Elucidating the role of CO2 in the soft oxidative dehydrogenation of propane over ceria-based catalysts
journal contributionposted on 30.05.2018, 12:40 by Ewa Nowicka, Christian Reece, Sultan M. Althahban, Khaled M. Mohammed, Simon Kondrat, David J. Morgan, Qian He, David J. Willock, Stanislaw Golunski, Christopher J. Kiely, Graham J. Hutchings
A mixed oxide support containing Ce, Zr, and Al was synthesized using a physical grinding method and applied in the oxidative dehydrogenation of propane using CO 2 as the oxidant. The activity of the support was compared with that of fully formulated catalysts containing palladium. The Pd/CeZrAlO x material exhibited long-term stability and selectivity to propene (during continuous operation for 140 h), which is not normally associated with dehydrogenation catalysts. From temperature-programmed desorption of NH 3 and CO 2 it was found that the catalyst possessed both acidic and basic sites. In addition, temperature-programmed reduction showed that palladium promoted both the reduction and reoxidation of the support. When the role of CO 2 was investigated in the absence of gas-phase oxidant, using a temporal analysis of products (TAP) reactor, it was found that CO 2 dissociates over the reduced catalyst, leading to formation of CO and selective oxygen species. It is proposed that CO 2 has the dual role of regenerating selective oxygen species and shifting the equilibrium for alkane dehydrogenation by consuming H 2 through the reverse water-gas-shift reaction. These two mechanistic functions have previously been considered to be mutually exclusive.
This work was funded by the European Research Council, through the following grant: After the Goldrush, ERC-AG-291319. C.J.K. gratefully acknowledges funding from the National Science Foundation Major Research Instrumentation program (GR# MRI/DMR-1040229). We thank Diamond Light Source for use of B18 (SP8071-12), with gratitude to Dr. Diego Gianolio. E.N. thanks the Technical University of Berlin and Marie Curie-Sklodowska Action for awarding her IPODI fellowship.