Zeolite Framework Research Articles

Synthesis Route to Single-Walled Zeolite Nanotubes Enabled by Tetrabutylammonium Hydroxide.

Single-walled zeolite nanotubes (ZNT) were recently synthesized in a narrow compositional window. ZNT structural features-thin zeolitic walls and large mesopores-can allow for easy access of small molecules to zeolite micropores, but they also impart processing limitations for these materials, such as challenges with conventional aqueous ion-exchange conditions. Conventional solid- and liquid-phase ion exchange of calcined NaOH-derived ZNT (NaH-ZNT) results in structural degradation to either 2D sheet-like phases, 3D nanocrystals, or amorphous phases, motivating different direct synthesis routes and unconventional ion-exchange procedures of uncalcined ZNT precursors. Here, a modified synthesis route for ZNT synthesis is introduced that facilitates facile ion exchange as well as incorporation of additional non-Al heteroatoms in the zeolite framework. Tetrabutylammonium hydroxide (TBAOH) is used as a hydroxide source and co-OSDA, enabling synthesis of new compositions of ZNT, otherwise unachievable by post-modification of previously reported NaH-ZNT. By varying the gel composition, synthesis temperature, crystallization time, hydroxide source, silicon source, and aluminum source, productive conditions for the new TBAOH synthesis are developed, leading to increased strong acid site density in the ZNT. The collected results demonstrate the sensitivity of the ZNT synthesis to many key parameters and show that the ZNT forms only when Si/(Al + T) ∼ 30 in these synthesis gels and with specific Si and Al sources, and always in the presence of trace Na+. Catalytic testing, via the tandem CO2 hydrogenation to methanol and methanol to aromatics reaction, shows that ZNTs provide adequate catalytic activity (acidity), relative to their conventional 3D counterparts in converting methanol to aromatic compounds.

Molecular interactions of photosystem I and ZIF-8 in bio-nanohybrid materials.

Bio-nanohybrid devices featuring natural photocatalysts bound to a nanostructure hold great promise in the search for sustainable energy conversion. One of the major challenges of integrating biological systems is protecting them against harsh environmental conditions while retaining, or ideally enhancing their photophysical properties. In this mainly computational work we investigate an assembly of cyanobacterial photosystem I (PS I) embedded in a metal-organic framework (MOF), namely the zeolitic imidazolate framework ZIF-8. This complex has been reported experimentally [Bennett et al., Nanoscale Adv., 2019, 1, 94] but so far the molecular interactions between PS I and the MOF remained elusive. We show via absorption spectroscopy that PS I remains intact throughout the encapsulation-release cycle. Molecular dynamics (MD) simulations further confirm that the encapsulation has no noticeable structural impact on the photosystem. However, the MOF building blocks frequently coordinate to the Mg2+ ions of chlorophylls in the periphery of the antenna complex. High-level quantum mechanical calculations reveal charge-transfer interactions, which affect the excitonic network and thereby may reversibly change the fluorescence properties of PS I. Nevertheless, our results highlight the stability of PS I in the MOF, as the reaction center remains unimpeded by the heterogeneous environment, paving the way for applications in the foreseeable future.

Synergy of pore size and silanols in an –SVR-type zeolite for efficient dynamic benzene/cyclohexane separation

The efficient purification of cyclohexane is critical, serving as an essential feedstock to produce resins, nylon fibers and pharmaceutical intermediates. However, efficient purification remains a challenging task due to the similarity of cyclohexane and benzene molecules in terms of size and boiling point. In this work, we reported on the synergy of pore size and silanols inside an -SVR-type zeolite for the efficient production of ultrapure cyclohexane (benzene <1 ppm) from benzene/cyclohexane mixture. Under ambient conditions, the SSZ-74 zeolite demonstrated the highest mass-based productivity of 14.5 L/kg for ultrapure cyclohexane among several common zeolites with a considerable dynamic selectivity of ~9.5. The separation ability was evaluated through density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations. The unique ordered silanols inside the zeolite frameworks demonstrated strong but reversible interactions with benzene through SiOH…π interactions, as revealed by in situ Fourier Transform infrared (FTIR) spectra.

