Adsorbed oxygen atoms for improving the oxidative dehydrogenation of ethane over B-site-doped layered perovskite La2Ti2O7

초록

In this study, Nd, Ga, and Sm were used to partially replace Ti in layered perovskite La2Ti2O7 (A(2)B(2)O(7) type) with the aim of developing a highly efficient low-temperature catalyst for the oxidative dehydrogenation of ethane (ODHE). Ethylene was successfully produced by the ODHE over the modified catalysts at temperatures of as low as 600 degrees C, and the Ga-doped catalyst exhibited the highest ethylene yield of 16.9 % at 625 degrees C with a high gas hourly space velocity of 35,273 h(-1) and short reactant-catalyst contact time of 0.1 s. Thermal activation improved the ethylene yield to 33.6-39.4 % at 650-700 degrees C with a short contact time (<0.1 s) and productivity of approximately 10 g(ethylene)<middle dot>g(catalyst)(-1)<middle dot>h(-1), which exceeds reported values. However, the pure catalytic activity could not be depicted at higher temperatures (>700 degrees C) because the reaction became more complex owing to thermally activated processes such as thermal dehydrogenation, thermal-oxidative dehydrogenation, and reforming reactions. The effects of B-site doping were explored through in situ characterization and density functional theory calculations, and a mechanism for the ODHE was proposed based on the results. Adsorbed oxygen atoms, which form by the dissociation of molecular oxygen at high temperatures, are responsible for the selective dehydrogenation of ethane to ethylene. Overall, the electronic modification of the B-site doped La2Ti2O7 catalysts improved the catalytic activity at 525-575 degrees C, and the experimental and calculation results confirmed that dissociatively adsorbed oxygen atoms were responsible for the improved ODHE.

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