The influence on gas-phase catalytic glycerol dehydration of crystal size (S: small, or L: large crystals), acidity, and synthesis procedure for isomorphous incorporation of gallium (Ga-S; Ga-L) or aluminum (Al-S; AlL) in MFI zeolites was studied. The main product observed was acrolein, with the undesirable parallel formation of deactivating coke molecules such as polyglycols and polyaromatics. The GaS zeolite showed the best performance in this reaction, as it provided a combination of adequate accessibility to the microporous system and weak Brønsted acid sites. The chemical and structural properties of the fresh MFI zeolites were studied by X-ray diffraction, nitrogen sorption measurements, scanning electron microscopy, temperature-programmed desorption of NH 3 , X-ray photoelectron spectroscopy, and 27 Al and 29 Si MAS-NMR. Solid-state 13 C MAS-NMR and thermogravimetric analyses of the spent MFI zeolites confirmed the differences in the nature and amounts of the carbonaceous deposits formed. The polyglycols were preferentially formed on the external surface of the zeolite crystals, as expected due to the greater exposed area. On the other hand, the polyaromatic compounds formed were more abundant inside the micropores of the MFI zeolites, especially those composed of larger crystals and with a greater number of strong Brønsted acid sites.
Mg substitution on B sites of La2Ti2O7 perovskites promoted changes in the surface active-site distribution leading to improvements in the C2 selectivity during the oxidative coupling of methane.
The one-step oxydehydration of glycerol to acrylic acid over molybdenum and vanadium mixed oxides was investigated. The Mo-V oxide catalysts were prepared by a simple hydrothermal method under different synthesis and calcination atmospheres and were characterized by in situ XRD, TPD-NH 3 , N 2 adsorption/ desorption, X-ray absorption near vanadium K-edge spectroscopy and thermogravimetry. The catalytic performance of the samples at different temperatures (290, 320 and 350°C) and under different gas flow compositions (20% O 2 in N 2 , 100% O 2 , or 100% N 2) revealed that the arrangement of the crystallographic structures of the active phases directly influenced the catalytic performance. It was found that the catalysts heattreated in oxidizing atmosphere gave superior catalytic results comparing with the catalysts heat-treated in inert atmosphere due to the equilibrium between the crystalline phases MoVO 5 and Mo 4.65 V 0.35 O 14 that contains V +4 and V +5. Catalytic oxydehydration at 320°C under a flow of 100% O 2 gave the best performance, achieving selectivity of 33.5% towards acrylic acid and 100% conversion of glycerol.
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