Meng-Fei Luo

Great improvement on the selective hydrogenation of crotonaldehyde over CrOx- and FeOx-promoted Ir/SiO2 catalysts

Catalytic selective hydrogenation of α,β-unsaturated aldehydes to α,β-unsaturated alcohols is very important in the synthesis of various fine chemicals. However, the development of highly efficient catalyst systems is challenging because of the low selectivity and severe deactivation of the currently employed catalysts such as Pt and Au. In this work, a series of CrOx- and FeOx-promoted Ir/SiO2 catalysts were prepared by a sequential impregnation method and tested for gas phase selective hydrogenation of crotonaldehyde. It was found that the addition of promoters could greatly enhance the catalytic performance. The Ir/SiO2 catalyst promoted with combined CrOx–FeOx with a (Cr + Fe)/Ir ratio of 0.05 showed the highest steady state crotyl alcohol yield of 64.5% at a selectivity of 86%, which is 4-fold higher than that of the unpromoted Ir/SiO2 (15.5%) catalyst. Such an enhancement was due to the formation of new active sites generated at the Ir–CrOx and/or Ir–FeOx interfaces. Also, catalysts with low loadings of promoters showed excellent stability due to their appropriate electronic properties, while the catalyst with a high loading of promoters deactivated quickly due to the strong adsorption of products on the surface.

Enhanced CO oxidation over potassium-promoted Pt/Al2O3 catalysts: Kinetic and infrared spectroscopic study

Abstract A series of K-promoted Pt/Al2O3 catalysts were tested for CO oxidation. It was found that the addition of K significantly enhanced the activity. A detailed kinetic study showed that the activation energies of the K-containing catalysts were lower than those of the K-free ones, particularly for catalysts with high Pt contents (51.6 kJ/mol for 0.42K-2.0Pt/Al2O3 and 63.6 kJ/mol for 2.0Pt/Al2O3). The CO reaction orders were higher for the K-containing catalysts (about −0.2) than for the K-free ones (about −0.5), with the former having much lower equilibrium constants for CO adsorption than the latter. In situ Fourier-transform infrared spectroscopy showed that surface CO desorption from the 0.42K-2.0Pt/Al2O3 catalyst was easier than from 2.0Pt/Al2O3. The promoting effect of K was therefore caused by weakening of the interactions between CO and surface Pt atoms. This decreased coverage of the catalyst with CO and facilitated competitive O2 chemisorption on the Pt surface, and significantly lowered the reaction barrier between chemisorbed CO and O2 species.

CO and C3H8 total oxidation over Pd/La-Al2O3 catalysts: Effect of calcination temperature and hydrothermal treatment

A series of Pd/La-Al2O3 (PLA) catalysts with La-Al2O3 (LA) support calcined at different temperatures (500, 700, 900 and 1050 °C) were prepared using an incipient wetness impregnation method. The activity of the fresh and hydrothermally aged PLA catalysts were tested for total oxidation of CO and C3H8. The activity of the fresh PLA catalysts for CO and C3H8 oxidation increased with increasing calcination temperature of the support, while the activities of the aged catalysts declined and became essentially the same. CO chemisorption results revealed that the suppressed activities of the aged catalysts were mainly due to the decline of palladium dispersion. The turnover frequency (TOF) of CO oxidation increased with increasing reduction ability of the catalysts, with a fresh catalyst calcined at 1050 °C having the highest value (0.048 s−1). However, the TOF of C3H8 total oxidation was affected by not only the redox properties of catalysts but also the size of Pd particle, and large Pd particles possessed higher TOF value of C3H8 oxidation, with the highest value (0.125 s−1) being obtained on an aged catalyst calcined at 500 °C.