Enhanced adsorption of radioactive cesium from nuclear wastewater using ZIF-67 laminated 2D MXene Ti3C2

Development of nuclear industry has caused severe water pollution. Adsorptive removal of radionuclides from wastewater has been regarded as effective solution for environment. However, developing adsorbents with high adsorption capacity and selectivity for removal of radionuclides (such as 137Cs) is still a challenge. Herein, we adopted an in situ assemble strategy to construct a novel composite, in which zeolitic imidazolate framework (ZIF-67) was grafted into two-dimension (2D) layers of transition metal carbides/nitrides (MXenes) Ti3C2, and used it in adsorptive removal of Cs+ from wastewater. Laminated and pillaring effect of ZIF-67 increased interlayer spacing and specific surface area of Ti3C2, significantly enhancing Cs+ adsorption. MXenes matrix provided the main adsorptive sites and interaction to stabilize Cs+, while the hybrid ZIF-67 assisted adsorption. The adsorbent achieved 96.2 % removal for 5 mg·L-1 of Cs+ within 6 h, and 50.0 mg·g−1 of maximum adsorption capacity, with good recyclability for 4 times. Ion competition, kinetics and thermodynamics were studied in detail to obtain the behavior of Cs+ adsorption. Finally, adsorption mechanism was proposed that [Ti − O] − H+ and [Ti − O] groups of 2D Ti3C2 were main adsorptive sites to participate in ion exchange and complexation with Cs+, respectively, while 2-methylimidazole (2-MI) ligands in ZIF-67 were synergetic adsorption sites.

8-Hydroxyquinoline incorporated ZIF-8 nanocomposites for efficient decomposition and detection of manganese ions in aquatic environments

The presence of potassium permanganate in aquatic environment poses a significant issue that requires resolution. In response, zeolitic imidazolate framework nanoparticles with large pore sizes, extensive surface areas, and high chemical stability in water were synthesized. Subsequently, 8-hydroxyquinoline was incorporated into ZIF-8 (named 8-HQ@ZIF-8) to enhance its capability to decompose potassium permanganate in aquatic environment. The synthesized material underwent thorough characterization using powder X-ray diffraction, Fourier-transform infrared spectroscopy, nitrogen isothermal adsorption-desorption at 77 K, thermogravimetric analysis, and scanning electron microscopy. Electrical conductivity tests revealed that the 8-HQ@ZIF-8 material can decompose potassium permanganate within 5 min and be recycled over five runs. Furthermore, the nanocomposite of 8-HQ and ZIF-8 exhibited greater stability than the original ZIF-8 under strong oxidizing conditions. This suggests that functionalizing with organic ligands can enhance the durability and performance of the material. In addition to its degradability, the 8-HQ@ZIF-8 material, which carries manganese oxide, also displays variable fluorescence properties, making it a potential sensor for detecting residual potassium permanganate in drinking water treatment systems. Therefore, the 8-HQ@ZIF-8 material shows considerable promise for both the treatment and detection of pollutants in aquatic environments.

Quantitative localisation of titanium in the framework of titanium silicalite-1 using anomalous X-ray powder diffraction

One of the biggest obstacles to developing better zeolite-based catalysts is the lack of methods for quantitatively locating light heteroatoms on the T-sites in zeolites. Titanium silicalite-1 (TS-1) is a Ti-bearing zeolite-type catalyst commonly used in partial oxidation reactions with H2O2, such as aromatic hydroxylation and olefin epoxidation. The reaction mechanism is controlled by the configuration of titanium sites replacing silicon in the zeolite framework, but these sites remain unknown, hindering a fundamental understanding of the reaction. This study quantitatively determines heteroatoms within the zeolite-type framework using anomalous X-ray powder diffraction (AXRD) and the changes in the titanium X-ray scattering factor near the Ti K-edge (4.96 keV). Two TS-1 samples, each with approximately 2 Ti atoms per unit cell, were examined. Half of the titanium atoms are primarily split between sites T3 and T9, with the remainder dispersed among various T-sites within both MFI-type frameworks. One structure showed significant non-framework titanium in the micropores of a more distorted lattice. In both samples, isolated titanium atoms were more prevalent than dinuclear species, which could only potentially arise at site T9, but with a significant energy penalty and were not detected.

