Illuminating the Black Box: A Perspective on Zeolite Crystallization in Inorganic Media.

ConspectusSince the discovery of synthetic zeolites in the 1940s and their implementation in major industrial processes involving adsorption, catalytic conversion, and ion exchange, material scientists have targeted the rational design of zeolites: controlling synthesis to crystallize zeolites with predetermined properties. Decades later, the fundamentals of zeolite synthesis remain largely obscured in a black box, rendering rational design elusive. A major prerequisite to rational zeolite design is to fully understand, and control, the elementary processes governing zeolite nucleation, growth, and stability. The molecular-level investigation of these processes has been severely hindered by the complex multiphasic media in which aluminosilicate zeolites are typically synthesized. This Account documents our recent progress in crystallizing zeolites from synthesis media based on hydrated silicate ionic liquids (HSIL), a synthesis approach facilitating the evaluation of the individual impacts of synthesis parameters such as cation type, water content, and alkalinity on zeolite nucleation, growth, and phase selection. HSIL-based synthesis allows straightforward elucidation of the relationship between the characteristics of the synthesis medium and the properties and structure of the crystalline product. This assists in deriving new insights in zeolite crystallization in an inorganic aluminosilicate system, thus improving the conceptual understanding of nucleation and growth in the context of inorganic zeolite synthesis in general. This Account describes in detail what hydrated silicate ionic liquids are, how they form, and how they assist in improving our understanding of zeolite genesis on a molecular level. It describes the development of ternary phase diagrams for inorganic aluminosilicate zeolites via a systematic screening of synthesis compositions. By evaluating obtained crystal structure properties such as framework composition, topology, and extraframework cation distributions, critical questions are dealt with: Which synthesis variables govern the aluminum content of crystallizing zeolites? How does the aluminum content in the framework determine the expression of different topologies? The crucial role of the alkali cation, taking center stage in all aspects of crystallization, phase selection, and, by extension, transformation is also discussed. New criteria and models for phase selection are proposed, assisting in overcoming the need for excessive trial and error in the development of future synthesis protocols.Recent progress in the development of a toolbox enabling liquid-state characterization of these precursor media has been outlined, setting the stage for the routine monitoring of zeolite crystallization in real time. Current endeavors on and future needs for the in situ investigation of zeolite crystallization are highlighted. Finally, experimentally accessible parameters providing opportunities for modeling zeolite nucleation and growth are identified. Overall, this work provides a perspective toward future developments, identifying research areas ripe for investigation and discovery.

Does Water Enable Porosity in Aluminosilicate Zeolites? Porous Frameworks versus Dense Minerals.

Recently identified zeolite precursors consisting of concentrated, hyposolvated homogeneous alkalisilicate liquids, hydrated silicate ionic liquids (HSIL), minimize correlation of synthesis variables and enable one to isolate and examine the impact of complex parameters such as water content on zeolite crystallization. HSIL are highly concentrated, homogeneous liquids containing water as a reactant rather than bulk solvent. This simplifies elucidation of the role of water during zeolite synthesis. Hydrothermal treatment at 170 °C of Al-doped potassium HSIL with chemical composition 0.5SiO2:1KOH:xH2O:0.013Al2O3 yields porous merlinoite (MER) zeolite when H2O/KOH exceeds 4 and dense, anhydrous megakalsilite when H2O/KOH is lower. Solid phase products and precursor liquids were fully characterized using XRD, SEM, NMR, TGA, and ICP analysis. Phase selectivity is discussed in terms of cation hydration as the mechanism, allowing a spatial cation arrangement enabling the formation of pores. Under water deficient conditions, the entropic penalty of cation hydration in the solid is large and cations need to be entirely coordinated by framework oxygens, leading to dense, anhydrous networks. Hence, the water activity in the synthesis medium and the affinity of a cation to either coordinate to water or to aluminosilicate decides whether a porous, hydrated, or a dense, anhydrous framework is formed.

Generation and Observation of Long-Lasting and Self-Sustaining Marangoni Flow.

