Hydrophobic Silicalite-1 Research Articles

Enhancing Water Tolerance and N2 Selectivity in NH3-SCR Catalysts by Protecting Mn Oxide Nanoparticles in a Silicalite-1 Layer.

Mn-based catalysts are promising candidates for eliminating harmful nitrogen oxides (NOx) via selective catalytic reduction with ammonia (NH3-SCR) due to their inherent strong redox abilities. However, poor water tolerance and low N2 selectivity are still the main limitations for practical applications. Herein, we succeeded in preparing an active catalyst for NH3-SCR with improved water tolerance and N2 selectivity based on protecting MnOx with a secondary growth of a hydrophobic silicalite-1. This protection suppressed catalyst deactivation by water adsorption. Interestingly, impregnating MnOx on MesoTS-1 followed by silicalite-1 protection allowed for a higher dispersion of MnOx species, thus increasing the concentration of acid sites. Consequently, the level of N2O formation is decreased. These improvements resulted in a broader operating temperature of NOx conversion and a modification of the NH3-SCR mechanism. Diffuse reflectance infrared Fourier transform spectroscopy analysis revealed that unprotected Mn/MesoTS-1 mainly followed the Eley-Rideal mechanism, while Mn/MesoTS-1@S1 followed both Langmuir-Hinshelwood and Eley-Rideal mechanisms.

Advancing highly selective low-temperature ammonia oxidation: Hydrophobic silicalite-1 shell confining silver nanoparticles on Cu/ZSM-5 core

A judiciously devised core–shell NH3-SCO catalyst featuring a Cu/ZSM-5 core enveloped by an Ag/silicalite-1 shell (Cu/ZSM-5@Ag/S-1) was rationally constructed. Integrating the silicalite-1 shell effectively suppresses the migration of Ag into Cu/ZSM-5 core, conserving the active Cu2+ sites for the catalytical conversion of byproducts NOx. Concurrently, the shell averts the formation of positively charged Ag species, facilitating the generation of abundant Ag0 nanoparticles encapsulated in the S-1 shell. Comprehensive characterizations reveal abundant Ag0 species within the core–shell Cu/ZSM-5@Ag/S-1 catalyst, boosting O2 activation and NH3 dehydrogenation and thereby contributing to superior low-temperature activity in NH3-SCO reactions. Furthermore, the hydrophobic S-1 shell effectively reinforces the hydrothermal stability of the core–shell Cu/ZSM-5@Ag/S-1. DRIFTS coupled with DFT studies elucidate that the core–shell sample follows the imide mechanism, while the shell-free sample adheres to the hydrazine mechanism. This work advances our understanding of catalyst design and presents a promising solution with practical implications for ammonia oxidation processes.

Adsorption and catalytic properties of enzymes on the surface of silicalite-1

Microporous hydrophobic silicalite-1 was used as a carrier for immobilization of different enzymes, such as horseradish peroxidase, calf intestinal alkaline phosphatase and two β-galactosidases of different origin, to create heterogeneous biocatalytic systems. The peculiarities of enzyme adsorption on the surface of silicalite-1, as well as catalytic properties of the obtained systems compared to enzyme activity in solution and on the surface of other carriers, are discussed.

Rapid synthesis of highly oriented hydrophobic silicalite-1 zeolite films on alloy steel at lower temperature for corrosion protection

