Diffusion of oxygen in ceria at elevated temperatures and its application to H2O/CO2 splitting thermochemical redox cycles

Abstract

Determination of reaction and oxygen diffusion rates at elevated temperatures is essential for modeling, design, and optimization of high-temperature solar thermochemical fuel production processes, but such data for state-of-the-art redox materials, such as ceria, is sparse. Here, we investigate the solid-state reduction and oxidation of sintered nonstoichiometric ceria at elevated temperatures relevant to solar thermochemical redox cycles for splitting H2O and CO2 (1673 K ≤ T ≤ 1823 K, 3 × 10-4 atm ≤ pO2 ≤ 2.5 × 10-3 atm). Relaxation experiments are performed by subjecting the sintered ceria to rapid oxygen partial pressure changes and measuring the time required to achieve thermodynamic equilibrium state. From such data, we elucidate information regarding ambipolar oxygen diffusion coefficients through comparison of experimental data to a numerical approximation of Fick's second law based on finite difference methods. In contrast to typically applied analytical approaches, where diffusion coefficients are necessarily concentration independent, such a numerical approach is capable of accounting for more realistic concentration dependent diffusion coefficients and also accounts for transient gas phase boundary conditions pertinent to dispersion and oxygen consumption/evolution. Ambipolar diffusion coefficients are obtained in the range 1.510-5 cm 2 s-1 ≤ D̃ ≤ 410-4 cm2 s-1 between 1673 and 1823 K. These results highlight the rapid nature of ceria reduction to help guide the design of redox materials for solar reactors, the importance of accounting for transient boundary conditions during relaxation experiments (either mass based or conductivity based), and point to the flexibility of using a numerical analysis in contrast to typical analytical approaches. © 2014 American Chemical Society.