Effects of Activation Atmospheres on Structure and Activity of Mo-based Catalyst for Synthesis of Higher Alcohols

Abstract

Activated carbon supported Mo-based catalysts were prepared and reduced under different activation atmospheres, including pure H2, syngas (H2/CO=2/1), and pure CO. The catalysts structures were characterized by X-ray diffraction , X-ray absorption fine structure, and in situ diffuse reflectance infrared Fourier transform spectroscopy. The catalytic performance for the higher alcohol synthesis from syngas was tested. The pure H2 treatment showed a high reduction capacity. The presence of a large amount of metallic Co0 and low valence state Moφ+ (0<φ<2) on the surface suggested a super activity for the CO dissociation and hydrogenation, which promoted hydrocarbons formation and reduced the alcohol selectivity. In contrast, the pure CO-reduced catalyst had a low reduction degree. The Mo and Co species at the catalyst mainly existed in the form of Mo4+ and Co2+. The syngas-reduced catalyst showed the highest activity and selectivity for the higher alcohols synthesis. We suggest that the syngas treatment had an appropriate reduction capacity that is between those of pure H2 and pure CO and led to the coexistence of multivalent Co species as well as the enrichment of Moδ+ on the catalyst's surface. The synergistic effects between these active species provided a better cooperativity and equilibrium between the CO dissociation, hydrogenation and CO insertion and thus contributed beneficially to the formation of higher alcohols.