• Rapid growth of oriented zeolite film on diverse substrates at lower temperature was studied. • Thickness of as-prepared zeolite films under three conditions is all around 1 μm. • Lower temperature leads to longer synthesis time and worse hydrophobicity of films. • Films prepared at 373 K for 4 h show terrific hydrophobicity and corrosion resistance. A method to quickly prepare highly oriented silicalite-1 zeolite films on different substrates at lower temperature was provided in this work. Compared with the traditional hydrothermal synthesis, rubbing a layer of seed pastes on the pretreated substrate surface in advance and using (NH 4 ) 2 SiF 6 as silicon source for subsequent secondary growth process can effectively reduce the synthesis temperature and shorten the contact time between the substrate and the strong alkaline synthesis solution. The thickness of the zeolite films prepared under three optimal conditions is all around 1 μm and the best contact angle value of 142.5° was achieved for the film prepared at 373 K for 4 h, while this values of the film prepared at 363 K for 6 h and 353 K for 10 h were 97.8° and 41.7°, respectively. The results of SECM showed that the detected localized current value of the film prepared at 353 K for 10 h was similar to that on bare steel after immersion in 0.62 M NaCl solution for 24 h (around 0.4 nA). At the same time, the current value measured under the other two preparation conditions was much higher, suggesting that the corrosion resistance of the film prepared under 353 K was unsatisfactory. In addition, EIS results demonstrated that the corrosion resistance of the films prepared at 363 K for 6 h also decreased significantly after 72 h immersion, while the films prepared at 373 K for 4 h still maintained excellent corrosion resistance and no obvious corrosion products were detected even immersion time up to 720 h. This work provides a new strategy for the application of zeolite in the field of material protection.

In-situ confinement of ultrasmall palladium nanoparticles in silicalite-1 for methane combustion with excellent activity and hydrothermal stability

Maximizing the use of palladium without compromises in catalytic activity and stability in the combustion of methane is extremely challenging due to the harsh operation conditions. To achieve this goal, a series of core-shell-structured catalysts with different amounts of palladium nanoparticles confined in hydrophobic silicalite-1 (Pd@S-1) was designed. Unexpectedly, a volcanic trend between catalytic activity and palladium loading was found as the loading increased from 0.3 wt% to 1.6 wt%, among which the 0.6 wt%Pd@S-1 exhibited the highest catalytic activity with a complete combustion temperature of 380 °C. Besides, the 0.6 wt%Pd@S-1 showed an ultrahigh stability in the high temperature applications due to the spatial confinement of palladium inside the rigid zeolite matrix. Moreover, owing to the hydrophobicity of the pure silica zeolite, the Pd@S-1 could selectively hinder the diffusion of water vapor into the palladium sites, leading to the outstanding water-resistance ability.

Improving hydrothermal stability of acid sites in MFI type aluminosilicate zeolite (ZSM-5) by coating MFI type all silica zeolite (silicalite-1) shell layer

Abstract Zeolites have been applied in various chemical processes due to their multi-functionality. In practical use of zeolites, their hydrothermal stability is one of the important factors. We focused on the coating with hydrophobic silicalite-1, which is all silica MFI zeolite. In this work, we investigated the hydrothermal stability of ZSM-5 (MFI type aluminosilicate zeolite) coated with silicalite-1 (all silica MFI zeolite) by the combination of steam treatment and NH3 temperature programed desorption (NH3-TPD). The peak area at higher temperature (h-peak area) in NH3-TPD profiles for core-shell MFI zeolite (ZSM-5/s-1) was unchanged even after steam treatment for 8 h in contrast to uncoated ZSM-5. These results strongly indicate that extremely high Si/Al ratio on the external surface coated with silicalite-1 is highly effective for improving the hydrothermal stability; the hydrophobicity of silicalite-1 probably prevents the penetration of steam into Al sites of ZSM-5. This work opens up a new function of the silicalite-1 layer on ZSM-5 other than improvement of shape selectivity.

High Water Tolerance of a Core-Shell-Structured Zeolite for CO2 Adsorptive Separation under Wet Conditions.

Dehumidification in CO2 adsorptive separation processes is an important issue, owing to its high energy consumption. However, available adsorbents such as low-silica zeolites show a significant decrease in CO2 adsorption capacity when water vapor is present. A core-shell-structured MFI-type zeolite with a hydrophilic ZSM-5 coated with a hydrophobic silicalite-1 shell layer was applied in CO2 adsorptive separation under wet conditions. This hybrid material demonstrated remarkably high water tolerance with stable CO2 adsorption performance without additional thermal treatment for regeneration, whereas a significant decrease in the CO2 adsorption amount because of water vapor was observed on the parent ZSM-5. The core-shell structure of zeolites with high pore volumes, such as LTA or CHA, could also be suitable candidates for high CO2 adsorption capacity and high water tolerance for practical applications.

