Effect of cobalt oxide on surface structure of alumina supported molybdena catalysts studied by in situ Raman spectroscopy

Abstract

A set of Co promoted 10% Mo/Al2O3 samples have been characterized by means of Raman spectroscopy under ambient as well as in situ dehydrated conditions. Under ambient conditions, the degree of the polymerization of surface molybdenum oxide species decreases with increasing Co loading. Under dehydrated conditions, the polymeric molybdenum oxide species is absent with the addition of only 0.2% Co. At low Co loadings (⩽2%), before the formation of CoMoO4 compound, the spectral features are very similar under ambient conditions. Dehydration causes the upward shift of the Mo=O symmetric stretching mode. A broad band around 920–930 cm−1 was thus observed. This band has been suggested to be associated with the Co-Mo interaction species. In contrast to crystalline CoMoO4, this species shows a reversibility on H2 reduction-O2 reoxidation treatments. From the results obtained, it is proposed that cobalt oxide interacts with the most polymerized molybdenum oxide species to form Co-Mo interaction species and/or crystalline CoMoO4; therefore, the amount of the surface molybdenum oxide species decreases with a change in the molecular structure as a function of the Co concentration.