Microscopic insights into the reaction mechanism of Fe-based oxygen carrier with CH4 in chemical-looping combustion

[Display omitted] •Reaction mechanism of CH4 by Fe2O3 was revealed via experimental and theoretical methods.•A microkinetic model combining oxygen supply and catalysis was developed for Fe2O3.•Methoxy(CH3O) is the key intermediate for CH4 complete oxidation.•CH3O* → CH2OO* + H* dominates the overall CH4 combustion reaction by Fe2O3. Fe-based oxygen carriers are regarded as a promising class of oxygen carriers in the field of chemical looping combustion. However, the elucidation of the detailed microscopic reaction mechanism of oxygen carriers remains a significant challenge. In this work, we combine in situ spectroscopy, density-functional theory (DFT) calculations, and micro-kinetic modelling to reveal the microscopic reaction mechanism of CH4 combustion on α-Fe2O3. The macroscopic reaction characterization of hematite with CH4 was carried out on a fixed bed, and gas chromatography (GC) was utilized to detect the combustion products (CO2, H2O and H2). Subsequently, in situ spectroscopy and DFT were combined to reveal the detailed pathways for the CH₄ oxidation process. The results indicated that the reaction intermediates evolve from methoxy (CH3O*) to the bridged bidentate formate (b-HCOO*) to the monodentate formate (m-HCOO*), which ultimately leads to the formation of CO2 through a combination of H transfer and lattice oxygen oxidation. A micro-kinetic model was developed which incorporates surface reaction with the oxygen transport. This revealed that CH3O* and CH3O* → CH2OO* are the key intermediates and radical reactions, respectively, for CO2 production. The elucidation of the reaction mechanism may prove beneficial for the future development of novel Fe-based oxygen carriers.