Adsorption of HMF from Water/DMSO Solutions onto Hydrophobic Zeolites: Experiment and Simulation

The adsorption of 5-hydroxymethylfurfural (HMF), DMSO, and water from binary and ternary mixtures in hydrophobic silicalite-1 and dealuminated Y (DAY) zeolites at ambient conditions was studied by experiments and molecular modeling. HMF and DMSO adsorption isotherms were measured and compared to those calculated using a combination of grand canonical Monte Carlo and expanded ensemble (GCMC-EE) simulations. A method based on GCMC-EE simulations for dilute solutions combined with the Redlich-Kister (RK) expansion (GCMC-EE-RK) is introduced to calculate the isotherms over a wide range of concentrations. The simulations, using literature force fields, are in reasonable agreement with experimental data. In HMF/water binary mixtures, large-pore hydrophobic zeolites are much more effective for HMF adsorption but less selective because large pores allow water adsorption because of H2 O-HMF attraction. In ternary HMF/DMSO/water mixtures, HMF loading decreases with increasing DMSO fraction, rendering the separation of HMF from water/DMSO mixtures by adsorption difficult. The ratio of the energetic interaction in the zeolite to the solvation free energy is a key factor in controlling separation from liquid mixtures. Overall, our findings could have an impact on the separation and catalytic conversion of HMF and the rational design of nanoporous adsorbents for liquid-phase separations in biomass processing.

Evolution of the energetic characteristics of {silicalite-1 + water} repulsive clathrates in a wide temperature range

Recently {lyophobic porous powders + liquid} systems were proposed to be used for nontraditional energy storage and conversion purposes. This article reports the experimental study of the mechanical behavior, within the pressure-volume (PV) diagram, of the {hydrophobic silicalite-1 + water} system in the temperature range 10-80 °C. Repeated recordings of PV-isotherms and thermal effects of the repulsive clathrate during successive compression-decompression runs were performed using scanning transitiometry. An unexpected steady decline in the intrusion-extrusion pressure and volume of embedded water was found during the forced (repeated) intrusion of water into the pores of silicalite-1 and its spontaneous extrusion at constant temperature. A discussion of possible reasons of unconventional behavior of these heterogeneous systems as well as a thermodynamic analysis is presented.

Spectroscopic characterization of Brooker’s merocyanine in Silicalite-1 and ZSM-5 leading to second harmonic generation

The use of porous materials has become increasingly significant in the pursuit of novel composite materials with nonlinear optical properties. The microporous channels in Silicalite-1 and ZSM-5, which have identical crystal frameworks but different chemical composition, were used to study the role of zeolite composition on dye adsorption and organization, leading to second-harmonic generation (SHG). The dye molecule, known as Brooker’s merocyanine (4-[(1-methyl-4(1H)-pyridinylidene)ethylidene]-2,5-cyclohexadien-1-one), exhibits one of the largest known molecular hyperpolarizabilities for small dye molecules, but it crystallizes centrosymmetrically. When Brooker’s merocyanine was adsorbed to Silicalite-1 powder, no SHG was detected, but when adsorbed to ZSM-5, the powder was SHG-active. Spectroscopic characterization of the new materials was used to determine the dye loading in each zeolite. The hydrophilic ZSM-5 channels proved to be essential for dye adsorption and alignment within the channels as compared to the hydrophobic Silicalite-1 which did not appreciably adsorb the dye. The effect of dye protonation and isomerization on adsorption to each zeolite was also studied, with neither having an effect on the amount of dye adsorbed.