Long cycle life aqueous zinc-ion battery enabled by a ZIF-N protective layer with electron-withdrawing group and zincophilicity on the Zn anode

Aqueous zinc-ion batteries (AZIBs) have garnered attention from researchers for their high theoretical capacity, safety, and low cost. However, the uncontrolled growth of zinc (Zn) dendrites and spontaneous corrosion reactions on the Zn anode significantly compromise the cycle life of AZIBs. This paper proposes the utilization of a novel zeolitic imidazole framework (ZIF-N) material with zincophilicity and hydrophilicity for modifying the Zn anode of AZIBs. ZIF-N incorporates numerous electron-withdrawing nitro groups at the Zn/ZIF-N interface to regulate the uneven electron distribution on the Zn anode. The modified Zn anode (Zn@ZIF-N) exhibits a lower polarization ratio (32.18 mV at 4 mA cm−2) and an extended cycle life (over 700 h at 4 mA cm−2). At a current density of 1 mA cm−2, the battery composed of a Zn@ZIF-N anode and NVO (NaV3O8) achieves a cycle life of 1600 cycles. This work provides a straightforward and cost-effective strategy for modifying the Zn anode to prolong the cycle life of AZIBs.

Sn-MFI zeolite nanosponge having high content of Lewis acid sites on external surfaces, exhibiting high activity in Baeyer-Villiger oxidation of bulky ketone

We developed a three-step synthesis strategy to obtain Sn-incorporated MFI-type zeolite nanosponge (Sn-MFI-ns) assembled by ultrathin (∼2.5 nm) zeolite frameworks possessing uniform-sized (∼4 nm) mesopores: 1) synthesis of MFI-type borosilicate nanosponge using a zeolite structure-directing-surfactant, 2) deboronation of the borosilicate using HNO3, and 3) gas-phase incorporation of Sn into the boron-vacant sites via silanol groups using (CH3)2SnCl2 as a precursor. The Sn-MFI-ns shows high crystallinity, consequently high thermal stability, and highly porous structure. The Sn content can be systematically controlled by the amount of the precursor, with Si/Sn ratios ranging from 30 to 200. The Sn species is highly dispersed over entire range of the zeolite surfaces, acting as Lewis acid sites. Due to the highly mesoporous structure, the Sn-MFI-ns has a significant number of Lewis acid sites on the external surfaces and mesopore walls, which are easily accessible to bulky molecules, compared to solely microporous zeolite (Sn-bulk-MFI). Consequently, the Sn-MFI-ns exhibits much higher catalytic activity than the Sn-bulk-MFI with high product selectivity in Baeyer-Villiger oxidation of 2-adamantanone, a molecule larger than the micropore apertures of MFI-type zeolite. The activity of Sn-MFI-ns is comparable to Sn-MCM-41 exposing almost all Sn to mesopore walls, advantageous to the bulky molecules’ reaction.

General In Situ Engineering of Carbon-Based Materials on Carbon Fiber for In Vivo Neurochemical Sensing.

