No abstract

Two series of Pt/γ-Al 2 O 3 catalysts for low temperature NH 3 oxidation were prepared using Pt(NO 3 ) 4 and H 2 PtCl 6 precursors. Using both precursors results in the formation of small Pt particles (d < 1.5 nm), however, Cl-containing Pt precursors give a higher fraction of highly dispersed Pt species. Such species show high stability against thermal or H 2 treatment probably due to the presence of a substantial amount of chlorine on the surface. Treatment of the samples prepared from Pt(NO 3 ) 4 with H 2 leads to the formation of metallic Pt nanoparticles accompanied by the improvement of catalytic activity in NH 3 oxidation at T < 200°C. The main products of ammonia oxidation at temperatures below 250°C were molecular nitrogen and nitrous oxide with the N 2 selectivity reaching 80 %. Operando XANES/ EXAFS revealed that even after H 2 pretreatment at least 40 % of Pt surface remains in oxidized state under reaction conditions resulting in the appearance of N 2 O as a by-product.

NAP-XPS and operando XAS study of Pt/TiO2 catalysts shows that Pt0 species stabilized on TiO2 surface have the highest activity at low-temperature NH3 oxidation.

Dependence of NH3 oxidation on the state and dispersion of Pt species in Pt/γ‐Al2O3 catalysts was investigated. Prereduced Pt/γ‐Al2O3 catalysts containing Pt0 nanoparticles exhibited significantly higher activity than preoxidized ones with the same Pt dispersion. The most significant improvement of the catalytic activity (TOF increased by 30 times) was observed when the size of Pt0 particles increased from ∼1 to ∼8 nm. N2 selectivity was found to be mainly determined by the reaction temperature, with a minor influence of Pt particle size. Preoxidized catalysts containing ionic Pt were activated by the reaction medium, while partial deactivation was observed for the prereduced ones. The activity improvement was associated with the presence of Pt4+/Pt2+ species on the surface of preoxidized catalysts. The activity decrease of the prereduced catalysts was due to the partial oxidation and subsequent redispersion of Pt particles. Introduction of H2O and CO2 to the reaction mixture only moderately influenced NH3 oxidation activity shifting NH3 conversion curves by about +15 °C.