Methanol oxidation over model cobalt catalysts: Influence of the cobalt oxidation state on the reactivity

X-ray photoelectron and absorption spectroscopies (XPS and XAS) combined with on-line mass spectrometry were applied under working catalytic conditions to investigate methanol oxidation on cobalt. Two cobalt oxidation states (Co3O4 and CoO) were prepared and investigated as regards their influence on the catalytic activity and selectivity. In addition adsorbed species were monitored in the transition of the catalyst from a non-active state, to an active one. It is shown that the surface oxidation state of cobalt is readily adapted to the oxygen chemical potential in the CH3OH/O2 reaction mixture. In particular, even in oxygen-rich mixtures the Co3O4 surface is partially reduced, with the extent of surface reduction following the methanol concentration. The reaction selectivity depends on the cobalt oxidation state, with the more reduced samples favouring the partial oxidation of methanol to formaldehyde. In the absence of oxygen, methanol effectively reduces cobalt to the metallic state, also promoting H2 and CO production. Direct evidence of methoxy and formate species adsorbed on the surface upon reaction was found by analysing the O 1s and C 1s photoelectron spectra. However, the surface coverage of those species was not proportional to the catalytic activity, indicating that they might also act as reaction inhibitors.

Graphical abstractMethanol oxidation on cobalt: the relation between the gas phase composition (I), the cobalt oxidation state (II) and the dominant reaction paths (III), observed by combined on-line mass spectrometry (QMS) and in situ X-ray absorption spectroscopy (XAS). The X-ray absorption spectra of Co L3,2 edge were obtained on a cobalt crystal under reaction mixture at 520 K, using different methanol-to-oxygen mixing ratios.Figure optionsDownload full-size imageDownload high-quality image (103 K)Download as PowerPoint slide