Developing real-time, dynamic, and in situ analytical methods with high spatial and temporal resolutions is crucial for exploring biochemical processes in the brain. Although in vivo electrochemical methods based on carbon fiber (CF) microelectrodes are effective in monitoring neurochemical dynamics during physiological and pathological processes, complex post modification hinders large-scale productions and widespread neuroscience applications. Herein, we develop a general strategy for the in situ engineering of carbon-based materials to mass-produce functional CFs by introducing polydopamine to anchor zeolitic imidazolate frameworks as precursors, followed by one-step pyrolysis. This strategy demonstrates exceptional universality and design flexibility, overcoming complex post-modification procedures and avoiding the delamination of the modification layer. This simplifies the fabrication and integration of functional CF-based microelectrodes. Moreover, we design highly stable and selective H+, O2, and ascorbate microsensors and monitor the influence of CO2 exposure on the O2 content of the cerebral tissue during physiological and ischemia-reperfusion pathological processes.

Binary-Cooperative Ultrathin Porous Membrane for Gas Separation.

The construction of ultrathin porous membranes with stable structures is critical for achieving efficient gas separation. Inspired by the binary-cooperative structural features of bones and teeth-composed of rigid hydroxyapatite and flexible collagen, which confer excellent mechanical strength-a binary-cooperative porous membrane constructed with gel-state zeolitic imidazolate frameworks (g-ZIFs), synthesized using a metal-gel-induced strategy, is proposed. The enlarged cavity size and flexible frameworks of the g-ZIF nanoparticles significantly improve gas adsorption and diffusion, respectively. After thermal treatment, the coordination structures forming rigid segments in the g-ZIF membranes appear at the stacked g-ZIF boundaries, exhibiting a higher Young's modulus than the g-ZIF nanoparticles, denoted as the flexible segments. The g-ZIF membranes demonstrate excellent tensile and compression resistances, attributed to the effective translation of binary-cooperative effects of rigidity and flexibility into the membranes. The resulting dual-aperture structure, composed of g-ZIF nanoparticles surrounded by nanoscale apertures at the boundaries, yields a membrane with a stable CO2 permeance of 4834 GPU and CO2/CH4 selectivity of 90 within 3.0MPa.

Laser‐Induced Transformation of ZIF‐8 into Highly Luminescent N‐Doped Nanocarbons for Flexible Sensors

AbstractMetal–organic frameworks (MOFs) like the zeolitic imidazolate framework (ZIF‐8) have a high surface area, tunable porosity, and robust thermal and chemical stability, making them attractive candidates for various applications. Here, a strategy is shown that spans that functionality and provides strong photoluminescence (PL) emission, unlocking ZIF‐8‐based materials for chemical and temperature sensors based on PL. The approach is based on laser processing that dramatically boosts the PL response of laser‐irradiated ZIF‐8 (LI ZIF‐8), achieving a 70‐fold increase in intensity relative to the pristine material. The PL characteristics of the irradiated material can be easily tuned by varying the laser power and irradiation time with in situ and real‐time spectroscopic analysis providing insights into the process dynamics. It is found that the observed PL enhancement is primarily due to the laser‐induced transformation of ZIF‐8 into nitrogen‐doped nanocarbons and ZnO nanostructures. The versatility of this laser processing approach is leveraged to create flexible electronics by integrating the LI ZIF‐8/nanocarbon architectures into thermoplastic polyurethane (TPU). The multifunctional composite material shows excellent performance as flexible electrodes for human‐body monitoring applications, as well as both temperature and flexure sensors with remarkable mechanical resilience.

Investigating the Structure of Defects in Heterometallic Zeolitic Imidazolate Frameworks ZIF-8(Zn/Cd) and Its Interaction with CO2 Using First-Principle Calculations