New insights in the formation of silanol defects in silicalite-1 by water intrusion under high pressure

The "water-silicalite-1" system is known to act as a molecular spring. The successive intrusion-extrusion cycles of liquid water in small crystallites (6 × 3 × 0.5 μm(3)) of hydrophobic silicalite-1 were studied by volumetric and calorimetric techniques. The experiments displayed a decrease of the intrusion pressure between the first intrusion-extrusion cycle and the consecutive ones, whereas the extrusion pressures remained unchanged. However, neither XRD studies nor SEM observations revealed any structural and morphological modifications of silicalite-1 at the long-range order. Such a shift in the value of the intrusion pressure after the first water intrusion-extrusion cycle is attributed to the creation of silanol groups during the first water intrusion. Detailed FTIR and solid-state NMR spectroscopic characterizations provided a molecular evidence of chemical modification of zeolite framework with the formation of local silanol defects created by the breaking of siloxane bonds.

Grand Canonical Monte Carlo Simulation Study of Water Adsorption in Silicalite at 300 K

This molecular simulation work focuses on the adsorption of water in a priori hydrophobic silicalite-1, a microporous ordered silica. The water-water interactions are described with the SPC model, while water-silica interactions are calculated in the framework of the PN-TrAZ model. The water adsorption isotherm at 300 K, the configurational energies, and the isosteric heat of adsorption are calculated by the grand canonical Monte Carlo (GCMC) simulation method. The thermodynamic integration scheme allows one to calculate the grand potential along the adsorption isotherm. The adsorption results are compared with experiments, showing only qualitative agreement. Indeed, the simulations do not reproduce the expected hydrophobicity of silicalite (Eroshenko, V.; Regis, R.-C.; Soulard, M.; Patarin, J. C. R. Phys. 2002, 3, 111). This indicates that common models used to describe confined polar molecules are far from being operative. In this work, it is shown, on the basis of periodic ab initio calculations, that confined water molecules in silicalite have a dipole value roughly 10% smaller than that in the bulk liquid phase, indicating that the environment felt by a confined water molecule in silicalite pores is not equivalent to that in the bulk liquid. This suggests that effective intermolecular potentials parametrized for bulk water are inefficient to describe ultraconfined water molecules. Reducing the SPC water dipole moment by 5% (i.e., decreasing water partial charges in magnitude) in GCMC calculations does allow reproducing the experimental water/silicalite isotherm at 300 K.

Mechanochemical characterisation of silica-based coatings on Nitinol substrates

Commercial Nitinol substrates have been coated with mesoporous and microporous silica-based materials. Different surface pre-treatments have been carried out in order to study the influence of the Nitinol external surface on the deposition of the coating materials. Hydrophilic mesoporous amorphous spherical silica microparticles (∼840 nm) and hydrophobic silicalite-1 (an aluminium-free zeolite) crystals (0.5–1.7 μm long) were the materials used to coat the Nitinol substrates. The influence of those coatings on the mechanical performance of the coated Nitinol substrates was analysed by means of flexion studies.

Molecular simulation studies of water physisorption in zeolites

We report a series of Grand Canonical Monte Carlo simulations of water adsorption in NaY and NaX faujasite, as well as in silicalite-1. Computed adsorption isotherms and heats of adsorption were in good agreement with the available experiments. The existence of cyclic water hexamers in NaX located in the 12-ring windows, recently disclosed by neutron diffraction experiments (Hunger et al., J. Phys. Chem. B, 2006, 110, 342-353) was reproduced in our simulations. Interestingly enough, such cyclic hexamer clusters were also observed in the case of NaY, in which no stabilizing cation is present in the 12-ring window. We also report cation redistribution upon water adsorption for sodium faujasite with varying cation contents (Si ratio Al ratio in the range 1.53-3). A simple and transferable forcefield was used, that enabled to reproduce the different aspects of water physisorption in stable zeolites. The high pressure water condensation in hydrophobic silicalite-1 was reproduced without any parameter readjustment. The method and forcefield used here should be useful for engineering oriented applications such as the prediction of multi-component mixture adsorptive separations in various stable zeolites. It allows to address the issue of the effect of the small amounts of water that are almost inevitably present in zeolite-based separation processes.

