One-Pot Transformation of Citronellal to Menthol Over H-Beta Zeolite Supported Ni Catalyst: Effect of Catalyst Support Acidity and Ni Loading

Citronellal was converted to menthol in a one-pot approach using H-Beta zeolite-based Ni catalyst in a batch reactor at 80 °C, under 20 bar of total pressure. The effects of H-Beta acidity (H-Beta-25 with the molar ratio SiO2/Al2O3 = 25 and H-Beta-300 with SiO2/Al2O3 = 300) and Ni loading (5, 10 and 15 wt %) on the catalytic performance were investigated. Ni was impregnated on H-Beta support using the evaporation-impregnation method. The physico-chemical properties of the catalysts were characterized by XRD, SEM, TEM, ICP-OES, N2 physisorption, TPR, and pyridine adsorption–desorption FTIR techniques. Activity and selectivity of catalysts were strongly affected by the Brønsted and Lewis acid sites concentration and strength, Ni loading, its particle size and dispersion. A synergetic effect of appropriate acidity and suitable Ni loading in 15 wt.% Ni/H-Beta-25 catalyst led to the best performance giving 36% yield of menthols and 77% stereoselectivity to (±)-menthol isomer at 93% citronellal conversion. Moreover, the catalyst was successfully regenerated and reused giving similar activity, selectivity and stereoselectivity to the desired (±)-menthol isomer as the fresh one. Graphical Abstract: [Figure not available: see fulltext.

Influence of Fe/Mo Stoichiometry on Structural and Magnetic Properties in Sr₂Fe_xMo_2-xO₆: A Theoretical and Experimental Study

The influence of nonstoichiometry on the structural and magnetic properties of Sr2FeMoO6(SFMO) has been investigated by varying the ratio of Fe in polycrystalline samples. We demonstrate that changes in the Fe/Mo ratio can elevate the Curie temperature (TC) in SFMO, even though the total magnetic moment is reduced at the same time. The discoveries of the stoichiometric imbalance between the cations Fe and Mo are discussed in the context of first-principles calculations on the electronic and magnetic structures of SFMO using the GGA+U method. Our theoretical results reveal that Fe deficiency reduces the TC due to the antiparallel alignment of Fe moments in Mo positions, which is consistent with experimental observations. In contrast, accurate TC trends for Fe excess are reproduced only by considering spin disorder, with both parallel and antiparallel Fe moment orientations. These insights provide a detailed understanding of the magnetic interactions in SFMO. Our findings lay the groundwork for developing innovative SFMO-based materials and emphasize the significance of stoichiometry control in optimizing SFMO properties

Thickness dependent properties of SFMO thin films grown on STO and LSAT substrates

Pure, fully textured and c-axis oriented Sr2FeMoO6, films were deposited on SrTiO3 and (LaAlO3)(0.3)(Sr2AlTaO6)(0.7) substrates with different thicknesses. A decrease in substrate induced strain was observed in films on SrTiO3 with increasing thickness, but the strain in the films on (LaAlO3)(0.3)(Sr2AlTaO6)(0.7) was nearly constant within the whole film thickness range. Despite the differences in the strain, the magnetic properties of the films showed similar thickness dependence on both substrates. The saturation magnetization and Curie temperature increased until around 150 nm thickness was reached. Semiconducting low temperature upturn in resistivity was observed in all the films and it was enhanced in the thinnest films. Thus, the band gap energy increases with increasing film thickness. According to these results, at least 150 nm thickness is required for high quality Sr2FeMoO6 films.</p

Thickness Dependent Properties of Sr2FeMoO6 Thin Films Grown on SrTiO3 and (LaAlO3)0.3(Sr2AlTaO6)0.7 Substrates

AbstractPure, fully textured and c-axis oriented Sr2FeMoO6 films were deposited on SrTiO3 and (LaAlO3)0.3(Sr2AlTaO6)0.7 substrates with different thicknesses. A decrease in substrate induced strain was observed in films on SrTiO3 with increasing thickness, but the strain in the films on (LaAlO3)0.3(Sr2AlTaO6)0.7 was nearly constant within the whole film thickness range. Despite the differences in the strain, the magnetic properties of the films showed similar thickness dependence on both substrates. The saturation magnetization and Curie temperature increased until around 150nm thickness was reached. Semiconducting low temperature upturn in resistivity was observed in all the films and it was enhanced in the thinnest films. Thus, the band gap energy increases with increasing film thickness. According to these results, at least 150nm thickness is required for high quality Sr2FeMoO6 films