Inducing defect in metal-organic frameworks (MOFs) is one of the strategies to modify the structure and properties of this functional material. Defect may occur in a pristine MOF due to missing organic linkers, metal centres and/or other structural behaviours. In this study, the structure of defects in multicomponent MOFs especially heterometallic MOFs of zeolitic imidazolate framework (ZIF-8(Zn/Cd)) was examined to unveil the possible preference defect formation due to missing 2-methylimidazolate (MeIm) and metal centres of Cd2+ and Zn2+. Assuming defect formation due to the reaction between ZIF-8(Zn/Cd) and water, MeIm linker removal is energetically lower than removing metal centres of either Cd2+ or Zn2+. But, the MeIm linker is easier to be removed when it is connected to Cd2+ (Cd-MeIm-Cd) than when it is connected to Zn2+ (Zn-MeIm-Zn). Defect in ZIF-8(Zn/Cd) affects the band gap energy to give slightly lower value than it in pristine ZIF-8(Zn/Cd). Non-covalent interaction (NCI) and interaction region indicator (IRI) analyses were also performed to indicate possible intermolecular forces such as van der Waals and attractive forces present in non-defective and defective ZIF-8(Zn/Cd). The presence of defects in mixed-metal ZIF-8(Zn/Cd) was also tested for its potential use on CO2 adsorption. The interaction energy of CO2 inside defective ZIF-8(Zn/Cd) indicates an exothermic behaviour where CO2 molecule has a preference to be adsorbed inside the framework. This is especially when the capping agents at the defective ZIF-8(Zn/Cd) sites are removed to give open metal sites. This study provides insight how defects in multicomponent MOFs might presence affecting the structural and properties changes. Copyright © 2024 by Authors, Published by BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Novel [plant essential oils@γ-CD MOF]/ZIF-8 strategy to remove bacteria and dye from bacterial staining wastewater

A novel MOF-on-MOF ([plant essential oils@γ-CD MOF]/ZIF-8) strategy was established in this work, in which a cyclodextrin metal–organic framework (γ-CD MOF) loaded with plant essential oils (cinnamon and oregano oils, COEO) was combined with zeolitic imidazolate framework (ZIF-8) to produce ([COEO@γ-CD MOF]/ZIF-8) for the removal of bacteria and dyes from bacterial staining wastewater. Adsorption isotherm and kinetic studies showed that [COEO@γ-CD MOF]/ZIF-8 could adsorb methylene blue (MB) by monolayer chemisorption with a Qmax of 111.6 mg/g. No bacterial colonies grew on plates treated with [COEO@γ-CD MOF]/ZIF-8, and scanning electron microscope (SEM) images showed a disruption of E. coli and S. aureus structures. This work offers a simple and green method for treating bacterial staining wastewater in microbiology labs.

Shaping Phenolic Resin-Coated ZIF-67 to Millimeter-Scale Co/N Carbon Beads for Efficient Peroxymonosulfate Activation.

Catalytic performance decline is a general issue when shaping fine powder into macroscale catalysts (e.g., beads, fiber, pellets). To address this challenge, a phenolic resin-assisted strategy was proposed to prepare porous Co/N carbon beads (ZACBs) at millimeter scale via the phase inversion method followed by confined pyrolysis. Specially, p-aminophenol-formaldehyde (AF) resin-coated zeolitic imidazolate framework (ZIF-67) nanoparticles were introduced to polyacrylonitrile (PAN) solution before pyrolysis. The thermosetting of the coated AF improved the interface compatibility between the ZIF-67 and PAN matrix, inhibiting the shrinkage of ZIF-67 particles, thus significantly improving the void structure of ZIF-67 and the dispersion of active species. The obtained ZACBs exhibited a 99.9% removal rate of tetracycline (TC) within 120 min, with a rate constant of 0.069 min-1 (2.3 times of ZIF-67/PAN carbon beads). The quenching experiments and electron paramagnetic resonance (EPR) tests showed that radicals dominated the reaction. This work provides new insight into the fabrication of high-performance MOF catalysts with outstanding recycling properties, which may promote the use of MOF powder in more practical applications.

ZIF-67@polyvinylidene fluoride mixed matrix membranes towards improved hydrogen separation performance.

