Kinetics and mechanism of solar-thermochemical H2 production by oxidation of a cobalt ferrite–zirconia composite

Abstract

Accurate knowledge of water splitting kinetics is essential for the design and optimization of high-temperature thermochemical cycles for solar-driven fuel production, but such crucial data are unavailable for virtually all redox materials of potential practical value. We describe an investigation of the redox activity and oxidation kinetics of cobalt ferrite, a promising material for this application that is representative of a broader class of metal-substituted ferrites. To enable repetitive cycling, ferrites must be supported on another oxide to avoid sintering and deactivation. Consequently, we synthesized a composite material using atomic layer deposition of cobalt and iron oxides on zirconia, a commonly used ferrite “support”, to create a well-controlled, uniformly distributed composition. Our results show that the support is not an innocent bystander and that dissolved iron within it reacts by a different mechanism than embedded iron oxide particles in the matrix. Samples were thermally reduced at 1450 °C under helium and oxidized with steam at realistic process temperatures ranging from 900 °C to 1400 °C. Experiments within a fluid-dynamically well-behaved stagnation-flow reactor, coupled with detailed numerical modelling of the transient H₂ production rates, allow us to effectively deconvolve experimental artefacts from intrinsic material behaviour over the entire time domain of the oxidation reaction. We find that second-order reaction and diffusion-limited mechanisms occur simultaneously at different oxidation rates and involve iron in two separate phases: (1) reduced Fe dissolved in the ZrO₂ support and (2) iron oxide located at the interface between embedded ferrite particles and the zirconia matrix. Surprisingly, we also identified a catalytic mechanism occurring at the highest temperatures by which steady-state production of H₂ and O₂ occurs. The results reported here, which include Arrhenius rate constants for both oxidation mechanisms, will enable high-fidelity computational simulation of this complex, but promising approach to renewable fuel production.