An investigation of the adsorption of aromatic hydrocarbons in zeolite Na–Y by solid-state NMR spectroscopy

The adsorption of toluene inside zeolite Na–Y was investigated by solid-state NMR spectroscopy. The environment of Na⁺ ions at different sites in Na–Y before and after adsorption was characterized by ²³Na magic-angle spinning (MAS) NMR. The information on the dynamic behavior of guest molecules inside the supercage of Na–Y was obtained by analyzing wideline ²H NMR spectra. The effect of loading level and temperature on molecular dynamics was also examined. The cation–sorbate interactions were directly probed by ²³Na{¹H} rotational-echo double-resonance (REDOR) experiments at different temperatures. Molecular Monte Carlo simulations were also performed to assist in the interpretation of the NMR data. ²³Na MAS and ²³Na{¹H} REDOR results show that each toluene molecule is facially coordinated to a Na⁺ ion at the SII site in the supercage, forming a π-complex. The adsorption also causes the Na⁺ ions initially located at the SI′ site to slightly shift to a new position within the sodalite cage, but has little effect on the Na⁺ at the SI site. The ²H NMR results indicate that the toluene molecules undergo a 2-site flip around the molecular long axis in addition to the methyl group rotation about its C₃ axis. ²³Na MAS spectra suggest that the adsorptive behavior of benzene and p-xylene in Na–Y is similar to that of toluene/Na–Y. ²³Na{¹H} REDOR results further indicate that inside the supercage, the degree of molecular motion follows the order of benzene > toluene > p-xylene.     

The study on the conductivity and morphology of polyurethaneurea electrolytes based on poly(ethylene glycol) 2000 and LiClO4

Polyurethaneureas (PUU), which were synthesized from 4,4′-diphenylmethane diisocyanate (MDI), poly(ethylene glycol) (PEG, MW=2000), and 3,5-diaminobenzoic acid, were used as the matrix of the polyelectrolytes in this study. Differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FT-IR), and ⁷Li magic angle spinning (MAS) solid-state NMR were used to monitor changes in the morphology of PUU electrolytes corresponding to the concentration of lithium perchlorate (LiClO₄) dopants. The results of DSC and FT-IR indicate the different polymer complexes formed by the interaction of the Li⁺ ions with the different coordination sites of PUU. The ⁷Li MAS solid-state NMR investigation of the PUU electrolytes points out that two different Li⁺ environments exist at lower temperature. The results of DSC and the ⁷Li MAS solid-state NMR show that Li⁺ ions are preferentially coordinated to the ether oxygen of the PEG soft-segment when the salt concentration is below 0.1 mmol LiClO₄(gPUU)⁻¹. Impedance spectroscopy measurements show that the conductivity behavior followed the Arrhenius equation and was influenced by the hard-segment T_g. One of the PUU electrolytes under the investigation has an ionic conductivity as high as 3.0×10⁻⁵ S cm⁻¹ at 30 °C.     

NMR Study on the Acidity of TS-1 Zeolite

The acidic properties of TS-1 and Silicalite-1 zeolites have been investigated by the solid-state MAS NMR technique capable of in situ sample pretreatment. As shown by a combination of the ³¹P MAS NMR and ¹H MAS NMR techniques with trimethylphosphine, not only Brønsted acid sites but also Lewis acid sites exist in the TS-1 zeolites. Moreover, TS-1 zeolite is more acidic compared with Silicalite-1. The ¹H, ²⁹Si MAS NMR spectra and the resonance related to Brønsted acid species in the ³¹P MAS NMR spectra demonstrate clearly that the presence of titanium in the framework results in the formation of a new hydroxy group, titanols, which is more acidic than silanols of Silicalite-1. The ³¹P MAS NMR measurements also illustrate convincingly the existence of at least two different Lewis acid species on the TS-1 zeolites. The conversion of propylene oxide into methoxypropanol catalyzed by TS-1 or Silicalite-1 zeolite in methanol solution as a test reaction has also been described. With the increase of titanium in zeolite, TS-1 appears to have a higher activity during the reaction of propylene oxide to methoxypropanol.     

