Cobalt molybdate support interactions

Molybdenum oxide - alumina systems have been studied in detail (4-8). Several authors have pointed out that a molybdate surface layer is formed, due to an interaction between molybdenum oxide and the alumina support (9-11). Richardson (12) studied the structural form of cobalt in several oxidic cobalt-molybdenum-alumina catalysts. The presence of an active cobalt-molybdate complex was concluded from magnetic susceptibility measurements. Moreover cobalt aluminate and cobalt oxide were found. Only the active cobalt molybdate complex would contribute to the activity and be characterized by octahedrally coordinated cobalt. Lipsch and Schuit (10) studied a commercial oxidic hydrodesulfurization catalyst, containing 12 wt% M0O3 and 4 wt% CoO. They concluded that a cobalt aluminate phase was present and could not find indications for an active cobalt molybdate complex. Recent magnetic susceptibility studies of the same type of catalyst (13) confirmed the conclusion of Lipsch and Schuit. 

The oxidation of propene to acrolein has been one of the most studied selective oxidation reaction. The catalysts used are usually pure bismuth molybdates owing to the fact that these phases are present in industrial catalysts and that they exhibit rather good catalytic properties (1). However the industrial catalysts also contain bivalent cation molybdates like cobalt, iron and nickel molybdates, the presence of which improves both the activity and the selectivity of the catdysts (2,3). This improvement of performances for a mixture of phases with respect to each phase component, designated synergy effect, has recently been attributed to a support effect of the bivalent cation molybdate on the bismuth molybdate (4) or to a synergy effect due to remote control (5) or to more or less strong interaction between phases (6). However, this was proposed only in view of kinetic data obtained on a prepared supported catalyst. 

However, the molybdenum-alumina and the high calcined cobalt-molybdenum-alumina samples still show an important difference. The pyridine spectra of MoCo-124 indicate a second Lewis acid site, characterized by the 1612 cm-1 band. This band differs from the weak Lewis acid sites of the alumina support (1614 cm- ) because the position is significantly different. It also appears that the strength of the bond between pyridine and the catalyst is stronger, for the 1612 cm-1 band is still present after evacuation at 250°C, while the weak Lewis band (1614 cm-1) of the alumina has disappeared at this desorption temperature. Obviously the second Lewis band for the MoCo-124 catalyst is introduced by the interaction of cobalt with the surface molybdate layer. This interaction is... 

Such an effect might be expected when boehmite supported cobalt is being calcined, viz. during the phase transition AIO(OH) - y-Al203. Figure 7 shows spectra of pyridine, adsorbed on the sample CoMo-124 B, which has been prepared in this way. Spectra for MoCo-122, -123 and -124, containing 2, 3 and 4 wt% CoO resp. are shown for comparison. All these catalysts have had a final calcination of 650°C. Comparison of the spectra of CoMo-124 B and MoCo-124 indicates that the intensity of the 1612 cm l band, which is introduced by the interaction of the cobalt ions and the molybdate layer, is lower for CoMo-124 B than for MoCo-124. The spectrum for CoMo-124 B resembles that of CoMo-123, indicating that a part of the cobalt ions does not participate in this interaction. 

---