Construction of diverse hollow MFI zeolites through regulating the micropore filling agents.

Constructing hollow structure into microporous zeolites can improve the accessibility of acid sites located at the inner part and the diffusion property. Hence, the development of an efficient synthesis strategy to acquire zeolites with tunable hollow structures and acidity has attracted much attention. In this work, an innovative tandem synthesis route was proposed to prepare MFI zeolites with diverse hollow structure while maintaining solid yields exceeding 90 %. The substitution of ethanol molecules, which previously occupied the micropores, with tetrapropylammonium cations was proved to be the key factor to construct hollow structure. And a crystallization-driven particle dissolution mechanism was proposed. The dimension of the hollow cavity, particle size, and Si/Al ratio can be flexibly regulated. Interestingly, hollow MFI samples featuring the common cavity structure, "eye-like" cavity structure, or double-cavity structure can be directly synthesized by controlling the dissolution of core parts. In the 1-butene catalytic cracking reactions, a much higher conversion of 67.2 % was acquired over hollow ZSM-5 compared with that over conventional ZSM-5 (35.8 %) after 64 h of reaction. This improvement can be attributed to the eightfold increase of diffusivity in hollow ZSM-5. This facile and efficient synthesis method endows accurate regulation of the hollow structure, which is meaningful for both fundamental research and industrial applications of hollow zeolites.

A facile top-down protocol for postsynthesis modification of hierarchical aluminum-rich MFI zeolites.

High aluminum content constitutes a major hurdle for the postsynthesis modification of hierarchical zeolites. A facile protocol comprising fluorination and sequential alkaline treatment is presented for the postsynthesis modification of hierarchical Al-rich MFI zeolites. By virtue of this protocol, uniform intracrystalline mesoporosity is introduced in an Al-rich MFI zeolite (Si/Al = 14.3). The obtained hierarchical zeolites exhibit a significant mesopore size distribution, centered around 6 nm, and show improved conversions in catalytic cracking of bulky aromatic molecules. The fundamental implications of the fluorination-alkaline treatment protocol are related to the formation of F-bearing tetrahedral aluminum species in the antecedent fluorination step, which alleviates the resistance of Al sites to the alkaline medium and causes Al-F complexation for regulated hydrolysis of the Al species during the alkaline treatment process. This top-down protocol and the derived mechanistic understandings are expected to be applied in the synthesis of hierarchical Al-rich zeolites with other framework topologies.

[Study on treatment of irritable bowel syndrome: based on relationship between heart and intestines].

The article puts forward the treatment of irritable bowel syndrome through regulating heart vitality since it is held that the pathological factors of the disease lay in dysfunction of heart and intestines as well as disorder of qi circulation. At the same time, the internal-external relationship between the heart the small intestine is discussed from the theory of Brain-gut Axis in modern medicine, which provides theoretical base of modern medicine for the treatment of irritable bowel syndrome through regulation of the heart functions.

Phase selection controlled by sodium ions in the synthesis of FAU/LTA composite zeolite.

Zeolite faujasite (FAU), Linde type A (LTA) and FAU/LTA composite have been synthesized using tetramethylammonium cation (TMA+) as template, by adjusting only the concentration of Na+ ions in the initial solution (1.00 Al2O3 4.36 SiO2 : 2.39 (TMA)2 O : ß Na2 O : 249.00H2 O). Na+ ions alter the phase composition of the product more than TMA+ or OH- ions. When Na2 O concentration [Na2 O] increases from 0.024 to 0.168, the product gradually changes from pure FAU to pure LTA via the formation of FAU/LTA composite with increasing LTA fraction. Interestingly, the induction periods of FAU and LTA in the FAU/LTA composite zeolite ([Na2 O] is 0.072) are both 13 h, quite different from the induction periods of their individual pure phases-45 h for FAU and 4 h for LTA. During the crystallization, the LTA/(FAU + LTA) fraction in the composite zeolite decreases in a nearly linear fashion. Scanning electron microscopy, thermogravimetry and differential thermal analysis indicate some difference between the properties of the FAU/LTA composite zeolite and of the mechanical mixture.

Probing the porosity of cocrystallized MCM-49/ZSM-35 zeolites by hyperpolarized 129Xe NMR.

One- and two-dimensional 129Xe NMR spectroscopy has been employed to study the porosity of cocrystallized MCM-49/ZSM-35 zeolites under the continuous flow of hyperpolarized xenon gas. It is found by variable-temperature experiments that Xe atoms can be adsorbed in different domains of MCM-49/ZSM-35 cocrystallized zeolites and the mechanically mixed counterparts. The exchange of Xe atoms in different types of pores is very fast at ambient temperatures. Even at very low temperature two-dimensional exchange spectra (EXSY) show that Xe atoms still undergo much faster exchange between MCM-49 and ZSM-35 analogues in the cocrystallized zeolites than in the mechanical mixture. This demonstrates that the MCM-49 and ZSM-35 analogues in cocrystallized zeolites may be stacked much closer than in the physical mixture, and some parts of intergrowth may be formed due to the partially similar basic structure of MCM-49 and ZSM-35.

Physical and chemical regeneration of zeolitic adsorbents for dye removal in wastewater treatment.

Natural zeolite and synthetic zeolite, MCM-22, were employed as effective adsorbents for a basic dye, methylene blue, removal from wastewater. Two methods, Fenton oxidation and high temperature combustion, have been used for regeneration of used materials. It is found that MCM-22 exhibits equilibrium adsorption at 1.7 x 10(-4) mol g(-1), much higher than the adsorption of natural zeolite (5 x 10(-5) mol g(-1)) at initial dye concentration of 2.7 x 10(-5)M and 30 degrees C. Solution pH will affect the adsorption behaviour of MCM-22. Higher solution pH results in higher adsorption capacity. The regenerated adsorbents show different capacity depending on regeneration technique. Physical regeneration by high temperature combustion will be better than chemical regeneration using Fenton oxidation in producing effective adsorbents. Regeneration of MCM-22 by high temperature treatment can make the adsorbent exhibit comparable or superior adsorption capacity as compared to the fresh sample depending on the temperature and time. The optimal temperature and time will be 540 degrees C and 1h. The Fenton oxidation will recover 60% adsorption capacity. For natural zeolite, regeneration can not fully recover the adsorption capacity with the two techniques and the regenerated natural zeolites by the two techniques are similar, showing 60% adsorption capacity of fresh sample. Kinetic studies indicate that the adsorption follows pseudo-second-order kinetics.

An investigation of the roles of surface aluminum and acid sites in the zeolite MCM-22.

Ammonia adsorption studies reveal that the observed Lewis acidity in the zeolite MCM-22 is derived from at least two types of framework aluminum sites (AlF), that is, octahedral AlF and three-coordinate AlF. Comparative ammonia or trimethylphosphine (TMP) adsorption experiments with MCM-22 confirm that octahedral Al species gives rise to the signal at delta(iso) approximately 0 in the 27Al NMR spectrum; this is a superposition of two NMR signals from the different Al species on the water-reconstructed zeolite surface. A sharp resonance assigned to framework Al reversibly transforms on ammonia adsorption to delta(iso)27Al approximately 55 from tetrahedral AlF, while the broad peak is assigned to nonframework aluminum which results from hydrothermal treatment. This study also demonstrates the effectiveness of 27Al magic angle spinning (MAS) and multiple quantum (MQ) MAS NMR spectroscopy as a technique for the study of zeolite reactions.