Structural Changes of Binary/Ternary Spinel Oxides During Ethanol Anaerobic Decomposition

Several M-modified iron oxides of the spinel family have proven to be effective electron and O2−vectors for the production of hydrogen in the chemical-loop reforming of bio-alcohols. The present work is specifically focused on investigation of ethanol anaerobic decomposition over spinel oxides, which results in significant structural changes of the oxygen carrier material itself and corresponds to a first step of the chemical-loop reforming process. In particular, a series of binary/ternary M-modified ferrospinels were prepared by a co-precipitation method and tested in terms of both redox properties and intrinsic catalytic activity in addition to a complex ex situ study that encompasses the solid-state chemistry investigations of the fresh and reduced oxygen carrier materials. It was found that Co/Cu incorporation facilitates total/partial oxidation of ethanol, giving rise to high yields of H2, COx, and H2O; whereas Mn incorporation predominantly favored dehydrogenation and condensation reactions, leading to the formation of acetaldehyde and acetone. In addition, the incorporation of Mn contributed to significantly reduce the amount of coke formed; however, it caused a lower intrinsic reducibility, which was explained by the formation of a thermodynamically stable and hardly reducible layer of MnxFeyO solid solution.