This work is primarily focused on overcoming the limitations of polymeric membranes in achieving the balance between permeability and selectivity of the separation performance. The filler, Zeolitic imidazole framework -67 (ZIF-67) nanoparticles were synthesised in cubical morphology using hexadecyltrimethylammonium bromide (CTAB) as a surfactant via the wet-chemical method. The uniform particles with particle sizes ranging between 120-180nm were incorporated into the polyvinylidene fluoride (PVDF) matrix to fabricate mixed matrix membranes via the phase inversion method. These mixed matrix membranes were systematically characterised to confirm the chemical, structural and morphological properties of the materials and membranes. Furthermore, the membranes showed a 56.5% improvement in their mechanical properties. The results confirm that 5 wt.% ZIF-67/PVDF membrane showed the best separation results compared to its pure counterpart. The permeability of H₂ gas was reported to be 1,094,511 Barrer, with selectivities of 3.03 for H₂/CO₂ and 3.06 for H₂/N₂. This represents a 210.6% increase in the permeability of H₂ gas. These results demonstrate the influence of ZIF-67 loading in the PVDF polymer matrix along with the potential of ZIF-67/PVDF mixed matrix membranes in the field of hydrogen separation and purification.

Direct propylene epoxidation with molecular oxygen over titanosilicate zeolites.

The direct epoxidation of propylene with molecular oxygen represents a desired route for propylene oxide (PO) production with 100% theoretical atomic economy. However, this aerobic epoxidation reaction suffers from the apparent trade-off between propylene conversion and PO selectivity, and remains a key challenge in catalysis. We report that Ti-Beta zeolites containing isolated framework Ti species can efficiently catalyze the aerobic epoxidation of propylene. Stable propylene conversion of 25% and PO selectivity of up to 90% are achieved at the same time, matching the levels of industrial ethylene aerobic epoxidation processes. H-terminated pentacoordinated Ti species in Beta zeolite frameworks are identified as the preferred active sites for propylene aerobic epoxidation and the reaction is initiated by the participation of lattice oxygen in Ti-OH. These results are expected to spark new technology for the industrial production of PO toward more sustainable chemistry and chemical engineering.

Crosslinked polyethyleneimine‐based structures in different morphologies as promising CO2 adsorption systems: A comprehensive study

AbstractAlthough there are many studies on CO2 adsorption via PEI‐modified carbon particles, metal–organic frameworks, zeolitic imidazolate frameworks, and silica‐based porous structures, only a limited number of studies on solely cross‐linked PEI‐based structures. Here, the CO2 adsorption capacities of PEI‐based microgels and cryogels were investigated. The effects of various parameters influencing the CO2 adsorption capacity of PEI‐based structures, for example, crosslinker types, PEI types (branched [bPEI] or linear [lPEI]), adsorbent types (microgel or cryogel), chemical‐modification including their complexes were examined. NaOH‐treated glycerol diglycidyl ether (GDE) crosslinked lPEI microgels exhibited higher CO2 adsorption capacity among other microgels with 0.094 ± 0.006 mmol CO2/g at 900 mm Hg, 25°C with 2‐ and 7.5‐fold increase upon pentaethylenehexamine (PEHA) modification and Ba(II) metal ion complexing, respectively. The CO2 adsorption capacity of bPEI and lPEI‐based cryogels were compared and found that lPEI‐GDE cryogels had higher adsorption capacity than bPEI‐GDE cryogels with 0.188 ± 0.01 mmol CO2/g at 900 mm Hg and 25°C. The reuse studies revealed that NaOH‐treated GDE crosslinked bPEI and lPEI microgels and cryogels showed promising potential, for example, after 10‐times repeated use &gt;50% CO2 adsorption capacity was retained. The results affirmed that PEI‐based microgels and cryogels are encouraging materials for CO2 capture and reuse applications.

