On the Role of Morphology of CoFeO4 Spinel in Methanol Anaerobic Oxidation

A CoFe2O4 inverse spinel calcined at two different temperatures (450 and 750 °C), in order to modulate the growth of the crystallites, has been employed in methanol anaerobic oxidation. A correlation between physicochemical properties and catalytic performances of the material has been pursued. The study of both surface and bulk properties has been carried out by means of different experimental techniques, among which are X-ray diffraction (XRD), transmission electron microscopy (TEM), and in situ FTIR spectroscopy. The FTIR study of both bulk and surface spectral features reveals that the calcination step is responsible for the different type of exposed surface sites and as a consequence for the different catalytic behavior. As the use of the spinel as the catalyst for methanol transformation into H2 necessarily implies a regeneration step with steam, in order to recover the oxidative capacity of the solid, both surface and bulk features of the reoxidized solids have been also studied. All results reveal that the two samples, originally morphologically quite different from one another, become very similar after just one redox cycle. Still, it has been also demonstrated that both used materials irreversibly modify their surface properties after the reduction/oxidation process.