Water Condensation in Hydrophobic Silicalite-1 Zeolite: A Molecular Simulation Study

We report grand canonical Monte Carlo simulations of the gas and liquid phase adsorption of water in silicalite-1 zeolite. Simple but effective models and simulation methods, found useful for studying gas adsorption in nanoporous materials, have been extended to describe the intrusion/extrusion cycle of water in this hydrophobic solid. The picture of water confined to hydrophobic spaces of nanoscopic dimensions that emerges from this study is one of a strongly depleted and highly inhomogeneous fluid.

Aligned inclusion of hemicyanine dyes into silica zeolite films for second harmonic generation.

Silicalite-1 films (thickness = 400 nm) supported on both sides of glass plates (SL/G) were prepared, and hemicyanine dyes (HC-n) with different alkyl chain lengths (n, n = 3, 6, 9, 12, 15, 18, 22, and 24) were included into the silicalite-1 films by dipping SL/Gs into each methanol solution of HC-n (1 mM) for 1 d. The included numbers of HC-n per channel (N(C)) generally decreased with increasing n; that is, they were 6.4, 23.1, 15.4, 8.2, 5.7, 3.5, 0.9, and 1.2 molecules per channel, respectively. The d(33) value gradually increased with increasing n but decreased when n > 18; that is, they were 1.12, 0.50, 2.25, 3.59, 4.99, 5.30, 1.71, and 2.57 pm V(-1), respectively. However, d(33)/N(C) progressively increased with increasing n. The d(31) values were approximately 100 times smaller than the corresponding d(33) values, and the average d(33)/d(31) ratio was 109, which is higher than those of Langmuir-Blodgett (LB) films and poled polymers of nonlinear optical (NLO) dyes, by approximately 2-5 and approximately 30-50 times, respectively. The estimated average tilted angle of the dyes with respect to the channel direction was 7.7 degrees, and the calculated average order parameter was 0.97, which is approximately 480 times higher than the values observed from poled polymers. The degree of uniform alignment (DUA) generally increased with increasing n. The progressive increase of both DUA and d(33)/N(C) with n is attributed to the increase in the tendency of HC-n to enter hydrophobic silicalite-1 channels with the hydrophobic alkyl chain first. A more than 134-fold increase in DUA was observed upon increasing n from 6 to 24. The DUA of HC-24 in the silicalite-1 film reached close to 1. Although the observed d(33) values were lower than those of the LB films of NLO dyes due to very small dye densities of the silicalite films, this methodology bears a great potential to be developed into the methods for preparing practically viable NLO films.

Pervaporation of Water/THF Mixtures Using Zeolite Membranes

Four types of hydrophilic zeolite membranes (A-type, Al−ZSM-5, mordenite, and Y-type) were used to dehydrate water/THF mixtures by pervaporation. At 303 K, the total fluxes increased with zeolite pore size, and membranes with lower Si/Al ratios had higher water/THF separation selectivities. The Y-type membrane, which was prepared using a template-free seeding technique, had the highest flux and selectivity; at 333 K, the total flux was 2.4 kg m-2 h-1 with a water/THF selectivity of 290. The total flux increased with water feed concentration, but the selectivity decreased. Separation was based on both preferential adsorption of water and differences in diffusion rates. During continuous operation, the water permeate concentrations were higher than 95 wt %. Hydrophobic silicalite-1 and Ge−ZSM-5 membranes were used to remove THF from water. The Ge−ZSM-5 membrane had a total flux of 0.3 kg m-2 h-1 and a THF/water separation selectivity of 890 at 333 K for a 5 wt % THF aqueous solution.

Organophilicity of MCM-41 adsorbents studied by adsorption and temperature-programmed desorption

In this paper, the organophilic property of MCM-41 was studied and compared with hydrophobic silicalite-1 using adsorption and temperature-programmed desorption (TPD) methods. The surface heterogeneity of MCM-41 was evaluated in terms of activation energy for desorption ( E d) and isosteric heat of adsorption ( q st) . Results show that MCM-41 has a higher affinity to polar organic compounds than to non-polar organics while silicalite-1 has a higher affinity to non-polar organic compounds than to polar organics. This organophilic behaviour of MCM-41 is attributed to its surface heterogeneity.