Ion and Molecular Transport in Solid Electrolytes Studied by NMR

NMR is the method of choice for molecular and ionic structures and dynamics investigations. The present review is devoted to solvation and mobilities in solid electrolytes, such as ion-exchange membranes and composite materials, based on cesium acid sulfates and phosphates. The applications of high-resolution NMR, solid-state NMR, NMR relaxation, and pulsed field gradient ¹H, ⁷Li, ¹³C, ¹⁹F, ²³Na, ³¹P, and ¹³³Cs NMR techniques are discussed. The main attention is paid to the transport channel morphology, ionic hydration, charge group and mobile ion interaction, and translation ions and solvent mobilities in different spatial scales. Self-diffusion coefficients of protons and Li⁺, Na⁺, and Cs⁺ cations are compared with the ionic conductivity data. The microscopic ionic transfer mechanism is discussed.     

Single crystal structure of fully dehydrated partially Co-exchanged zeolite X: Comparison with partially dehydrated partially Co-exchanged zeolites X

The crystal structure of the fully dehydrated Co, Na–X zeolite (Na₁₆Co₃₈Al₉₂Si₁₀₀O₃₈₄) is investigated and compared to that of three partially hydrated zeolites. In the fully dehydrated crystal, cobalt ions almost entirely occupy Site I, and partially Site II while the residual sodium cations partly occupy Site II and Site III. The dehydration induces a migration of Co²⁺ cations from Site I′ to Site I and severely affects the structure, the structural strain being released by changes of framework valence angles or, to a less extent, by distortions of TO₄ tetrahedra. Comparison with dehydrated M–X zeolite structures (M = Ba, Na, Ca, Tl, Li) confirms the relation between the size of the charge compensating cation and the stresses on the skeleton that are mainly explained by cation–oxygen electrostatic interactions.     

The effect of the inner particle structure on the electronic structure of the nano-crystalline Li-Ti-O spinels

The effect of the inner particle structure on Li insertion activity and electronic structure of the nano-crystalline Li-Ti-O spinels was studied on materials prepared by solid state and solvothermal synthesis. The high temperature prepared materials of composition corresponding to Li₄Ti₅O₁₂ feature particles with characteristic size of ca. 200 nm with randomly distributed defects. The products of solvothermal synthesis with composition Li_1.1Ti_1.9O_4+δ, feature cubic particles of characteristic dimension of ca. 50 nm; the characteristic particle size differs from that of the coherent domain determined by X-ray diffraction. The reduction of the solvothermal and high temperature synthesized nano-crystalline spinels in Li containing solutions leads according to ⁶Li MAS NMR spectra to Li insertion into tetrahedral 8b and octahedral 16c position, respectively. Additional broad NMR signal attributable to a Knight shift was observed in spectra of partially reduced high temperature spinels. In the case of solvothermal spinels is the Knight shift signal less pronounced and appears only in spectra of samples in which the phase transition occurs on the local level. The UV-vis-NIR spectra of the partially reduced Li-Ti-O spinel samples correspond to expected semiconductor character of Li-Ti-O spinels. Both types of materials are characterized by band gap of 3.8 eV (high temperature spinel) and 3.5 eV (solvothermal material). Partial reduction accompanied with Li insertion causes additional optical transition in the visible to near infrared region, which can be attributed to formation of trivalent Ti, character of which changes with degree of reduction. The behavior observed for partially reduced high temperature spinels is similar to that reported for TiO₂ (anatase). The spectral behavior of the partially reduced solvothermal spinels is more complex and reflects suppressed phase transition.     

