Understanding the solar-driven reduction of CO₂ on doped ceria

With the appropriate materials, one can construct redox cycles that use CO2 as the oxidant, generating CO as the product. Here, we investigate thermochemical cycles using doped ceria compounds as the oxygen exchange medium. Doped samples are prepared using La, Cr, W, Zr, V, Y, and Ti as dopants. Studying the redox kinetics, we show that doping the pure ceria with zirconium strongly increases overall CO production, albeit at lower reaction rates. This is because the CO2 reduction step is second-order with respect to Ce(III). Doping the fluorite lattice with zirconium cations decreases the number of Ce(III) ions at the surface, and consequently slows down the reaction. This result is counter-intuitive, since normally you would think that the more reduction, the better. But the reactivity towards CO2 is actually determined by the surface Ce(III) ions, and so migration of dopant ions on the surface reduces its reactivity, even though the bulk Ce(III) concentration is higher. Our results demonstrate the importance of understanding surface kinetics when designing oxygen exchange materials for solar reactors.