Monolayer- and crystal-type MoO3 catalysts: Their catalytic properties in relation to their surface structures

Abstract

Various MoO3 catalysts have been prepared by means of adsorption of molybdenum on supports from molybdate solutions or from the gas phase. Complete monomolecular layers of Mo 6+ oxide can be prepared on the carriers Al2Oz, CrzOz, TiO2, CeO2, and ZrO2, whereas on SiO2 crystallites of MoO3 are formed. Reduction experiments show that the higher valencies of Mo are stabilized in the case of a monomolecular layer. Alcohol dehydration, pentene hydrogenation, and poisoning of these reactions with pyridine reveal that MoO2 present as a monolayer is less acidic than crystalline MOO2. On the complete monolayer catalysts investigated, mostly more than 70% of the dehydration and hydrogenation activities can be correlated with sites showing a relatively high acidity which are equivalent to 10-20% of the Mo content. The CO oxidation rates on the oxidized catalysts are antiparallel to those of the reactions on the reduced ones mentioned above; relatively basic sites preferentially chemisorb CO. The conclusion is that the activity pattern of the catalysts is a function of the acidity of the supports. It is suggested that Mo 5+ ions contribute to the formation of the active acid sites after reduction with hydrogen.