Tetrahedral chalcogenide clusters and open frameworks

By integrating porosity with electrical or optical properties, microporous chalcogenides may have unique applications. Here we review recent advances and discuss concepts in the synthesis and crystal structure of tetrahedral clusters and their frameworks. These chalcogenides can be viewed as trivalent metal chalcogenides doped with tetra-, di-, or monovalent metal cations. Low-valent cations help to increase the cluster size, while high-valent cations have the opposite effect.     

Fine structures of zeolite-Linde-L (LTL): surface structures, growth unit and defects

High-resolution electron microscopy (HREM) has been used to image the surface structure of nano- and micrometer-sized synthetic crystals of zeolite-Linde-L (LTL). Columnar holes and rotational, nano-sized, wheel-like defects were observed within the crystals, where the hole has a minimum size equal to that of the rotational defect. Predictions of surface structure from atomistic computer simulation concur with the observations from HREM and provide insight into the crystal growth mechanism of perfect and defective LTL. Analysis of the energetics of the formation of rotational defect structures reveals that the driving force for defect creation is thermodynamic and furthermore, the rotational defects could be created in high concentrations. Formation of a columnar hole is found to be slightly energetically unfavourable and therefore we speculate that the incidence of both rotational and nano-sized vacancy defects is strongly dependent on kinetic factors and reaction conditions. The morphology of nano- and microcrystalline LTL is contradistinct and we use insights from simulation to propose an explanation of the disparity in crystal shape.     

Inorganic electrides

Inorganic electrides are a novel kind of ionic compounds in which the anions are electrons confined in a complex array of cavities or channels and the cations are nanoscale arrays of alkali metal ions that provide charge balance. In electrides the donated electron behaves like a low-density correlated electron gas, whereby the dimensionality of the electron gas and its electronic and magnetic properties are determined by the topology of the cavities in the host matrix. Unlike traditional electrides, in which alkali cations are encapsulated within an organic cage, inorganic electrides are thermally stable. The current inorganic electrides based on alkali metal loaded zeolites can be designed as useful reduced-dimensionality materials. Inorganic electrides are powerful reducing agents, and they are able to reduce small aromatic molecules to the radical anions within the channels of the zeolite.     

Synthesis of dicationic ionic liquids and their application in the preparation of hierarchical zeolite Beta

Piperidine- and imidazole-based dicatoinic ionic liquids have been developed for the synthesis of zeolite Beta. Hierarchical Beta has a larger surface area and pore volume than conventional Beta. Beta derived from a dicationic ionic liquid exhibited remarkably higher catalytic activity than the conventional Beta. Experimental evidence and DFT calculations suggest that only a suitable conformation of such dicationic ionic liquids is able to form zeolite Beta (see scheme).     

Thermal stability of products prepared by the combination of cyclodextrins and zeolites

Derivatographic and calorimetric measurements were used to study the thermal properties of combined inclusion compounds of zeolite-cyclodextrin type and of zeolite-cyclodextrin-pharmaceutical type. There were differences in the characteristic decomposition temperature intervals and in the modes of cyclodextrin and pharmaceutical liberation from the products. Calorimetric measurements revealed that the process in the newly-formed complex host is connected with a glass transition. The products are intended for use in veterinary medicine.     

Studies on basicity of alkali metal catron exchanged β and X zeolites by pyrrole-IR spectroscopy

The strength of basic sites has been measured by pyrrole-IR on alkali metal cation exchanged β and X zeolites, as well as NaOH loaded Naβ. The influence of cation type and the structure of zeolites on their basicity has been studied. The acidic and basic properties of the samples were investigated by NH3-TPD and isopropanol reaction. It was shown that the strength of basic sites on samples could be characterized by the shift of vNH band in the pyrrole-IR spectra. The framework oxygen charges were calculated from the Sanderson electronegativity. The changes in basic properties with various alkali metal cation are consistent with the changes of local oxygen charges of the zeolite framework.     

Local Distortions in a Prototypical Zeolite Framework Containing Double Four-Ring Cages: The Role of Framework Composition and Organic Guests**

Cube-like double four-ring (d4r) cages are among the most frequent building units of zeolites and zeotypes. In materials synthesised in fluoride-containing media, the fluoride anions are preferentially incorporated in these cages. In order to study the impact of framework composition and organic structure-directing agents (OSDAs) on the possible occurrence of local distortions of fluoride-containing d4r cages, density functional theory (DFT) calculations and DFT-based molecular dynamics simulations were performed for AST-type zeotypes, considering four different compositions (SiO₂, GeO₂, AlPO₄, GaPO₄) and two different OSDA cations (tetramethylammonium [TMA] and quinuclidinium [QNU]). All systems except SiO₂-AST show significant deformations, with a pyritohedron-like distortion of the d4r cages occurring in GeO₂- and GaPO₄-AST, and a displacement of the fluoride anions towards one of the corners of the cage in AlPO₄- and GaPO₄-AST. While the distortions occur at random in TMA-containing zeotypes, they exhibit a preferential orientation in systems that incorporate QNU cations. In addition to providing detailed understanding of the local structure of a complex host-guest system on the picosecond timescale, this work indicates the possibility to stabilise ordered distortions through a judicious choice of the OSDA, which might enable a tuning of the material's properties.     

Hierarchical Zeolites as Catalysts for Biodiesel Production from Waste Frying Oils to Overcome Mass Transfer Limitations

Hierarchical crystals with short diffusion path, conventional microcrystals and nanocrystals of ZSM-5 zeolites were used for biodiesel production from waste frying oils and were assessed for their catalytic activity in regard to their pore structure and acidic properties. Produced zeolites were characterized using XRD, nitrogen adsorption–desorption, SEM, TEM, X-ray fluorescence, and FTIR. Pore size effect on molecular diffusion limitation was assessed by Thiele modulus calculations and turnover frequencies (TOF) were used to discuss the correlation between acidic character and catalytic performance of the zeolites. Owing to the enhanced accessibility and mass transfer of triglycerides and free fatty acids to the elemental active zeolitic structure, the catalytic performance of nanosponge and nanosheet hierarchical zeolites was the highest. A maximum yield of 48.29% was reached for the transesterification of waste frying oils (WFOs) using HZSM-5 nanosheets at 12:1 methanol to WFOs molar ratio, 180 °C, 10 wt % catalyst loading, and 4 h reaction time. Although HZSM-5 nanosponges achieved high conversions, these more hydrophilic zeolites did not function according to their entire acidic strength in comparison to HZSM-5 nanosheets. NSh-HZSM5 catalytic performance was still high after 4 consecutive cycles as a result of the zeolite regeneration.     

Polymer colloids formed by polyelectrolyte complexation of vinyl polymers and polysaccharides in aqueous solution

The polyelectrolyte complex formed from the polyanion and polycation was studied by turbidimetry, static and electrophoretic light scattering, and elementary analysis. Sodium salts of polyacrylate (PA) and heparin (Hep) were chosen as the polyanion, and hydrochloric salts of poly(vinyl amine) (PVA) and chitosan (Chts) as the polycation. Although these vinyl polymers and polysaccharides have remarkably different backbone chemical structures and linear charge densities, all the four combinations PA-PVA, PA-Chts, Hep-PVA, and Hep-Chts provide almost stoichiometric polyelectrolyte complexes which are slightly charged owing to the adsorption of the excess polyelectrolyte component onto the neutral complex. The charges stabilize the complex colloids in aqueous solution of a non-stoichiometric mixture, and the aggregation number of the complex colloids increases with approaching to the stoichiometric mixing ratio. The mixing ratio dependence of the aggregation number for the four complexes is explained by the model proposed in the previous study.