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.

Hydrogen-Bonded Water-Aminium Assemblies for Synthesis of Zeotypes with Ordered Heteroatoms.

Water plays a central role in the crystallization of a variety of organic, inorganic, biological, and hybrid materials. This is also true for zeolites and zeolite-like materials, an important class of industrial catalysts and adsorbents. Water is always present during their hydrothermal synthesis, either with or without organic species as structure-directing agents. Apart from its role as a solvent or a catalyst, structure direction by water in zeolite synthesis has never been clearly elucidated. Here, we report the crystallization of phosphate-based molecular sieves using rationally designed, hydrogen-bonded water-aminium assemblies, resulting in molecular sieves exhibiting the crystallographic ordering of heteroatoms. We demonstrate that a 1:1 assembly of water and diprotonated N,N-dimethyl-1,2-ethanediamine acts as a structure-directing agent in the synthesis of a silicoaluminophosphate material with phillipsite (PHI) topology, using SMARTER crystallography, which combines single-crystal X-ray diffraction and nuclear magnetic resonance spectroscopy, as well as ab initio molecular dynamics simulations. The molecular arrangement of the hydrogen-bonded assembly matches well with the shape and size of subunits in the PHI structure, and their charge distributions result in the strict ordering of framework tetrahedral atoms. This concept of structure direction by water-containing supramolecular assemblies should be applicable to the synthesis of many classes of porous materials.

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.

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.

NMR Crystallography Reveals Carbonate Induced Al-Ordering in ZnAl Layered Double Hydroxide.

Layered double hydroxides (LDHs) serve a score of applications in catalysis, drug delivery, and environmental remediation. Smarter crystallography, combining X-ray diffraction and NMR spectroscopy revealed how interplay between carbonate and pH determines the LDH structure and Al ordering in ZnAl LDH. Carbonate intercalated ZnAl LDHs were synthesized at different pH (pH 8.5, pH 10.0, pH 12.5) with a Zn/Al ratio of 2, without subsequent hydrothermal treatment to avoid extensive recrystallisation. In ideal configuration, all Al cations should be part of the LDH and be coordinated with 6 Zn atoms, but NMR revealed two different Al local environments were present in all samples in a ratio dependent on synthesis pH. NMR-crystallography, integrating NMR spectroscopy and X-ray diffraction, succeeded to identify them as Al residing in the highly ordered crystalline phase, next to Al in disordered material. With increasing synthesis pH, crystallinity increased, and the side phase fraction decreased. Using 1 H-13 C, 13 C-27 Al HETCOR NMR in combination with 27 Al MQMAS, 27 Al-DQ-SQ measurements and Rietveld refinement on high-resolution PXRD data, the extreme anion exchange selectivity of these LDHs for CO3 2- over HCO3 - was linked to strict Al and CO3 2- ordering in the crystalline LDH. Even upon equilibration of the LDH in pure NaHCO3 solutions, only CO3 2- was adsorbed by the LDH. This reveals the structure directing role of bivalent cations such as CO3 2- during crystallization of [M2+ 4 M3+ 2 (OH)2 ]2+ [A2- ]1 ⋅yH2 O LDH phases.

Alumina: discriminative analysis using 3D correlation of solid-state NMR parameters.

Synthetic transition aluminas (χ, κ, θ, γ, δ, η, ρ) exhibit unique adsorptive and catalytic properties leading to numerous practical applications. Generated by thermal transformation of aluminium (oxy)hydroxides, structural differences between them arise from the variability of aluminium coordination numbers and degree of dehydroxylation. Unequivocal identification of these phases using X-ray diffraction has proven to be very difficult. Quadrupolar interactions of 27Al nuclei, highly sensitive to each site symmetry, render advanced 27Al solid-state NMR a unique spectroscopic tool to fingerprint and identify the different phases. In this paper, 27Al NMR spectroscopic data on alumina reported in literature are collected in a comprehensive library. Based on this dataset, a new 3D correlative method of NMR parameters is presented, enabling fingerprinting and identification of such phases. Providing a gold standard from crystalline samples, this approach demonstrates that any sort of crystalline, ill crystallized or amorphous, mixed periodic or aperiodically ordered transition alumina can now be assessed beyond the current limitations of characterisation. Adopting the presented approach as a standard characterisation of alumina samples will readily reveal NMR parameter-structure-property relations suitable to develop new or improved applications of alumina. Methodological guidance is provided to assist consistent implementation of this characterisation throughout the fields involved.

