Search Results (5)

Two multifunctional catalytic systems comprising Sn-based/doped crystalline zeolite Beta were synthesized, and they were employed as heterogeneous catalysts in the selective conversion of glycerol to methyl lactate. The first catalytic system, named Au-Pd-Sn-deAl-7.2-Beta-DP, was created through the post-synthesis dealumination of the parent zeolite Beta (Si/Al = 10) using 7.2 M HNO₃. Subsequently, it was grafted with 27 mmol of SnCl₄, resulting in Sn-deAl-7.2-Beta. Following this, Au and Pd nanoparticles were supported on this catalyst using the deposition–precipitation (DP) method. The second catalytic system was a physical mixture of Au and Pd nanoparticles supported on functionalized carbon nanotubes (Au-Pd-F-CNTs) and Sn-containing zeolite Beta (Sn-deAl-7.2-Beta). Both catalytic systems were employed in glycerol partial oxidation to methyl lactate under the following conditions: 140 °C for 4.5 h under an air pressure of 30 bar. The Au-Pd-Sn-deAl-7.2-Beta-DP catalytic system demonstrated 34% conversion of glycerol with a 76% selectivity for methyl lactate. In contrast, the physical mixture of Au-Pd-F-CNTs and Sn-deAl-7.2-Beta exhibited higher activity, achieving 58% glycerol conversion and a nearly identical selectivity for methyl lactate (77%). The catalytic results and catalyst structure were further analyzed using various characterization techniques, such as X-ray diffraction (XRD), N₂ physisorption, scanning electron microscopy (SEM), X-ray fluorescence (XRF), transmission electron microscopy (TEM), UV-vis spectroscopy, and pyridine Fourier transform infrared (FTIR). These analyses emphasized the significance of adjusting the quantity of active sites, particle size, and active sites proximity under the chosen reaction conditions. Full article

The Baeyer-Villiger Oxidation (BVO) of ketones and aldehydes produce lactones and formates, while aerobic carboxylation of aldehydes manufactures carboxylic acids, both having high added value. This work prepared a series of Al-containing silicates modified with organic ligands and SnO₂ nanoparticles, which were then employed as catalyst in BVO and carboxylation. Characterizations revealed the morphology of the synthesized catalyst was changed from micron-sized thin sheets to smaller blocks, and then to uniform nanoparticles (size of 50 nm) having the doped SnO₂ nanoparticles with a size of 29 nm. All catalysts showed high BET surface areas featuring silt-like mesopores. In determining the priority of BVO and carboxylation, an influence evaluation of the parameters showed the order to be substrate > oxidant > solvent > catalyst. Cyclic aliphatic ketones were suitable for BVO, but linear aliphatic and aromatic aldehydes for carboxylation. Coordination of (S)-binaphthol or doping of Sn into catalyst showed little influence on BVO under m-CPBA, but the Sn-doped catalyst largely increased BVO under (NH₄)₂S₂O₈ and H₂O₂. Calculations revealed that the catalyst containing both Al and Sn could give BVO intermediates lower energies than the Sn-beta zeolite model. The present system exhibited merits including wider substrate scope, innocuous catalytic metal, greener oxidant, as well as lower catalyst cost. Full article

Beta zeolites with different heteroatoms incorporated into the lattice at two loadings (Si/M = 100 or 200, where M = Al, Fe, Ga, B) were hydrothermally synthesised and used as starting materials for the preparation of Sn-Beta using Solid-State Incorporation. ¹¹⁹Sn CPMG MAS NMR showed that various Sn species were formed, the distribution of which depended on the identity of the initial heteroatom and the original Si/M ratio. The final Sn-Beta materials (with Si/Sn = 200) were explored as catalysts for the retro-aldol fragmentation of glucose to α-hydroxy-esters in the continuous regime. Amongst these materials, B-derived Sn-Beta was found to exhibit improved levels of selectivity and stability, particularly compared to Sn-Beta catalysts synthesised from commercially available Al-Beta materials, achieving a combined yield of methyl lactate and methyl vinyl glycolate > 80% at short times on the stream. Given that B atoms can be removed from the Beta lattice in mild conditions without the use of highly concentrated acidic media, this discovery demonstrates that B-Beta is an attractive starting material for the future post-synthetic preparation of Lewis acidic zeolites. Full article

Bimetallic zeolite Beta in bead format and containing Al sites with Brønsted acid behavior and Sn, Zr or Hf sites with Lewis acid character, were prepared using a two-step synthetic route. First, zeolite Beta in the format of macroscopic beads (400 to 840 μm) with hierarchical porosity (micropores accessed through meso- and macropores in the range of 30 to 150 nm) were synthesized by hydrothermal crystallization in the presence of anion-exchange resin beads as hard template and further converted into their H-form. Next, the zeolite beads were partially dealuminated using different concentrations of HNO₃ (i.e., 1.8 or 7.2 M), followed by grafting with one of the above-mentioned metals (Sn, Zr or Hf) to introduce Lewis acid sites. These bimetallic zeolites were tested as heterogeneous catalysts in the conversion of dihydroxyacetone (DHA) to methyl lactate (ML). The Sn-containing zeolite Beta beads treated by 1.8 M HNO₃ and grafted with 27 mmol of SnCl₄ (Sn-deAl-1.8-Beta-B) demonstrated the best catalytic activity among the prepared bimetallic zeolite beads, with 99% selectivity and 90% yield of ML after 6 h at 90 °C. This catalyst was also tested in combination with Au-Pd nanoparticles supported on functionalized carbon nanotubes (CNTs) as multifunctional catalytic system for the conversion of glycerol to ML, achieving 29% conversion of glycerol and 67% selectivity towards ML after 4.5 h at 140 °C under 30 bar air. The catalytic results were rationalized by means of a thorough characterization of the zeolitic beads with a combination of techniques (XRD, N₂-physisorption, SEM, XRF, TEM, UV-vis spectroscopy and pyridine-FT-IR). Full article

With the growing global propylene demand, propane dehydrogenation (PDH) has attracted great attention for on-purpose propylene production. However, its industrial application is limited because catalysts suffer from rapid deactivation due to coke deposition and metal catalyst sintering. To enhance metal catalyst dispersion and coke resistance, Pt-based catalysts have been widely investigated with various porous supports. In particular, zeolite can benefit from large surface area and acid sites, which favors high metal dispersion and promoting catalytic activity. In this work, we investigated the PDH catalytic properties of Beta zeolites as a support for Pt-Sn based catalysts. In comparison with Pt-Sn supported over θ-Al₂O₃ and amorphous silica (Q6), Beta zeolite-supported Pt-Sn catalysts exhibited a different reaction trend, achieving the best propylene selectivity after a proper period of reaction time. The different PDH catalytic behavior over Beta zeolite-supported Pt-Sn catalysts has been attributed to their physicochemical properties and reaction mechanism. Although Pt-Sn catalyst supported over Beta zeolite with low acidity showed low Pt dispersion, it formed a relatively lower amount of coke on PDH reaction and maintained a high surface area and active Pt surfaces, resulting in enhanced stability for PDH reaction. This work can provide a better understanding of zeolite-supported Pt-Sn catalysts to improve PDH catalytic activity with high selectivity and low coke formation. Full article