The Structure and Catalytic Properties of MoVTeNbO Catalysts Modified by Adding Cr, Fe, Ce and W

Cr, Fe, Ce and W doped MoVTeNbO M2 phase catalysts were synthesized and used in the selective oxidation of propylene to acrylic acid (AA). Results show that the introduction of Cr, Fe, Ce and W substantially affects the physicochemical properties and catalytic performance of MoVTeNbO-based catalysts. Un-doped catalyst consists of M2 phase and TeO₂, while Cr, Fe, Ce and W-doped catalysts are mainly composed of M2 and MoO₃. It is indicated that doping of Cr, Fe, Ce and W can restrain the formation of TeO₂, but favour the formation of MoO₃. Un-doped, Cr and W-doped catalysts display irregular-shaped particles morphology, while Fe and Ce-doped catalysts display nanosheets morphology. In addition, the valence of superficial elements of catalysts changed greatly with the doping elements. For catalytic performance, in addition to Cr, the propylene conversion of the catalyst decreases obviously with doping of other elements, probably due to the drastically reduced specific surface area with doping of Fe, Ce and W. The existence of Cr and Ce can increase the selectivity to AA at all test temperatures (360–440 ℃), while Fe and W-doped catalysts only show higher selectivity than the un-doped one at high temperature of 420 and 440 ℃. It is illustrated that the catalysts with redox ability at relatively low temperature is more favorable for the selectivity to AA. Among them, Cr-doped catalyst shows the highest selectivity (85.3%) and yield (63.5%) of AA at test temperature of 380 ℃, which are 15.3 and 7.5% higher than that of un-doped catalyst, respectively.

Graphic Abstract

The M2 phase MoVTeNbO catalysts doped with Cr, Fe, Ce and W have been synthesized. It is demonstrated that the addition of Cr improves the stability of Te⁴⁺, and Cr-doped M2 phase shows excellent catalytic performance in the selective oxidation of propylene to acrylic acid.