Zr-Doping-Induced Structural and Lattice-Oxygen Regulation in CeZrOₓ Solid Solutions for Chemical-Looping Oxidative Dehydrogenation of Propane
DOI:
https://doi.org/10.15377/2409-983X.2026.13.2Keywords:
Redox cycle, Propylene synthesis, CeO₂-ZrO₂ solid solution, Lattice oxygen selectivity, Crystal facet engineeringAbstract
Chemical-looping oxidative dehydrogenation of propane (CL-ODHP) separates hydrocarbon conversion from gas-phase oxygen and uses a redox-active solid as the oxygen source. Here, Ce₁₋ᵧZrᵧOₓ (y = 0–0.50) oxygen carriers were prepared by co-precipitation to examine how moderate Zr doping changes fluorite-lattice structure, mesoporosity, oxygen speciation, and transient CL-ODHP performance at 550 °C under identical fixed-bed conditions using a 10% propane feed. X-ray diffraction showed progressive lattice contraction and a composition-dependent relative intensity of the (111) reflection, with Ce₀.₉₀Zr₀.₁₀Oₓ giving the largest relative (111) intensity among the mixed oxides. This composition also exhibited the highest BET surface area (111.24 m² g⁻¹), pore volume (0.36 cm³ g⁻¹), mean pore diameter (17.79 nm), and XPS lattice-oxygen fraction (O_I, 47.87%), while maintaining a lower defect-associated O_II fraction (28.37%) than the more Zr-rich samples. From the data points plotted over 3–15 min, Ce₀.₉₀Zr₀.₁₀Oₓ provided the highest mean propane conversion (16.85%), propylene selectivity (63.57%), and propylene yield (10.71%) within the evaluated series. Its apparent oxygen-depletion/deactivation constant was 0.0113 min⁻¹, lower than those of CeO₂ (0.0258 min⁻¹) and Ce₀.₉₅Zr₀.₀₅Oₓ (0.0144 min⁻¹). The novelty of this work is the within-series correlation of relative (111) diffraction intensity, mesoporous structure, and standardized O_I/O_II/O_III surface-oxygen components with transient propane conversion and selectivity, identifying moderate Zr substitution as a balance between accessible lattice oxygen and defect-associated oxygen. These results are consistent with, but do not by themselves prove, a Mars-van Krevelen pathway. Because the study comprises single-run reduction-half-cycle screening without independent replication or multicycle regeneration, the quantitative performance should be regarded as preliminary rather than a record benchmark.
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