The catalytic performances and characterization of the catalysts La1.6Sr0.4CuO3.852, La1.6Sr0.4CuO3.857F0.143, and La1.6Sr0.4 CuO3.856Cl0.126 have been investigated for the oxidative dehydrogenation of ethane (ODE) to ethene. X‐ray diffraction results indicated that
the three catalysts have a single‐phase tetragonal K2NiF4-type structure. The incorporation of fluoride or chloride ions in the La1.6Sr0.4CuO4-δ lattice can significantly enhance C2H6 conversion and C2H4 selectivity. We observed 83.2% C2H6 conversion, 76.7% C2H4 selectivity, and 63.8% C2H4 yield over La1.6Sr0.4CuO3.857F0.143>
and 79.6% C2H6 conversion, 74.6% C2H4 selectivity, and 59.4% C2H4 yield over La1.6Sr0.4CuO3.856Cl0.126 under the reaction conditions of C2H6/O2/N2 molar ratio 2/1/3.7, temperature 660°C, and space velocity 6000 ml h-1 g-1. With the rise in space velocity, C2H6 conversion decreased, whereas C2H4 selectivity increased. Life studies showed that the two catalysts were durable within 60 h of on‐stream ODE reaction. Based
on the results of X‐ray photoelectron spectroscopy, O2 temperature-programmed desorption, and C2H6 and C2H6/O2/N2 (2/1/3.7 molar ratio) pulse studies, we conclude that (i) the inclusion of halide ions in the La1.6Sr0.4CuO4δ lattice could promote lattice oxygen mobility, and (ii) the O- species accommodated in oxygen vacancies and desorbed below 600°C favor ethane complete oxidation whereas the lattice oxygen
species desorbed in the 600–700°C range are active for ethane selective oxidation to ethene. By regulating the oxygen vacancy
density and Cu3/Cu ratio in the K2NiF4-type halo-oxide catalyst, one can generate a durable catalyst with good performance for the ODE reaction.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
The adsorption of low-coverage of F and Cl adatoms on the Mg (0001) surface was investigated using first-principles calculations based on the density functional theory (DFT). The stability of the (2 × 2) structures formed by halogen atoms adsorbed at different sites was determined. The difference between the adsorption of F and Cl on Mg (0001) surface was also discussed. The calculation results show that hollow sites are the energetically most favorable at the low-coverage. It can be concluded from the Mulliken charges and density of states that electrons transfer from the substrate Mg atoms to the adatoms, which leads to the formation of adsorbate bond and further causes the stronger interaction between Mg atom and adatom. The interaction between Cl and Mg atoms is weaker than the interaction between F and Mg. 相似文献
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