Aine Desikusumastuti

Interaction of NO2 with Model NSR Catalysts: Metal–Oxide Interaction Controls Initial NOx Storage Mechanism

Using scanning tunneling microscopy (STM), molecular-beam (MB) methods and time-resolved infrared reflection absorption spectroscopy (TR-IRAS), we investigate the mechanism of initial NO(x) uptake on a model nitrogen storage and reduction (NSR) catalyst. The model system is prepared by co-deposition of Pd metal particles and Ba-containing oxide particles onto an ordered alumina film on NiAl(110). We show that the metal-oxide interaction between the active noble metal particles and the NO(x) storage compound in NSR model catalysts plays an important role in the reaction mechanism. We suggest that strong interaction facilitates reverse spillover of activated oxygen species from the NO(x) storage compound to the metal. This process leads to partial oxidation of the metal nanoparticles and simultaneous stabilization of the surface nitrite intermediate.

Nitrite and nitrate formation on model NOx storage materials: on the influence of particle size and composition

A well-defined model-catalyst approach has been utilized to study the formation and decomposition of nitrite and nitrate species on a model NO(x) storage material. The model system comprises BaAl(2x)O(1+3x) particles of different size and stoichiometry, prepared under ultrahigh-vacuum (UHV) conditions on Al(2)O(3)/NiAl(110). Adsorption and reaction of NO(2) has been investigated by molecular beam (MB) methods and time-resolved IR reflection absorption spectroscopy (TR-IRAS) in combination with structural characterization by scanning tunneling microscopy (STM). The growth behavior and chemical composition of the BaAl(2x)O(1+3x) particles has been investigated previously. In this work we focus on the effect of particle size and stoichiometry on the reaction with NO(2). Particles of different size and of different Ba(2+) : Al(3+) surface ion ratio are prepared by varying the preparation conditions. It is shown that at 300 K the reaction mechanism is independent of particle size and composition, involving initial nitrite formation and subsequent transformation of nitrites into surface nitrates. The coordination geometry of the surface nitrates, however, changes characteristically with particle size. For small BaAl(2x)O(1+3x) particles high temperature (800 K) oxygen treatment gives rise to particle ripening, which has a minor effect on the NO(2) uptake behavior, however. STM shows that the morphology of the particle system is largely conserved during NO(2) exposure at 300 K. The reaction is limited to the formation of surface nitrites and nitrates, which are characterized by low thermal stability and completely decompose below 500 K. As no further sintering occurs before decomposition, NO(2) uptake and release is a fully reversible process. For large BaAl(2x)O(1+3x) particles, aggregates with different Ba(2+) : Al(3+) surface ion ratio were prepared. It was shown that the stoichiometry has a major effect on the kinetics of NO(2) uptake. For barium-aluminate-like particles with high Al(3+) concentration, the formation of nitrites and nitrates on the BaAl(2x)O(1+3x) particles at 300 K is slow, and kinetically restricted to the formation of surface species. Only at elevated temperature (500 K) are surface nitrates converted into well-defined bulk Ba(NO(3))(2). This bulk Ba(NO(3))(2) exhibits substantially higher thermal stability and undergoes restructuring and sintering before it decomposes at 700 K. For Ba(2+)-rich BaAl(2x)O(1+3x) particles, on the other hand, nitrate formation occurs at a much higher rate than for the barium-aluminate-like particles. Furthermore, nitrate formation is not limited to the surface, but NO(2) exposure gives rise to the formation of amorphous bulk Ba(NO(3))(2) particles even at 300 K.

Model NOx Storage Materials at Realistic NO2 Pressures

The interaction of NO2 with single‐crystal‐based model NOx storage materials, consisting of barium aluminate nanoparticles on Al2O3/NiAl(110), are investigated by time‐resolved infrared reflection absorption spectroscopy (TR‐IRAS) at realistic NO2 partial pressures up to 1.75 mbar. The data is compared to spectra obtained under ultrahigh vacuum (UHV) conditions on the same model system. At 300 K, the NO2 uptake at pressures around 1 mbar proceeds through rapid initial formation of surface nitrites and nitrates, similar to that under UHV conditions. The vibrational spectra of the surface species formed at realistic NO2 pressures are comparable to those for species formed under UHV conditions. Beyond the formation of surface species, the formation of bulk nitrates occurs, but is kinetically strongly hindered. At a very low rate, the formation of a disordered barium bulk nitrate is detected. At 500 K, this kinetic hindrance is overcome and the available Ba2+ is quantitatively converted to bulk Ba(NO3)2. The IRAS spectrum of these Ba(NO3)2 particles differs characteristically from those obtained for nitrate multilayers formed upon incomplete conversion under UHV conditions. In addition to the formation of bulk Ba(NO3)2, a more weakly bound disordered nitrate species is formed. This species gives rise to a dynamic NO2 uptake and release well below the decomposition temperature of bulk Ba(NO3)2. The experiments show that model studies under UHV conditions mainly provide information on the initial reaction mechanism, whereas the observation of actual bulk NOx storage phases requires experiments at realistic temperatures and pressures.