When solute molecules in a liquid evaporate at the surface, concentration gradients can lead to surface tension gradients and provoke fluid convection at the interface, a phenomenon commonly known as the Marangoni effect. Here, we demonstrate that minute quantities of ethanol in concentrated sodium hydroxide solution can induce pronounced and long-lasting Marangoni flow upon evaporation at room temperature. By employing particle image velocimetry and gravimetric analysis, we show that the mean interfacial speed of the evaporating solution sensitively increases with the evaporation rate for ethanol concentrations lower than 0.5 mol %. Placing impermeable objects near the liquid-gas interface enforces steady concentration gradients, thereby promoting the formation of stationary flows. This allows for contact-free control of the flow pattern as well as its modification by altering the objects shape. Analysis of bulk flows reveals that the energy of evaporation in the case of stationary flows is converted to kinetic fluid energy with high efficiency, but reducing the sodium hydroxide concentration drastically suppresses the observed effect to the point where flows become entirely absent. Investigating the properties of concentrated sodium hydroxide solution suggests that ethanol dissolution in the bulk is strongly limited. At the surface, however, the co-solvent is efficiently stored, enabling rapid adsorption or desorption of the alcohol depending on its concentration in the adjacent gas phase. This facilitates the generation of large surface tension gradients and, in combination with the perpetual replenishment of the surface ethanol concentration by bulk convection, to the generation of long-lasting, self-sustaining flows.

HSIL-Based Synthesis of Ultracrystalline K,Na-JBW, a Zeolite Exhibiting Exceptional Framework Ordering and Flexibility.

A reproducible synthesis strategy for ultracrystalline K,Na-aluminosilicate JBW zeolite is reported. The synthesis uses a Na-based hydrated silicate ionic liquid (HSIL) as a silicon source and gibbsite as the aluminum source. 27Al and 23Na NMR spectra exhibit crystalline second-order quadrupole patterns in the hydrated as well as dehydrated states and distinct resonances for different T-sites demonstrating an exceptional degree of order of the elements of the JBW framework, observed for the first time in a zeolite. Detailed structural analysis via NMR crystallography, combining powder X-ray diffraction and solid-state NMR of all elements (27Al, 29Si, 23Na, 39K, and 1H), reveals remarkable de- and rehydration behavior of the JBW framework, transforming from its as-made hydrated structure via a modified anhydrous state into a different rehydrated symmetry while showing astonishing flexibility for a semicondensed aluminosilicate. Its crystallinity, exceptional degree of ordering of the T atoms and sodium cations, and the fully documented structure qualify this defect-free K,Na-aluminosilicate JBW zeolite as a suitable model system for developing NMR modeling methods.

Ion-Pairs in Aluminosilicate-Alkali Synthesis Liquids Determine the Aluminum Content and Topology of Crystallizing Zeolites.

Using hydrated silicate ionic liquids, phase selection and framework silicon-to-aluminum ratio during inorganic zeolite synthesis were studied as a function of batch composition. Consisting of homogeneous single phasic liquids, this synthesis concept allows careful control of crystallization parameters and evaluation of yield and sample homogeneity. Ternary phase diagrams were constructed for syntheses at 90 °C for 1 week. The results reveal a cation-dependent continuous relation between batch stoichiometry and framework aluminum content, valid across the phase boundaries of all different zeolites formed in the system. The framework aluminum content directly correlates to the type of alkali cation and gradually changes with batch alkalinity and dilution. This suggests that the observed zeolites form through a solution-mediated mechanism involving the concerted assembly of soluble cation-oligomer ion pairs. Phase selection is a consequence of the stability for a particular framework at the given aluminum content and alkali type.

Nucleation of Porous Crystals from Ion-Paired Prenucleation Clusters.

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.

How Water and Ion Mobility Affect the NMR Fingerprints of the Hydrated JBW Zeolite: A Combined Computational-Experimental Investigation.

An important aspect within zeolite synthesis is to make fully tunable framework materials with controlled aluminium distribution. A major challenge in characterising these zeolites at operating conditions is the presence of water. In this work, we investigate the effect of hydration on the 27 Al NMR parameters of the ultracrystalline K,Na-compensated aluminosilicate JBW zeolite using experimental and computational techniques. The JBW framework, with Si/Al ratio of 1, is an ideal benchmark system as a stepping stone towards more complicated zeolites. The presence and mobility of water and extraframework species directly affect NMR fingerprints. Excellent agreement between theoretical and experimental spectra is obtained provided dynamic methods are employed with hydrated structural models. This work shows how NMR is instrumental in characterising aluminium distributions in zeolites at operating conditions.