A Porous POSiSil Suited for Pressure-Driven Reversible Confinement of Solutions: PSS-2.

Polyoligosiloxysilicone (POSiSil; designated PSS-2) is a copolymer of double four-ring (D4R) cyclosilicate and dimethylsiloxane. It is synthesized by linking D4R units in tetrabutylammonium cyclosilicate crystals with dimethyldichlorosilane. The structure of PSS-2 was revealed using solid state NMR spectroscopy. In this 3D copolymer D4R units are connected systematically by short siloxane chains most likely composed of 2 to 3 dimethylsiloxane monomers. Controlling the conversion of the parent material allows for tuning the porosity of PSS-2. Residual parent material is embedded inside PSS-2 polymer and can be eliminated by calcination. This leaves nanovoids inside PSS-2, which is moderately hydrophobic. Pressure-driven intrusion-extrusion cycles of aqueous solution exhibit hysteresis, thus, PSS-2 can be used as reversible confinement for liquids with a capacity of around 1000 mm3 g-1 in porosity.

1D-2D-3D Transformation Synthesis of Hierarchical Metal-Organic Framework Adsorbent for Multicomponent Alkane Separation.

A new hierarchical MOF consisting of Cu(II) centers connected by benzene-tricarboxylates (BTC) is prepared by thermoinduced solid transformation of a dense CuBTC precursor phase. The mechanism of the material formation has been thoroughly elucidated and revealed a transformation of a ribbon-like 1D building unit into 2D layers and finally a 3D network. The new phase contains excess copper, charge compensated by systematic hydroxyl groups, which leads to an open microporous framework with tunable permanent mesoporosity. The new phase is particularly attractive for molecular separation. Energy consumption of adsorptive separation processes can be lowered by using adsorbents that discriminate molecules based on adsorption entropy rather than enthalpy differences. In separation of a 11-component mixture of C1-C6 alkanes, the hierarchical phase outperforms the structurally related microporous HKUST-1 as well as silicate-based hierarchical materials. Grand canonical Monte Carlo (GCMC) simulation provides microscopic insight into the structural host-guest interaction, confirming low adsorption enthalpies and significant entropic contributions to the molecular separation. The unique three-dimensional hierarchical structure as well as the systematic presence of Cu(II) unsaturated coordination sites cause this exceptional behavior.

Absolute Quantification of Water in Microporous Solids with 1H Magic Angle Spinning NMR and Standard Addition.

Zeolites are microporous materials driving industrial scale adsorption, ion exchange, and catalytic processes. Their water content dramatically impacts their properties, but its quantification with Karl Fisher titration or thermal gravimetric analysis is problematic. When standard addition of water is combined with 1H magic angle spinning (MAS) NMR detection, absolute quantification of water in microporous materials becomes possible. The method was demonstrated on five different, commercially available zeolites.

Alternating Copolymer of Double Four Ring Silicate and Dimethyl Silicone Monomer-PSS-1.

A new copolymer consisting of double four ring (D4R) silicate units linked by dimethylsilicone monomer referred to as polyoligosiloxysilicone number one (PSS-1) was synthesized. The D4R building unit is provided by hexamethyleneimine cyclosilicate hydrate crystals, which were dehydrated and reacted with dichlorodimethylsilane. The local structure of D4R silicate units and dimethyl silicone monomers was revealed by multidimensional solid-state NMR, FTIR and modeling. On average, D4R silicate units have 6.8 silicone linkages. Evidence for preferential unidirectional growth and chain ordering within the PSS-1 copolymer was provided by STEM and TEM. The structure of PSS-1 copolymer consists of twisted columns of D4R silicate units with or without cross-linking. Both models are consistent with the spectroscopic, microscopic and physical properties. PSS-1 chains are predicted to be mechanically strong compared to silicones such as PDMS, yet more flexible than rigid silica materials such as zeolites.

Zeolite Beta Formation from Clear Sols: Silicate Speciation, Particle Formation and Crystallization Monitored by Complementary Analysis Methods.

