Mechanism of ammonia oxidation over oxides studied by temporal analysis of products

A temporal analysis of products (TAP) reactor was used to study the mechanism of ammonia oxidation at high temperature (1073 K) over Fe2O3, Cr2O3, and CeO2. The results were compared with those obtained over the industrially applied Pt-95-Rh-5 alloy. Analysis of characteristic times of the transient responses of N-2 and NO made it possible to gain insight into the sequence of their formation. A common feature of both metal oxide and noble metal catalysts is that NO is a primary product of NH3 oxidation, whereas N-2 results mainly from secondary transformations of NO. The amount of N2O formed over the oxides was minimal. Multipulse NH3 experiments in the absence of gas-phase O-2 give unequivocal evidence of the participation of surface lattice oxygen of the metal oxides in the reaction of NH3 to NO. The degree of reduction of the oxide surface determines the product distribution but does not alter the catalytic activity for NH3 conversion. Greater reduction favors the reaction channel to N-2 over that to NO. The desired reaction follows a Mars-van Krevelen-type scheme involving the participation of lattice oxygen in the NH3 conversion to NO and regeneration of the so-formed vacancies by gas-phase 02 and bulk lattice oxygen. Replenishment of surface vacancies by the diffusion of bulk oxygen occurs to a significant extent over Fe2O3. However, when NH3 and 02 are fed together, dissociative adsorption of gas-phase oxygen can be considered the main mechanism for vacancy regeneration. (c) 2007 Elsevier Inc. All rights reserved.