Search

The synthesis of hierarchical meso-/microporous zeolite materials with spatially controlled morphology, meso-/microporosity, and acidity is an expanding area of research interest for a wide range of applications. Here, we report a one-step dual template synthesis method for integration of 3-dimensional (3D) BEA nanosponge and ultra-thin 2D lamellar MFI into a new type of hierarchical meso-/microporous zeolite composite structures. Specifically, the 2D layered MFI nanosheets were laid over the surface of or interdigitated into the 3D BEA particles in the bulk BEA nanosponge-lamellar MFI (BBLM) zeolite structure, which generated a unique morphology of interconnected micropores and mesopores underneath the ‘skinning’ shell (∼3–10 nm) of MFI nanosheets. The BBLM zeolites have higher mesoporosity than either bare BEA or lamellar MFI zeolites. The micropore size decreases with increasing lamellar MFI component in the composite. The fraction of external acid sites of BBLM zeolite composite, represented by the percentage of active sites accessible to bulky organic base molecules, decreases with increasing MFI component. Additionally, the types of acid sites are diversified in the BBLM composites compared to either bare BEA or lamellar MFI zeolites. The catalysis tests using conversion of benzyl alcohol in mesitylene showed that BBLM zeolites had significant higher activity and durability than single zeolites or their physical mixture. The BBLM zeolite composite provides a good model catalyst with integrated 2D-3D structures and meso-/microporosity for studying a series of important catalytic reactions in hierarchical zeolites. The one-step dual template synthesis method described herein is versatile and facile, which may prove to be a general platform for hierarchical zeolite composite design at the unit-cell scales of zeolites and with potentially broader applicability to other porous materials. [ABSTRACT FROM AUTHOR]

Direct non-oxidative methane coupling (NMC) is one of the promising pathways for methane upgrading into value-added olefin and aromatic hydrocarbons. The silica-supported iron (i.e., Fe/SiO 2) catalyst has been reported effective for NMC, but the effects of silica support on the catalyst property and NMC performance have rarely been explored. In this work, we prepared a vitreous silica-supported iron (Fe/SiO 2 -V) catalyst by flame fusion of a mixture of quartz silica and fayalite. The physicochemical properties and NMC performance of the as-prepared catalysts were measured. Compared to crystalline cristobalite support in Fe/SiO 2 catalyst that has been studied previously, vitreous silica support has disordered Si-O bonds and structural defects, enabling better iron dispersion and more vital metal-support interaction. The as-prepared Fe/SiO 2 -V catalyst had a shorter induction period in methane activation and lower coke yield in NMC. The increase in iron concentration in Fe/SiO 2 -V catalysts elongated the catalyst induction period and promoted aromatics and coke formation. The coke type of the spent Fe/SiO 2 -V catalyst is more uniform than the cristobalite-supported iron catalyst. [Display omitted] • Vitreous silica-supported iron catalysts were prepared by an oxyhydrogen flame fusion method. • The amorphous vitreous silica support contains disordered and defective Si-O bonds. • Iron has higher dispersion and more uniform bonding in the vitreous silica support. • Vitreous silica-supported iron enabled fast methane activation and low coking in NMC. • Increase in iron loading in vitreous silica support promoted aromatics formation. [ABSTRACT FROM AUTHOR]

• Characteristics of the coke deposits on lamellar metal (Ga or Zn)-modified zeolites were studied. • Mesoporous lamellar structure decreases the coke formation by facilitating the external coke deposition. • Metal modification decreases the coke formation by changing the acidity of zeolite. • Highest fraction of light coke is obtained for Zn-modified lamellar zeolite. • Both zeolite structure and metal-modified acidity affect the coke formation. The effects of meso-/microporous structure and metal-additive (Ga or Zn) of lamellar MFI catalysts on the characteristics of coke deposits during ethylene-to-aromatic liquids conversion were investigated. The nature, composition, and location of coke deposits in spent lamellar catalysts were analyzed and compared to those on the microporous MFI counterparts, using FTIR, UV–Vis, GC–MS, and argon adsorption-desorption. The total amount of coke and the changes in coke nature during catalyst regeneration were studied by MS/FTIR combined with temperature programmed oxidation. The lamellar meso-/microporous structure of MFI reduces the coke quantity and the heavy coke fractions. The coke preferentially deposites on external surface of lamellar zeolite due to the lower diffusion limitation for bulky coke precursors. Metal-additive changes the catalyst acidity and decreases the coke formation rate, especially when zinc is used. Therefore, the coke formation on zeolite can be tuned by modulating the textural and acidity properties of the metal-modified catalyst. [ABSTRACT FROM AUTHOR]