The formation of silicate nanoaggregates (NAs) at the very early stages of precursor sols and zeolite beta crystallization from silicate nanoparticles (NPs) are investigated in detail using a combination of different analysis methods, including liquid-state 29 Si, 27 Al, 14 N, and 1 H NMR spectroscopy, mass spectrometry (MS), small-angle X-ray scattering (SAXS), X-ray diffraction (XRD), and transmission electron microscopy at cryogenic temperatures (cryo-TEM). Prior to hydrothermal treatment, silicate NAs are observed if the Si/OH ratio in the reaction mixture is greater than 1. Condensation of oligomers within the NAs then generates NPs. Aluminum doped into the synthesis mixtures is located exclusively in the NPs, and is found exclusively in a state that is fourfold connected to silicate, favoring their condensation and aggregation. These results are in agreement with general trends observed for other systems. Silicate NAs are essential intermediates for zeolite formation and are generated by the aggregation of hydrated oligomers, aluminate, and templating cations. Subsequent further intra-nanoaggregate silicate condensation results in the formation of NPs. 1 H and 14 N liquid NMR as well as diffusion ordered spectroscopy (DOSY) experiments provide evidence for weakly restricted rotational and translational mobility of the organic template within NAs as a consequence of specific silicate-template interactions. NAs thus appear as key species in clear sols, and their presence in the precursor sol favors silicate condensation and further crystallization, promoted either by increasing the Si/OH ratio or by heating.

Intrusion-extrusion spring performance of -COK-14 zeolite enhanced by structural changes.

-COK-14 zeolite, the variant of COK-14 (OKO topology) with a systematically interrupted framework, exhibits unusual behaviour in high pressure intrusion-extrusion cycles of 20 M LiCl solution. After the first cycle with deviating behaviour and partially irreversible intrusion, subsequent cycles show stable reversible behaviour. The system behaves like a spring with unique progressive intrusion in the range of 10-120 MPa followed by enhanced uptake before saturation. While the intrusion-extrusion cycling leads to fragmented crystals, powder diffraction reveals high crystallinity of the fragments. Based on the detailed characterisation of the zeolite samples with XRD, Rietveld refinement, N2 adsorption, TGA and (29)Si MAS NMR before and after intrusion-extrusion experiments, a model of the structure of the intruded -COK-14 samples is proposed. Intrusion-extrusion of LiCl solution systematically breaks the most strained bonds in the structure which results in a new framework connectivity with enhanced stability, which persists during the harsh intrusion-extrusion conditions.

Chabazite: stable cation-exchanger in hyper alkaline concrete pore water.

To avoid impact on the environment, facilities for permanent disposal of hazardous waste adopt multibarrier design schemes. As the primary barrier very often consists of cement-based materials, two distinct aspects are essential for the selection of suitable complementary barriers: (1) selective sorption of the contaminants in the repository and (2) long-term chemical stability in hyperalkaline concrete-derived media. A multidisciplinary approach combining experimental strategies from environmental chemistry and materials science is therefore essential to provide a reliable assessment of potential candidate materials. Chabazite is typically synthesized in 1 M KOH solutions but also crystallizes in simulated young cement pore water, a pH 13 aqueous solution mainly containing K(+) and Na(+) cations. Its formation and stability in this medium was evaluated as a function of temperature (60 and 85 °C) over a timeframe of more than 2 years and was also asessed from a mechanistic point of view. Chabazite demonstrates excellent cation-exchange properties in simulated young cement pore water. Comparison of its Cs(+) cation exchange properties at pH 8 and pH 13 unexpectedly demonstrated an increase of the KD with increasing pH. The combined results identify chabazite as a valid candidate for inclusion in engineered barriers for concrete-based waste disposal.

Cation exchange properties of zeolites in hyper alkaline aqueous media.

Construction of multibarrier concrete based waste disposal sites and management of alkaline mine drainage water requires cation exchangers combining excellent sorption properties with a high stability and predictable performance in hyper alkaline media. Though highly selective organic cation exchange resins have been developed for most pollutants, they can serve as a growth medium for bacterial proliferation, impairing their long-term stability and introducing unpredictable parameters into the evolution of the system. Zeolites represent a family of inorganic cation exchangers, which naturally occur in hyper alkaline conditions and cannot serve as an electron donor or carbon source for microbial proliferation. Despite their successful application as industrial cation exchangers under near neutral conditions, their performance in hyper alkaline, saline water remains highly undocumented. Using Cs(+) as a benchmark element, this study aims to assess the long-term cation exchange performance of zeolites in concrete derived aqueous solutions. Comparison of their exchange properties in alkaline media with data obtained in near neutral solutions demonstrated that the cation exchange selectivity remains unaffected by the increased hydroxyl concentration; the cation exchange capacity did however show an unexpected increase in hyper alkaline media.