High speed enrichment of benzoylurea insecticides by hierarchical pore nitrogen doped carbon materials induced with hydrogen-bonded organic frameworks

The high speed enrichment of benzoylurea insecticides (BUs) in complex matrices is an essential and challenging step. The present study focuses on the synthesis of a hierarchical pore nitrogen-doped carbon material for magnetic solid phase extraction (MSPE) of BUs. This material was prepared through the carbonization of a composite material ZIF-67@MCA which assembly with hydrogen-bonded organic frameworks (melamine-cyanurate, MCA) and zeolitic imidazolate framework (ZIF-67) at room temperature. The optimal adsorption effect is achieved when the mass ratio of ZIF-67 to MCA is 1/3, and the carbonization was performed at 600 °C, the such obtained carbon material was denoted as 1/3ZIF-67@MCA-DCs-600. The material was characterized with various physical methods including X-ray diffractometry (XRD), Fourier transform infrared spectrometry (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), Brunauer–Emmett–Teller (BET), vibrating sample magnetometer (VSM), water contact angle measurement, Raman spectrometry. 1/3ZIF-67@MCA-DCs-600 exhibits a macro-mesoporous 3D structure with a high degree of nitrogen doping and relatively large specific surface area, making it suitable for magnetic solid phase extraction (MSPE). The adsorption of BUs with concentration of 100 ng mL-1 can reach equilibrium within 5 s. The interaction between BUs and the adsorbent, facilitated by π-π stacking, hydrophobic interactions, hydrogen bonding forces, as well as the material's porosity, enables efficient extraction recoveries ranging from 45 % to 92 %. The enrichment of BUs was achieved through the establishment of an MSPE method under optimized conditions, which was further coupled with high performance liquid chromatography (HPLC) for the determination of the four BUs. The linear range spans from 5 ng ml-1 to 1000 ng ml-1 with the correlation coefficient (R2) of ≥ 0.99, Meanwhile, the detection limit for these four BUs falls within the range of 0.01 to 0.10 ng ml-1. The material exhibits good reusability and can be reused for at least 5 cycles. Inter day and intra-day precision ranges from 2.1-7.9 % and 1.0-5.4 %, respectively. The method demonstrates a high level of reliability in practical applications for the determination of BUs.

Constructing Hierarchical Zeolites with Highly Complete Framework via Controlled Desilication.

Desilication in alkaline medium has been widely used in construction of hierarchical zeolites for industrially relevant catalytic processes. The built of hierarchy in zeolites, especially with low aluminum stability or high Si/Al ratio, often suffers from uncontrolled destruction of zeolitic framework, accompanied by a significant loss of microporous domains and intrinsic acidity after desilication. Here, we report a novel and simple methodology for preparation of hierarchical zeolites with highly complete framework and minimum sacrifice of microporosity and acidity. The pre-impregnated amines in zeolite micropores act as inner pore-directing agents (iPDAs), largely protecting the zeolitic framework and moderating the silicon extraction during the alkaline treatment. The resulting hierarchical zeolites exhibit high crystallinity, tunable hierarchy, stable framework, and well-preserved acidity, endowing them with significantly improved mass transport properties and enhanced activities in catalytic conversion of methanol or furfural.

Adsorption of difluoromethane (HFC-32) and pentafluoroethane (HFC-125) and their mixtures in silicalite-1: An experimental and Monte Carlo simulation study.

Hydrofluorocarbons are a class of fluorinated molecules used extensively in residential and industrial refrigeration systems. This study examines the potential of using adsorption processes with the silicalite-1 zeolite to separate a mixture of difluoromethane (CH2F2, HFC-32) and pentafluoroethane (CF3CF2H, HFC-125) at various concentrations. Pure adsorption data were measured using a XEMIS gravimetric microbalance, whereas binary data were determined using the Integral Mass Balance method. Grand canonical Monte Carlo molecular simulations were performed with the Cassandra package. We found that the results from molecular simulations are in satisfactory agreement with experimental loading measurements. Moreover, we show that ideal adsorbed solution theory could not quantitatively match the experimental or computational measurements of binary adsorption or selectivity. Molecular simulations show that refrigerant molecules do not have a uniform distribution in the zeolite framework.