Compositional and operational impacts on the thermochemical reduction of CO2 to CO by iron oxide/yttria-stabilized zirconia

Abstract

Ferrites have potential for use as active materials in solar-thermochemical cycles because of their versatile redox chemistry. Such cycles utilize solar-thermal energy for the production of hydrogen from water and carbon monoxide from carbon dioxide. Although ferrites offer the potential for deep levels of reduction (e.g., stoichiometric conversion of magnetite to wüstite) and correspondingly large per-cycle product yields, in practice reactions are limited to surface regions made smaller by rapid sintering and agglomeration. Combining ferrites with zirconia or yttria-stabilized zirconia (YSZ) greatly improves the cyclability of the ferrites and enables a move away from powder to monolithic systems. We have studied the behavior of iron oxides composited with YSZ using thermogravimetric analysis under operando conditions. Samples in which the iron was fully dissolved within the YSZ matrix showed greater overall extent of thermochemical redox and higher rate of reaction than samples with equal iron loading but in which the iron was only partially dissolved, with the rest existing as agglomerates of iron oxide within the ceramic matrix. Varying the yttria content of the YSZ revealed a maximum thermochemical capacity (yield per cycle) for 6 mol% Y₂O₃ in YSZ. The first thermochemical redox cycle performed for each sample resulted in a net mass loss that was proportional to the iron oxide loading in the material and was stoichiometrically consistent with complete reduction of Fe₂O₃ to Fe₃O₄ and further partial reduction of the Fe₃O₄ to FeO. Mass gains upon reaction with CO₂ were consistent with re-oxidation of the FeO fraction back to Fe₃O₄. The Fe dissolved in the YSZ matrix, however, is capable of cycling stoichiometrically between Fe³⁺ and Fe²⁺. Varying the re-oxidation temperature between 1000 and 1200 °C highlighted the trade-off between re-oxidation rate and equilibrium limitations.