This review showcases how 27Al MQMAS NMR in combination with 3D correlation of the chemical shift and quadrupolar parameters, enables unambiguously identifying and assigning alumina phases (e.g. transition alumina's α, χ, κ, θ, γ, δ, η, ρ), independent of their crystallinity, even in physical mixtures.
Current nucleation models propose manifold options for the formation of crystalline materials. Exploring and distinguishing between different crystallization pathways on the molecular level however remain a challenge, especially for complex porous materials. These usually consist of large unit cells with an ordered framework and pore components and often nucleate in complex, multiphasic synthesis media, restricting in-depth characterization. This work shows how aluminosilicate speciation during crystallization can be documented in detail in monophasic hydrated silicate ionic liquids (HSILs). The observations reveal that zeolites can form via supramolecular organization of ion-paired prenucleation clusters, consisting of aluminosilicate anions, ion-paired to alkali cations, and imply that zeolite crystallization from HSILs can be described within the spectrum of modern nucleation theory.
Water is the most sustainable solvent, but its polarity limits the solubility of non-polar solutes. Confining water in hydrophobic nanopores could be a way to modulate water solvent properties and enable using water as tuneable solvent (WaTuSo).
Framework deformation, driven by the cations in the channels, determines the CO2 ad- and desorption behavior of zeolites. This allows to tune the zeolite properties to efficient temperature swing adsorption processes.
In inorganic zeolite formation, a direct correspondence between liquid state species in the synthesis and the supramolecular decoration of the pores in the as-made final zeolite has never been reported....
The morphology of zeolite W (MER topology) synthesized from Hydrated Silicate Ionic Liquids (HSILs) shows a distinct temperature dependence, reflected in a fundamental difference in the underlying crystal growth mechanism as revealed by Atomic Force Microscopy (AFM). Zeolite W crystals obtained at 90 °C develop in a highly supersaturated solution through birth and spread growth, whereas synthesis at 175 °C results in elongated, spiral grown zeolite W particles. Supersaturation was measured through the concentration of dissolved aluminate, being the limiting species. The evolution of the aluminum concentration during crystallization at different temperatures was monitored with 27 Al Nuclear Magnetic Resonance (NMR) spectroscopy. Supersaturation conditions determine the nucleation rate, the prevailing crystal growth mechanism, and resulting crystal morphology.
The reaction mechanism of etherification of β-citronellene with ethanol in liquid phase over acid zeolite beta is revealed by in situ solid-state (13)C NMR spectroscopy. Comparison of (13)C Hahn-echo and (1)H-(13)C cross-polarization NMR characteristics is used to discriminate between molecules freely moving in liquid phase outside the zeolite and molecules adsorbed inside zeolite pores and in pore mouths. In the absence of ethanol, β-citronellene molecules enter zeolite pores and react to isomers. In the presence of ethanol, the concentration of β-citronellene inside zeolite pores is very low because of preferential adsorption of ethanol. The etherification reaction proceeds by adsorption of β-citronellene molecule from the external liquid phase in a pore opening where it reacts with ethanol from inside the pore. By competitive adsorption, ethanol prevents the undesired side reaction of β-citronellene isomerization inside zeolite pores. β-citronellene etherification on zeolite beta is suppressed by bulky base molecules (2,4,6-collidine and 2,6-ditertiarybutylpyridine) that do not enter the zeolite pores confirming the involvement of easily accessible acid sites in pore openings. The use of in situ solid-state NMR to probe the transition from intracrystalline catalysis to pore mouth catalysis depending on reaction conditions is demonstrated for the first time. The study further highlights the potential of this NMR approach for investigations of adsorption of multicomponent mixtures in general.
Molecular-sized
micropores of ZSM-5 zeolite catalysts provide spatial
restrictions around catalytic sites that allow for shape-selective
catalysis. However, the fact that ZSM-5 has two main pore systems
with different geometries is relatively unexploited as a potential
source of additional shape selectivity. Here, we use confocal laser-scanning
microscopy to show that by changing the polarity of the solvent, the
acid-catalyzed furfuryl alcohol oligomerization can be directed to
selectively occur within either of two locations in the microporous
network. This finding is confirmed for H-ZSM-5 particles with different
Si/Al ratios and indicates a general trend for shape-selective catalytic
reactions.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.