Zeolite ZnY catalysts prepared by solid-state ion exchange

Zeolites ZnY with various overall zinc contents were prepared from mixtures of zeolite NH₄Y and crystalline zinc chloride by solid-state ion exchange. The obtained materials were investigated with carbon monoxide, xenon, and nitrogen adsorption as well as with ¹²⁹Xe NMR and XRF spectroscopy. From the results of these measurements, the zinc cation distributions between the different types of cages of the faujasite framework as well as between the crystallographic positions SIII and SII within the large voids (supercages) were quantitatively determined. The concentrations of zinc cations in the supercages of the presently prepared zeolites are considerably higher than in materials obtained from NaY by conventional wet ion exchange using aqueous zinc salt solutions. Experimental evidence is provided for salt inclusion under certain conditions of preparation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Spectroscopic characterisation of the strength and stability of the acidic sites of Al-rich microporous micelle-templated silicates

A micelle-templated material with Si/Al=2.5 has been synthesised, then either calcined to provide the H form of the sample or partially exchanged with Li⁺ and Na⁺ ions. After surfactant removal, all samples were microporous, with average diameter around 18 Å.In the H form, sizeable formation of octahedral and pentacoordinated Al was found, whereas, with Na sample, ²⁷Al NMR spectra showed minimal occurrence of octahedral Al, so indicating that Na⁺ cations, in contrast with protons, do compensate tetrahedral Al in the silicate structure.All samples have been characterised via FT-IR spectroscopy of surface hydroxyl species and adsorbed probe molecules acting as Lewis bases (carbon monoxide, ammonia, propene).Although the Si/Al ratio is close to that of Y zeolites, these systems showed definitely weaker acidity, similar to that of amorphous silica–aluminas of low Al content. With H sample, no zeolite-like Brønsted site has been observed, the more acidic hydroxyls being those absorbing at 3660 cm⁻¹, ascribed to SiOAl(OH)OSi groups, able to transfer a proton to ammonia, but not to propene, and undergoing with CO a shift of about 220 cm⁻¹.With Na sample, the nearly complete exchange caused the disappearance of more acidic hydroxyls and of Al³⁺ Lewis sites; a fraction of Na⁺ cations resulted not accessible to probe molecules, being probably buried into the thick walls. With Li sample, some AlOH species and Al³⁺ Lewis sites are at the surface, as a consequence of the lower degree of exchange.     

Evaluation of strong acid properties of layered HNbMoO6 and catalytic activity for Friedel–Crafts alkylation

The acid properties and catalytic activity of layered HNbMoO₆ for liquid-phase Friedel–Crafts alkylation are examined. ³¹P MAS NMR spectroscopy using trimethylphosphine oxide as a probe molecule reveals that HNbMoO₆ possesses strong acid sites in the interlayer region. Layered HNbMoO₆ is demonstrated to display remarkable catalytic performance for this reaction, substantially exceeding the activities of niobic acid, niobium–molybdenum mixed oxide, ion-exchange resins, and zeolites. It is determined that benzyl alcohol is intercalated into the HNbMoO₆ interlayer during alkylation to form a monolayer configuration, allowing the strong interlayer acid sites to participate in the reaction.     

Evidence for non-site-isolation in ZSM-5 from ion-exchange and catalytic studies

Ion exchange of HZSM-5 samples with alkali metal cations, using metal chloride solutions, results in partially exchanged zeolites, MHZSM-5, M = Li, Na, K or Cs. The degree of exchange is found to increase with increasing ionic radius of the cations. The catalytic properties of the alkalized zeolites were evaluated using the reaction conditions under which the catalytic activity of the HZSM-5 samples in terms of n-hexane cracking is proportional to the aluminium content. From the residual catalytic activity exhibited by the Na-, K- and CsHZSM-5 samples it is concluded that each of the larger Na⁺, K⁺ and Cs⁺ ions is influencing more than one AlO ₄ ^– tetrahedron, implying that the aluminium sites in ZSM-5 are not isolated. The ion-exchange results are then interpreted in terms of non-isolated aluminium sites. The ion-exchange and catalytic properties of the zeolites as a function of aluminium content are also discussed.     

