51. Two-step hydrothermally synthesized Ce1-xZrxO2 for oxidative dehydrogenation of ethylbenzene with carbon dioxide
- Author
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Yong-Hong Song, Zhao-Tie Liu, Huan Wang, Fang-Xian Cao, Han-Qing Ge, Zhong-Wen Liu, Yongquan Qu, and Guo-Qing Yang
- Subjects
Process Chemistry and Technology ,Ethylbenzene ,Redox ,Hydrothermal circulation ,Catalysis ,chemistry.chemical_compound ,symbols.namesake ,chemistry ,symbols ,Chemical Engineering (miscellaneous) ,Dehydrogenation ,Cubic zirconia ,Raman spectroscopy ,Waste Management and Disposal ,Solid solution ,Nuclear chemistry - Abstract
Ceria, zirconia, Ce0.9Zr0.1O2, Ce0.75Zr0.25O2, and Ce0.5Zr0.5O2 samples were synthesized via the two-step hydrothermal method by using Ce(NO3)3·6H2O and Zr(NO3)4·5H2O as the precursors, respectively. The oxides were applied as catalysts for the dehydrogenation of ethylbenzene by using carbon dioxide as a soft oxidant (CO2-ODEB) at 550 °C and 0.1 MPa. Reaction results indicate that ceria was the most active catalyst while the zirconia with a cubic structure was inactive for CO2-ODEB. In the cases of the oxides by inserting Zr into CeO2, the activity indexed by either the initial ethylbenzene (EB) conversion or the calculated turnover frequency (TOF) at a time on stream of 1 h was changed in the sequence of Ce0.9Zr0.1O2 >> Ce0.75Zr0.25O2 > Ce0.5Zr0.5O2 while the decreasing pattern of the stability was observed in the order of Ce0.5Zr0.5O2 ≈ Ce0.75Zr0.25O2 >> Ce0.9Zr0.1O2. As revealed from the characterization results of XRD and Raman, the pure cubic solid solution of Ce1-xZrxO2 without any phase separations was obtained irrespective of the compositions. By correlating the characterization results, the activity of Ce1-xZrxO2 for CO2-ODEB was determined by the amount of the Ce3+ oxidized by CO2 and the rate of Ce3+/Ce4+ redox cycles. Moreover, both the coking rate and the promoting effect of the deposited coke on CO2-ODEB were responsible for the stability of Ce1-xZrxO2.
- Published
- 2019
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