ABSTRACT
Towards a better understanding of novel catalytic materials consisting of supported noble metal catalysts modified by an ionic liquid (IL) film, we have performed a study under ultrahigh-vacuum (UHV) conditions. The model surface consists of Pd nanoparticles grown in UHV on an ordered alumina film on NiAl(110). Thin films of the room temperature IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [BMIM][Tf(2)N] are deposited onto this surface by means of physical vapor deposition (PVD). The interaction of the IL with clean and CO-covered Pd/Al(2)O(3)/NiAl(110) at 300 K and the thermal behavior of the deposited IL films on Pd/Al(2)O(3)/NiAl(110) are investigated by time-resolved infrared reflection absorption spectroscopy (TR-IRAS) and X-ray photoelectron spectroscopy (XPS). At 300 K, the IL adsorbs molecularly both onto the Pd particles and onto the alumina. The IR spectra suggest that the [Tf(2)N](-) anions interact with Pd sites preferentially via the sulfonyl groups. CO pre-adsorbed on the Pd particles is partially displaced by the IL, even at 300 K, and only the part of CO adsorbed onto hollow sites on (111) facets of the Pd particles remains in place. Upon heating to temperatures higher than the desorption temperature of the IL (>400 K), molecular desorption of the IL competes with decomposition. The decomposition products, atomic species and small fragments, remain preferentially adsorbed onto the Pd nanoparticles and strongly modify their surface properties. Most of the decomposition products originate from the [BMIM](+) cations, whereas the [Tf(2)N](-) anions desorb for the most part.
ABSTRACT
Aiming at a better understanding of the interaction of ionic liquid (IL) thin films with oxide supports, we have performed a model study under ultrahigh vacuum (UHV) conditions. We apply infrared reflection absorption spectroscopy (IRAS) in combination with density functional theory (DFT). Thin films of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [BMIM][Tf(2)N] are grown on an atomically flat, well-ordered alumina film on NiAl(110) using a novel UHV-compatible evaporator. Time-resolved IRAS measured during the growth and subsequent thermal desorption points toward reversible molecular adsorption and desorption. There was no indication of decomposition. The vibrational bands are assigned with the help of DFT calculations. Strong relative intensity changes in individual [Tf(2)N](-) bands are observed in the monolayer region. This indicates pronounced orientation effects for the anion. The adsorption geometry of [Tf(2)N](-) is determined on the basis of a detailed comparison with DFT. The results suggest that [Tf(2)N](-) anions adopt a cis conformation in the submonolayer region. They adsorb in a slightly tilted orientation with respect to the surface, mainly interacting with the support via the sulfonyl groups.
Subject(s)
Aluminum Oxide/chemistry , Computer Simulation , Imidazoles/chemistry , Imides/chemistry , Ionic Liquids/chemistry , Membranes, Artificial , Models, Chemical , Sulfonamides/chemistry , Anions/chemistry , Catalysis , Molecular Conformation , Surface PropertiesABSTRACT
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.