A Flexible Photoactive Titanium Metal-Organic Framework Based on a [Ti(IV)3(µ3-O)(O)2(COO)6] Cluster.

The synthesis of titanium-carboxylate metal-organic frameworks (MOFs) is hampered by the high reactivity of the commonly employed alkoxide precursors. Herein, we present an innovative approach to titanium-based MOFs by the use of titanocene dichloride to synthesize COK-69, the first breathing Ti MOF, which is built up from trans-1,4-cyclohexanedicarboxylate linkers and an unprecedented [Ti(IV)3(µ3-O)(O)2(COO)6] cluster. The photoactive properties of COK-69 were investigated in depth by proton-coupled electron-transfer experiments, which revealed that up to one Ti(IV) center per cluster can be photoreduced to Ti(III) while preserving the structural integrity of the framework. The electronic structure of COK-69 was determined by molecular modeling, and a band gap of 3.77 eV was found.

Gallium oxide nanorods: novel, template-free synthesis and high catalytic activity in epoxidation reactions.

Gallium oxide nanorods with unprecedented small dimensions (20-80 nm length and 3-5 nm width) were prepared using a novel, template-free synthesis method. This nanomaterial is an excellent heterogeneous catalyst for the sustainable epoxidation of alkenes with H2 O2 , rivaling the industrial benchmark microporous titanosilicate TS-1 with linear alkenes and being much superior with bulkier substrates. A thorough characterization study elucidated the correlation between the physicochemical properties of the gallium oxide nanorods and their catalytic performance, and underlined the importance of the nanorod morphology for generating a material with high specific surface area and a high number of accessible acid sites.

Design of zeolite by inverse sigma transformation.

Although the search for new zeolites has traditionally been based on trial and error, more rational methods are now available. The theoretical concept of inverse σ transformation of a zeolite framework to generate a new structure by removal of a layer of framework atoms and contraction has for the first time been achieved experimentally. The reactivity of framework germanium atoms in strong mineral acid was exploited to selectively remove germanium-containing four-ring units from an UTL type germanosilicate zeolite. Annealing of the leached framework through calcination led to the new all-silica COK-14 zeolite with intersecting 12- and 10-membered ring channel systems. An intermediate stage of this inverse σ transformation with dislodged germanate four-rings still residing in the pores could be demonstrated. Inverse σ transformation involving elimination of germanium-containing structural units opens perspectives for the synthesis of many more zeolites.

Adsorption and separation of CO2 on KFI zeolites: effect of cation type and Si/Al ratio on equilibrium and kinetic properties.

Selective separation of CO2 is becoming one of the key technologies in the (petro-) chemical industry. This study focuses on the adsorption and separation of CO2 from CH4 on a new low-silica (LS) type of the eight-membered ring KFI zeolite. A series of alkali (Li, Na, K) and alkaline-earth (Mg, Ca, Sr) exchanged samples of the new LS KFI were synthesized and characterized. LS Li-KFI showed the largest pore volume, whereas LS Na-KFI and LS K-KFI were inaccessible for Argon at 87 K. Adsorption of CO2 at 303 K demonstrated the dominant quadrupolar interaction on alkali-exchanged LS KFI samples. LS Li-KFI showed the largest capacities upon high pressure isotherm measurements of CO2 (4.8 mmol/g), CH4 (2.6 mmol/g), and N2 (2.2 mmol/g) up to 40 bar at 303 K. The performance of the new LS KFI was compared to a KFI sample (ZK-5) with a higher Si/Al ratio. Isotherm measurements and dynamic breakthrough experiments demonstrated that ZK-5 samples show larger working capacities for CO2/CH4 separations at low pressure. Li-ZK-5 and Na-ZK-5 show the highest capacities and high selectivities (similar to benchmark 13X).

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.