Brønsted acidity of amorphous silica–aluminas studied by 1H NMR

¹H broad-line (4 K) and MAS (room temperature) NMR have been used to study the acid strength of two amorphous silica–aluminas interacting or not with adsorbed water. The study is more difficult than for zeolites, because the acidic SiO(H)Al bridges are reversibly destroyed by dehydration. However, an acidity coefficient value (H₃O⁺ concentration per Brønsted acid site when one water molecule interacts with each Brønsted site) of 0.34±10%; has been determined. This value is equal to that obtained for H-faujasite and H-mordenite samples with Si/Al ratios high enough for maximum acid strength.     

Structural dependence of crystallization in glasses along the nepheline (NaAlSiO4) ‐ eucryptite (LiAlSiO4) join

Lithium and sodium aluminosilicates are important glass‐forming systems for commercial glass‐ceramics, as well as being important model systems for ion transport in battery studies. In addition, uncontrolled crystallization of LiAlSiO₄ (eucryptite) in high‐Li₂O compositions, analogous to the more well‐known problem of NaAlSiO₄ (nepheline) crystallization, can cause concerns for long‐term chemical durability in nuclear waste glasses. To study the relationships between glass structure and crystallization, nine glasses were synthesized in the Li_xNa_1‐xAlSiO₄ series, from x = 0 to x = 1. Raman spectra, nuclear magnetic resonance (NMR) spectroscopy (Li‐7, Na‐23, Al‐27, Si‐29), and X‐ray diffraction were used to study the quenched and heat‐treated glasses. It was found that different LiAlSiO₄ and NaAlSiO₄ crystal phases crystallize from the glass depending on the Li/Na ratio. Raman and NMR spectra of quenched glasses suggest similar structures regardless of alkali substitution. Li‐7 and Na‐23 NMR spectra of the glass‐ceramics near the endmember compositions show evidence of several differentiable sites distinct from known Li_xNa_1‐xAlSiO₄ crystalline phases, suggesting that these measurements can reveal subtle chemical environment differences in mixed‐alkali systems, similar to what has been observed for zeolites.     

Effects of Difference in Ionic Radii on Chemical Ordering in Mixed‐Cation Silicate Glasses: Insights from Solid‐State 17O and 7Li NMR of Li–Ba Silicate Glasses

Understanding of the extent of cation disorder and its effect on the properties in glasses and melts is among the fundamental puzzles in glass sciences, materials sciences, physical chemistry, and geochemistry. Particularly, the nature of chemical ordering in mixed‐cation silicate glasses is not fully understood. The Li–Ba silicate glass with significant difference in the ionic radii of network‐modifying cations (~0.59 Å) is an ideal system for revealing unknown details of the effect of network modifiers on the extent of mixing and their contribution to the cation mobility. These glasses also find potential application as energy and battery materials. Here, we report the detailed atomic environments and the extent of cation mixing in Li–Ba silicate glasses with varying X_BaO [BaO/(Li₂O + BaO)] using high‐resolution solid‐state nuclear magnetic resonance (NMR) spectroscopy. The first ¹⁷O MAS and 3QMAS NMR spectra for Li–Ba silicate glasses reveal the well‐resolved peaks due to bridging oxygen (Si–O–Si) and those of the nonbridging oxygens including Li–O–Si and mixed {Li, Ba}–O–Si. The fraction of Li–O–Si decreases with an increase in X_BaO and is less than that predicted by a random Li–Ba distribution. The result demonstrates a nonrandom distribution of Li⁺ and Ba⁺ around NBOs characterized by a prevalence of the dissimilar Li–Ba pair. Considering the previously reported experimental results on chemical ordering in other mixed‐cation silicate glasses, the current results reveal a hierarchy in the degree of chemical order that increases with an increase in difference in ionic radius of the cation in the glasses [e.g., K–Mg (~0.66 Å) ≈Ba–Mg (~0.63 Å) ≈Li–Ba (~0.59 Å) > Na–Ba (~0.33 Å) > Na–Ca (~0.02 Å)]. The ⁷Li MAS NMR spectra of the Li–Ba silicate glasses show that the peak maximum increases with increasing X_BaO, suggesting that the average Li coordination number and thus Li–O distance decrease slightly with increasing X_BaO, potentially leading to an increased activation energy barrier for Li diffusion. Current experimental results confirm that the degree of chemical ordering due to a large difference in ionic radii controls the transport properties of the mixed‐cation silicate glasses.     

