Unlocking Enhanced Butadiene Selectivity: The Crucial Role of Zeolite Channel Confinement in the Selective Decarbonylation of γ-Valerolactone.

Herein, we report a highly selective production route for butadiene from γ-valerolactone over zeolite catalysts. The catalytic performance of eight zeolites with different framework topologies were compared, revealing that zeolites with narrower 10-membered ring channels exhibit enhanced selectivity of butadiene. Specifically, ZSM-35 and ZSM-22, featuring the narrowest 10-membered ring channels, demonstrate the highest butadiene selectivity to 61 % and 59 %, respectively. Notably, surface passivation of ZSM-35 leads to a remarkable increase in butadiene selectivity to 82 %, maintaining a 99 % conversion. Additionally, we propose a reaction network and identify cyclopentenone as a key intermediate in the transformation of γ-valerolactone to butadiene. Both experimental and theoretical results conclude that confinement effect of 10-membered ring channels improves the selectivity of butadiene.

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.

Construction of a One-Dimensional Al-Rich ZSM-48 Zeolite with a Hollow Structure.

Diffusion limitation and acid deficiency are two main challenges that the ZSM-48 zeolite faces in practical application. To date, there have been few effective strategies to solve both problems, simultaneously. Also, it is also a challenge to construct a hollow structure in a one-dimensional (1D) zeolite. Herein, an Al-rich ZSM-48 zeolite with a hollow structure is constructed through an alumination-recrystallization strategy, thereby solving the problems related to diffusion and acidity simultaneously. The hollowness and enrichment of aluminum can be controlled by judiciously matching the desilication and recrystallization. The silica to alumina ratio (SAR) of the ZSM-48 zeolite can be tuned from 130 to 45, which breaks the SAR limitation of conventional synthesis. On the basis of the different characterization results, the whole crystallization can be divided into two stages: rapid desilication-alumination and time-consuming recrystallization. In the selective desilication-recrystallization process, the preferential special distribution of the organic template leads to the formation of a hollow structure and the healing of mesopores at the outer shell, as evidenced by structured illumination microscopy images. Due to the enhancement in diffusion ability and acid density, the obtained hollow Al-rich ZSM-48 zeolite exhibits excellent catalytic stability and high p-xylene yield (∼26%) in the m-xylene isomerization reaction (WHSV = 18 h-1), indicating its strong industrial application potential.

Direct Preparation of *MRE Zeolites with Ultralarge Mesoporosity: Strategy and Working Mechanism.

Introduction of mesopore is critical for applications where mass-transport limitations within microporous networks, especially for zeolite with one-dimensional microporous network, hinder their performance. Generally, the creation of mesopore in zeolite through a direct synthesis route is strongly dependent on complex and expensive organic molecules, which limits their commercial application. Here, we successfully developed a facile synthesis route for preparing ZSM-48 zeolite (*MRE topology) with ultralarge mesoporosity in which typical 1,6-hexylenediamine worked as an organic structure-directing agent, innovatively assisted by a simple crystal growth modifier (tetraethylammonium bromide, TEABr). The working mechanism of TEABr during crystallization was revealed and proposed on the basis of TEM, thermal gravimetric mass spectrum, and 13C cross-polarization magic angle spinning NMR characterization results. In the process, TEA+ ions preferentially interacted with the solid during the induction period, which effectively suppressed the aggregation of ZSM-48 primary nanorods. As a result, ultralarge mesoporosity of 0.97 cm3·g-1 was constructed through the stacking of the nanorods. Interestingly, TEA+ ions only took part in the crystallization process and did not occlude in the pores of the final zeolites indicating its potential in recyclability. Moreover, similar synthesis strategy could be applied for the preparation of hierarchical ferrierite zeolites, implying the universality of this strategy. Compared with a conventional sample, ZSM-48 zeolite with ultralarge mesoporosity showed superior catalytic stability in the m-xylene isomerization reaction due to its significantly enhanced diffusion and mass transfer capability, which will greatly promote the practical application of ZSM-48 zeolite.

A Highly Ion-Selective Zeolite Flake Layer on Porous Membranes for Flow Battery Applications.

Zeolites are crystalline microporous aluminosilicates with periodic arrangements of cages and well-defined channels, which make them very suitable for separating ions of different sizes, and thus also for use in battery applications. Herein, an ultra-thin ZSM-35 zeolite flake was introduced onto a poly(ether sulfone) based porous membrane. The pore size of the zeolite (ca. 0.5 nm) is intermediary between that of hydrated vanadium ions (>0.6 nm) and protons (<0.24 nm). The resultant membrane can thus be used to perfectly separate vanadium ions and protons, making this technology useful in vanadium flow batteries (VFB). A VFB with a zeolite-coated membrane exhibits a columbic efficiency of >99 % and an energy efficiency of >81 % at 200 mA cm(-2), which is by far the highest value ever reported. These convincing results indicate that zeolite-coated membranes are promising in battery applications.

Metathesis of 1-Butene to Propene over Mo/Al2O3@SBA-15: Influence of Alumina Introduction Methods on Catalytic Performance.

A series of Mo-based catalysts for 1-butene metathesis to propene were prepared by supporting Mo species on SBA-15 premodified with alumina. The effects of the method of introduction of the alumina guest to the host SBA-15 on the location of the Mo species and the corresponding metathesis activity were studied. As revealed by N2 adsorption isotherms and TEM results, well-dispersed alumina was formed on the pore walls of SBA-15 if the ammonia/water vapor induced hydrolysis (NIH) method was employed. The Mo species preferentially interacted with alumina instead of SBA-15, as evidenced by X-ray photoelectron spectroscopy, time-of-flight secondary-ion mass spectrometry, and IR spectroscopy of adsorbed pyridine. Furthermore, new Brønsted acid sites favorable for the dispersion of the Mo species and low-temperature metathesis activity were generated as a result of the effective synergy between the alumina and SBA-15. The Mo/Al2O3@SBA-15 catalyst prepared by the NIH method showed higher metathesis activity and stability under the conditions of 120 °C, 0.1 MPa, and 1.5 h(-1) than catalysts prepared by other methods.