship, in addition to how flexibility can be connected to the synthesis of these open-framework materials. This is of interest for the synthesis of novel zeolites, which require organic additives to permutate the resulting geometry and symmetry of the framework. Here, we have used high-pressure powder X-ray diffraction to study the three zeolites: Na-X, RHO and ZK-5, which can all be prepared using 18-crown-6 ether as an organic additive. We observe significant differences in how the occluded 18-crown-6 ether influences the framework flexibility—this being dependent on the geometry of the framework. We use these differences as an indicator to define the role of 18-crown-6 ether during zeolite crystallization. Furthermore, in conjunction with previous work, we predict that pressure-induced symmetry transitions are intrinsic to body-centred cubic zeolites. The high symmetry yields fewer degrees of freedom, meaning it is energetically favourable to lower the symmetry to facilitate further compression.

The roles of organic additives in the assembly and crystallisation of zeolites are still not fully understood. This is important when attempting to prepare novel frameworks to produce new zeolites. We consider 18-crown-6 ether (18C6) as an additive, which has previously been shown to differentiate between the zeolite EMC-2 (EMT) and faujasite (FAU) frameworks. However, it is unclear whether this distinction is dictated by influences on the metastable free-energy landscape or geometric templating. Using high-pressure synchrotron X-ray diffraction, we have observed that the presence of 18C6 does not impact the EMT framework flexibility—agreeing with our previous geometric simulations and suggesting that 18C6 does not behave as a geometric template. This was further studied by computational modelling using solid-state density-functional theory and lattice dynamics calculations. It is shown that the lattice energy of FAU is lower than EMT, but is strongly impacted by the presence of solvent/guest molecules in the framework. Furthermore, the EMT topology possesses a greater vibrational entropy and is stabilised by free energy at a finite temperature. Overall, these findings demonstrate that the role of the 18C6 additive is to influence the free energy of crystallisation to assemble the EMT framework as opposed to FAU.

Rare earth elements (REEs) are essential raw materials in a variety of industries including clean energy technologies such as electric vehicles and wind turbines. This places an ever-increasing demand on global rare earth element production. Coal fly ash (CFA) possesses appreciable levels of REEs. CFA, a waste by-product of coal combustion, is therefore a readily available source of REEs that does not require mining. CFA valorisation to zeolites has been achieved via various synthesis pathways. This study aimed to evaluate one such pathway by monitoring how REEs partition during CFA processing by the wet, magnetic separation process and zeolitisation. South African CFA was subjected to wet, magnetic separation and subsequent zeolitisation of the nonmagnetic fraction (NMF); solid products were characterised by XRD, SEM, XRF and LA-ICP-MS. The wet, magnetic separation process resulted in the partitioning of a specific set of transition metals (such as Fe, Mn, Cr, V, Ni, Zn, Cu, Co and Mo) into the magnetic fraction (MF) of CFA, while REEs partitioned into the NMF with a total REE content of 530.2 ppm; thus, the matrix elements of CFA were extracted with ease. Zeolitisation resulted in a solid zeolite product (hydroxysodalite) with a total REE content of 537.6 ppm. The process of zeolitisation also resulted in the selective enrichment of Ce (259.1 ppm) into the solid zeolite product (hydroxysodalite), while other REEs were largely partitioned into the liquid phase. CFA valorisation by wet, magnetic separation and zeolitisation therefore allowed for the partitioning of REEs into various extraction products while recovering the matrix elements of CFA such as Fe, Si and Al. The findings of this study highlight the geopolitical importance of REEs in terms of the development of alternative processes for REE recovery from waste and alternative sources, which may potentially give countries that employ and develop the technology a key advantage in the production of REEs for the global market.