Catalytic synthesis of chalcone and flavanone using Zn–Al hydrotalcite adhere ionic liquid

The Claisen–Schmidt condensation of 2′-hydroxy acetophenone and benzaldehyde to chalcone and flavanone show that calcined Zn–Al (6) hydrotalcite is active for this synthesis. Coating of ionic liquid ‘1-(tri-ethoxy-silyl-propyl)-3-methyl-imidazolium chloride’ on Zn–Al hydrotalcites was accomplished employing incipient wetness process and on NaY, NaX, MK-5 and silica gel employing co-condensation methodology. Impregnated IL on calcined Zn–Al (6) catalysts were characterized by XRD, SEM, BET, ¹³C and ²⁷Al NMR analysis and the activity of these catalysts were investigated for chalcone and flavanone synthesis. ²⁷Al CP MAS NMR technique was used to show that interaction of IL with hydrotalcite modifies the acid–base sites and is responsible for enhancement of catalyst activity. Several aromatic aldehydes were screened to assess the general applicability of the system.     

Niobium oxide acidity studied by proton broad-line NMR at 4 K and MAS NMR at room temperature

The quantitative study of the Brønsted acidity of niobic acid (Nb₂O₅·xH₂O) using broad-line¹H NMR at 4 K has been performed by interacting niobic acid, pretreated at 573 K under vacuum, with water molecules. The number of oxyprotonated species (H₃O⁺ and H₂O...HO species formed, unreacted acidic OH groups or excess H₂O molecules) deduced from the simulations of the broad-line¹H NMR spectra shows a continuous increase in the number of H₃O⁺ species with adsorbed water molecules. This increase may be due to a classical dilution effect or to a synergistic interaction between Brønsted and Lewis acid sites. These results are compared with those of some HY zeolites with or without framework defects.     

Synthesis, X-ray structure and Hg, Se CP MAS NMR studies on the first tris(imidazolidine-2-selone) mercury complex: {Chloro-tris[N-methyl-2(3H)-imidazolidine-2- selone]mercury(II)}chloride

A novel cationic Hg(II) complex has been synthesized with N-methyl-imidazolidine-2-selone ligand. The tris(N-Methyl-imidazolidine-2-selone) mercury(II) complex, [(MeImSe)₃HgCl]⁺Cl⁻ (1), has been characterized by single crystal X-ray analysis and CP MAS ¹⁹⁹Hg and ⁷⁷Se NMR.     

Surface complexes in zeolite-catalysed acylation reactions detected by13C MAS NMR spectroscopy

The state of the acylating agent acetyl chloride, adsorbed on a series of proton and metal ion exchanged zeolites X, Y (faujasite) and ZSM-5, was investigated by¹³C MAS NMR spectroscopy. The observed carbonyl signals were assigned to two species: chemisorbed acetyl chloride bound to lattice oxygen (signals near 182 ppm), and acetyl chloride complexed with counter cations in the lattice (signals near 172 ppm). In a few cases signals were observed which have been assigned to free acylium cation stabilized on the surface of the solid (signal 160–165 ppm). Experiments in which toluene was adsorbed on to ZnY pretreated with acetyl chloride showed the participation of various adsorbed species in the acylation reaction of toluene.     

