First principle based rate equation (1pRE) for random pore model in Fe2O3 reduction reaction with CO

Abstract The redox kinetics of the oxygen carriers are crucial in Chemical‐Looping Combustion (CLC) systems. The random pore model (RPM) was widely used to investigate the macroscale redox kinetics of oxygen carriers in previous studies, in which the reaction rate constants were obtained just by fitting the experimental data. This study presents a first principle based rate equation (1pRE) applied to the RPM to calculate the reaction rate constants directly using density functional theory (DFT). The 1pRE is integrated with the RPM that accounts for the effect of pore size distribution derived from the surface area evolution of reaction interface and product layer diffusion, thus bridging the gap between the microscale elementary surface reactions and macroscale overall conversion. The developed 1pRE predicts the reduction kinetics of Fe 2 O 3 oxygen carriers accurately, thereby facilitating the optimization of design processes for oxygen carrier materials and the scale up of CLC reactors.