A zeolite crystallisation model confirmed by in situ observation.

Probing nucleation and growth of porous crystals at a molecular level remains a cumbersome experimental endeavour due to the complexity of the synthesis media involved. In particular, the study of zeolite formation is hindered as these typically form in multiphasic synthesis media, which restricts experimental access to crystallisation processes. Zeolite formation from single phasic hydrated silicate ionic liquids (HSiL) opens new possibilities. In this work, HSiL zeolite crystallisation is investigated in situ using a specifically designed conductivity measurement set-up yielding access to crystallisation kinetics. Based on the conductivity data and final yields, a crystallisation model explaining the results based on a surface growth mechanism was derived. The excellent agreement between experiment and theory indicates zeolite crystallisation from highly ionic media proceeds via a multi-step mechanism, involving an initial reversible surface condensation of a growth unit, followed by incorporation of that unit into the growing crystal. The first step is governed by the liquid phase concentration and surface energy, while the final step shows a correlation to the mobility of the cation involved.

Structural Aspects Affecting Phase Selection in Inorganic Zeolite Synthesis.

A guideline for zeolite phase selection in inorganic synthesis media is proposed, based on a systematic exploration of synthesis from inorganic media using liquid Na+, K+, and Cs+ aluminosilicate. Although the Si/Al ratio of the zeolites is a continuous function of the synthesis conditions, boundaries between topologies are sharp. The here-derived phase selection criterion relates the obtained zeolite topology to the Si/Al ratio imposed by the synthesis medium. For a given Si/Al ratio, the framework with the highest occupation of topologically available cation sites is favored. The large number of published zeolite syntheses supporting the observation provides strong indication that the concept is applicable in a larger context. The proposed criterion explains how minor variations in the composition of inorganic synthesis media induce the commonly occurring, abrupt changes in topology. It highlights underlying reasons causing the strict demarcation of stability fields of the as-synthesized zeolites experimentally observed in inorganic synthesis.

Super-ions of sodium cations with hydrated hydroxide anions: inorganic structure-directing agents in zeolite synthesis.

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. In this paper, a direct link between the sodium speciation in the synthesis mixture and the pore structure and content of the final zeolite is demonstrated in the example of hydroxysodalite. Super-ions with 4 sodium cations bound by mono- and bihydrated hydroxide are identified as structure-directing agents for the formation of this zeolite. This documentation of inorganic solution species acting as a templating agent in zeolite formation opens new horizons for zeolite synthesis by design.

Chlorination of a Zeolitic-Imidazolate Framework Tunes Packing and van der Waals Interaction of Carbon Dioxide for Optimized Adsorptive Separation.

Molecular separation of carbon dioxide (CO2) and methane (CH4) is of growing interest for biogas upgrading, carbon capture and utilization, methane synthesis and for purification of natural gas. Here, we report a new zeolitic-imidazolate framework (ZIF), coined COK-17, with exceptionally high affinity for the adsorption of CO2 by London dispersion forces, mediated by chlorine substituents of the imidazolate linkers. COK-17 is a new type of flexible zeolitic-imidazolate framework Zn(4,5-dichloroimidazolate)2 with the SOD framework topology. Below 200 K it displays a metastable closed-pore phase next to its stable open-pore phase. At temperatures above 200 K, COK-17 always adopts its open-pore structure, providing unique adsorption sites for selective CO2 adsorption and packing through van der Waals interactions with the chlorine groups, lining the walls of the micropores. Localization of the adsorbed CO2 molecules by Rietveld refinement of X-ray diffraction data and periodic density functional theory calculations revealed the presence and nature of different adsorption sites. In agreement with experimental data, grand canonical Monte Carlo simulations of adsorption isotherms of CO2 and CH4 in COK-17 confirmed the role of the chlorine functions of the linkers and demonstrated the superiority of COK-17 compared to other adsorbents such as ZIF-8 and ZIF-71.