Synthesis, Characterization, and Thermochemical Redox Performance of Hf4+, Zr4+, and Sc3+ Doped Ceria for Splitting CO2

We present results on the thermochemical redox performance and analytical characterization of Hf 4+, Zr 4+, and Sc 3+ doped ceria solutions synthesized via a sol–gel technique, all of which have recently been shown to be promising for splitting CO 2 . Dopant concentrations ranging from 5 to 15 mol % have been investigated and thermally cycled at reduction temperatures of 1773 K and oxidation temperatures ranging from 873 to 1073 K by thermogravimetry. The degree of reduction of Hf and Zr doped materials is substantially higher than those of pure ceria and Sc doped ceria and increases with dopant concentration. Overall, 10 mol % Hf doped ceria results in the largest CO yields per mole of oxide (∼0.5 mass % versus 0.35 mass % for pure ceria) based on measured mass changes during oxidation. However, these yields were largely influenced by their rate of reoxidation, not necessarily thermodynamic limitations, as equilibrium was not achieved for either Hf or Zr doped samples after 45 min exposure to CO 2 at all oxidation temperatures. Additionally, sample preparation and grain size strongly affected the oxidation rates and subsequent yields, resulting in slightly decreasing yields as the samples were cycled up to 10 times. X-ray diffraction, Raman, FT-IR, and UV/vis spectroscopy in combination with SEM-EDX have been applied to characterize the elemental, crystalline, and morphological attributes before and after redox reactions.