A zeolite with structure type MFI is an aluminosilicate or silicate material that has a three-dimensionally connected pore network, which enables molecular recognition in the size range 0.5-0.6 nm. These micropore dimensions are relevant for many valuable chemical intermediates, and therefore MFI-type zeolites are widely used in the chemical industry as selective catalysts or adsorbents. As with all zeolites, strategies to tailor them for specific applications include controlling their crystal size and shape. Nanometre-thick MFI crystals (nanosheets) have been introduced in pillared and self-pillared (intergrown) architectures, offering improved mass-transfer characteristics for certain adsorption and catalysis applications. Moreover, single (non-intergrown and non-layered) nanosheets have been used to prepare thin membranes that could be used to improve the energy efficiency of separation processes. However, until now, single MFI nanosheets have been prepared using a multi-step approach based on the exfoliation of layered MFI, followed by centrifugation to remove non-exfoliated particles. This top-down method is time-consuming, costly and low-yield and it produces fragmented nanosheets with submicrometre lateral dimensions. Alternatively, direct (bottom-up) synthesis could produce high-aspect-ratio zeolite nanosheets, with improved yield and at lower cost. Here we use a nanocrystal-seeded growth method triggered by a single rotational intergrowth to synthesize high-aspect-ratio MFI nanosheets with a thickness of 5 nanometres (2.5 unit cells). These high-aspect-ratio nanosheets allow the fabrication of thin and defect-free coatings that effectively cover porous substrates. These coatings can be intergrown to produce high-flux and ultra-selective MFI membranes that compare favourably with other MFI membranes prepared from existing MFI materials (such as exfoliated nanosheets or nanocrystals).
Methanol‐to‐olefin (MTO) catalysis is a very active field of research because there is a wide variety of sometimes conflicting mechanistic proposals. An example is the ongoing discussion on the initial C−C bond formation from methanol during the induction period of the MTO process. By employing a combination of solid‐state NMR spectroscopy with UV/Vis diffuse reflectance spectroscopy and mass spectrometry on an active H‐SAPO‐34 catalyst, we provide spectroscopic evidence for the formation of surface acetate and methyl acetate, as well as dimethoxymethane during the MTO process. As a consequence, new insights in the formation of the first C−C bond are provided, suggesting a direct mechanism may be operative, at least in the early stages of the MTO reaction.
Nanosized ZrO2 powders with near pure monoclinic, tetragonal, and cubic structures synthesized by various methods were used as catalysts for photocatalytic degradation of methyl orange. The structural and textural properties of the samples were analyzed by X-ray diffraction, Raman spectroscopy, TEM, UV-vis, X-ray photoelectron spectroscopy (XPS), and N2 adsorption measurements. The performance of synthesized ZrO2 nanoparticles in the photocatalytic degradation of methyl orange under UV light irradiation was evaluated. The photocatalytic activity of the pure monoclinic ZrO2 sample is higher than that of the tetragonal and cubic ZrO2 samples under optimum identical conditions. The characterization results revealed that monoclinic ZrO2 nanoparticles possessed high crystallinity and mesopores with diameter of 100 Å. The higher activity of the monoclinic ZrO2 sample for the photocatalytic degradation of methyl orange can be attributed to the combining effects of factors including the presence of small amount of oxygen-deficient zirconium oxide phase, high crystallinity, large pores, and high density of surface hydroxyl groups.
Layered double hydroxides (LDHs) show great potential as CO 2 adsorbent materials, but require improvements in stability and CO 2 adsorption capacity for commercial applications. In the current study, graphene oxide provides a light-weight, chargecomplementary, two-dimensional (2D) material that interacts effectively with the 2D LDHs, in turn enhancing the CO 2 uptake capacity and multicycle stability of the assembly. As a result, the absolute capacity of the LDH was increased by 62% using only 7 wt % graphene oxide (GO) as a support. The experimental procedure for the synthesis of the materials is based on a direct precipitation of the LDH nanoparticles onto GO followed by a structural and physical characterization by electron microscopy, X-ray diffraction, thermogravimetric analysis, and Brunauer−Emmett− Teller (BET) surface area measurements. Detailed titration confirmed the compatibility of the surface chemistry. After thermal decomposition, mixed metal oxides (MMOs) are obtained with the basic sites required for the CO 2 adsorption. A range of samples with different proportions of GO/MMO were prepared, fully characterized, and correlated with the CO 2 sorption capacity, established via TGA.
A zeolite membrane fabrication process combining 2D-zeolite nanosheet seeding and gel-free secondary growth is described. This process produces selective molecular sieve films that are as thin as 100 nm and exhibit record high permeances for xylene- and butane-isomers.
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