Isomerization of α-pinene over dealuminated ferrierite-type zeolites

Isomerization of α-pinene was performed on a series of dealuminated ferrierite (FER)-type zeolites in liquid phase at 363 K using a batch reactor. The course of zeolite dealumination was followed in detail using ²⁹Si, ²⁷Al, ¹H MAS NMR, XRD, FTIR, and sorption of nitrogen. The ammonium form of FER was dealuminated with aqueous solutions of HCl. While retaining the crystallinity of the zeolite particles, the treatments removed up to 53% of the tetrahedrally coordinated aluminum atoms from the FER framework. According to ²⁹Si MAS NMR studies, the framework aluminum atoms located at the 10-membered rings in the main channels of FER (T_B sites) were depleted preferentially from their positions. Even relatively mild dealumination of FER led to an active catalyst containing both Brønsted and Lewis centers, yielding up to 97% conversion of α-pinene at 363 K, in contrast to the 72% observed for the parent hydrogen form. Such catalytic behavior was discussed in terms of the conversion of a reactant inside micropores of the zeolite catalyst, on Brønsted acid centers with enhanced strength located probably in the vicinity of Lewis sites. The selectivity toward camphene and limonene changed smoothly with the dealumination level; thus, a higher selectivity toward limonene was observed at the expense of camphene formation with increasing the n_Si/n_Al ratio of the catalysts. The selectivity toward camphene and limonene was close to 85% for all of the materials studied. The initial rates of α-pinene transformations over FER-type materials exceeded those observed for other catalytic systems, heteropoly acid/SiO₂ and H₂SO₄/ZrO₂. This study demonstrates the successful application of a medium-pore zeolite for the catalytic transformation of α-pinene in liquid phase.     

Synthesis and Characterization of Gallosilicate Molecular Sieve with the MCM-22 Framework Topology

Ga-MCM-22 with high gallium content has been synthesized with hydrothermal method and characterized by means of X-ray diffraction, SEM, TGA, ⁷¹Ga and ²⁹Si MAS NMR, BET surface area, and NH₃-TPD. Ga-MCM-22 was obtained as very homogeneous particles of about 5-7 m diameters and showed very similar morphologies to its Al analogue. The Na/Ga ratio of Ga-MCM-22 was much lower than 1.0, indicating that most of the negative framework charges should be compensated by protonated template, HMI. The results from ⁷¹Ga and ²⁹Si MAS NMR demonstrated that gallium was incorporated into the tetrahedral framework of Ga-MCM-22. Also, the ²⁹Si MAS NMR spectra showed that the as-synthesized Ga-MCM-22 has a different distribution of tetrahedral Si sites from its Al analogue. After calcination, however, the distribution of tetrahedral Si sites significantly changed, due to a large degallation from the framework of Ga-MCM-22. The NH₃-TPD showed that Ga-MCM-22 possesses Brönsted and Lewis acid sites.     

Mixed‐cation LiCa‐LSX zeolite with minimum lithium for air separation

The aim of this work was to reduce/minimize Li in Li‐LSX by replacing the 70% Li⁺ cations in Li‐LSX that are bonded to the interior or inaccessible sites which are not used for adsorption. Thus, mixed‐cation LiCa‐LSX containing minimum lithium were prepared by exchanging small fractions of Li⁺ into Ca‐LSX, followed by dehydration under mild conditions to avoid migration/equilibration of Li cations. Comparisons of adsorption isotherms of N₂/O₂ and heats of adsorption for the LiCa‐LSX samples with that for pure‐cation Li‐LSX and Ca‐LSX provided strong evidence that significant amounts of these Li cations indeed remained on the exposed sites (SIII). The mixed‐cation LiCa‐LSX samples were compared against the pure‐cation Ca‐LSX and Li‐LSX based on their performance for oxygen production by PSA, via model simulation. The results showed that the mixed‐cation LiCa‐LSX samples yielded significantly higher O₂ product productivities at the same product purity and recovery than their pure‐cation precursor (Ca‐LSX). © 2017 American Institute of Chemical Engineers AIChE J, 64: 406–415, 2018