Dopant-Enhanced harmonization of α-Fe2O3 oxygen migration and surface catalytic reactions during chemical looping reforming of methane

The rate-matching between oxygen migration and surface catalytic reaction of oxygen carrier (OC) is a critical determinant for the reaction selectivity of the chemical looping reforming (CLR) of methane. However, the theoretical mechanism behind this rate-matching relationship is still unclear. Herein, we propose to use density functional theory (DFT) combined with microkinetic simulations to establish a model integrating the methane oxidation reactions with oxygen migration kinetics on α-Fe2O3 oxygen carrier. Our calculated results reveal that the transition metals (TMs)-doping such as Co, Ni, and Cu after Fe element in the periodic table can accelerate the oxygen migration rate as it promotes the upshift of the O p-band center. Moreover, a suitable oxygen migration energy barrier of about 1.0 eV is helpful to enhance the harmonization of α-Fe2O3 oxygen migration and surface catalytic reactions. Based on this, Ni-doping in α-Fe2O3 is predicted to be able to enhance the oxygen migration rate to match the rate of first-step methane dissociation, thereby simultaneously improving the reaction rate and the selectivity in the CLR of methane to syngas. These results could help to understand the relationship between oxygen migration and surface catalytic reaction rates and pave the way for the rational design of metal oxide oxygen carriers.