Sara Blomberg

In Situ X-Ray Photoelectron Spectroscopy of Model Catalysts : At the Edge of the Gap

We present high-pressure x-ray photoelectron spectroscopy (HP-XPS) and first-principles kinetic Monte Carlo study addressing the nature of the active surface in CO oxidation over Pd(100). Simultaneously measuring the chemical composition at the surface and in the near-surface gas phase, we reveal both O-covered pristine Pd(100) and a surface oxide as stable, highly active phases in the near-ambient regime accessible to HP-XPS. Surprisingly, no adsorbed CO can be detected during high CO(2) production rates, which can be explained by a combination of a remarkably short residence time of the CO molecule on the surface and mass-transfer limitations in the present setup.

Reversible formation of a PdCx phase in Pd nanoparticles upon CO and O-2 exposure

The structure and chemical composition of Pd nanoparticles exposed to pure CO and mixtures of CO and O(2) at elevated temperatures have been studied in situ by a combination of X-ray Diffraction and X-ray Photoelectron Spectroscopy in pressures ranging from ultra high vacuum to 10 mbar and from room temperature to a few hundred degrees celsius. Our investigation shows that under CO exposure, above a certain temperature, carbon dissolves into the Pd particles forming a carbide phase. Upon exposure to CO and O(2) mixtures, the carbide phase forms and disappears reversibly, switching at the stoichiometric ratio for CO oxidation. This finding opens new scenarios for the understanding of catalytic oxidation of C-based molecules.

Bulk and surface characterization of In2O3(001) single crystals

A comprehensive bulk and surface investigation of high-quality In2O3(001) single crystals is reported. The transparent-yellow, cube-shaped single crystals were grown using the flux method. Inductively coupled plasma mass spectrometry (ICP-MS) reveals small residues of Pb, Mg, and Pt in the crystals. Four-point-probe measurements show a resistivity of 2.0 +/- 0.5 x 10(5) Omega cm, which translates into a carrier concentration of approximate to 10(12) cm(-3). The results from x-ray diffraction (XRD) measurements revise the lattice constant to 10.1150(5) angstrom from the previously accepted value of 10.117 angstrom. Scanning tunneling microscopy (STM) images of a reduced (sputtered/annealed) and oxidized (exposure to atomic oxygen at 300 degrees C) surface show a step height of 5 angstrom, which indicates a preference for one type of surface termination. The surfaces stay flat without any evidence for macroscopic faceting under any of these preparation conditions. A combination of low-energy ion scattering (LEIS) and atomically resolved STM indicates an indium-terminated surface with small islands of 2.5 angstrom height under reducing conditions, with a surface structure corresponding to a strongly distorted indium lattice. Scanning tunneling spectroscopy (STS) reveals a pronounced surface state at the Fermi level (E-F). Photoelectron spectroscopy (PES) shows additional, deep-lying band gap states, which can be removed by exposure of the surface to atomic oxygen. Oxidation also results in a shoulder at the O 1s core level at a higher binding energy, possibly indicative of a surface peroxide species. A downward band bending of 0.4 eV is observed for the reduced surface, while the band bending of the oxidized surface is of the order of 0.1 eV or less.

An in situ set up for the detection of CO(2) from catalytic CO oxidation by using planar laser-induced fluorescence.

We report the first experiment carried out on an in situ setup, which allows for detection of CO(2) from catalytic CO oxidation close to a model catalyst under realistic reaction conditions by the means of planar laser-induced fluorescence (PLIF) in the mid-infrared spectral range. The onset of the catalytic reaction as a function of temperature was followed by PLIF in a steady state flow reactor. After taking into account the self-absorption of CO(2), a good agreement between the detected CO(2) fluorescence signal and the CO(2) mass spectrometry signal was shown. The observed difference to previously measured onset temperatures for the catalytic ignition is discussed and the potential impact of IR-PLIF as a detection technique in catalysis is outlined.

Real-Time Gas-Phase Imaging over a Pd(110) Catalyst during CO Oxidation by Means of Planar Laser-Induced Fluorescence

The gas composition surrounding a catalytic sample has direct impact on its surface structure, which is essential when in situ investigations of model catalysts are performed. Herein a study of the gas phase close to a Pd(110) surface during CO oxidation under semirealistic conditions is presented. Images of the gas phase, provided by planar laser-induced fluorescence, clearly visualize the formation of a boundary layer with a significantly lower CO partial pressure close to the catalytically active surface, in comparison to the overall concentration as detected by mass spectrometry. The CO partial pressure variation within the boundary layer will have a profound effect on the catalysts’ surface structure and function and needs to be taken into consideration for in situ model catalysis studies.

Spatially and temporally resolved gas distributions around heterogeneous catalysts using infrared planar laser-induced fluorescence

Visualizing and measuring the gas distribution in close proximity to a working catalyst is crucial for understanding how the catalytic activity depends on the structure of the catalyst. However, existing methods are not able to fully determine the gas distribution during a catalytic process. Here we report on how the distribution of a gas during a catalytic reaction can be imaged in situ with high spatial (400 μm) and temporal (15 μs) resolution using infrared planar laser-induced fluorescence. The technique is demonstrated by monitoring, in real-time, the distribution of carbon dioxide during catalytic oxidation of carbon monoxide above powder catalysts. Furthermore, we demonstrate the versatility and potential of the technique in catalysis research by providing a proof-of-principle demonstration of how the activity of several catalysts can be measured simultaneously, either in the same reactor chamber, or in parallel, in different reactor tubes.

2D and 3D imaging of the gas phase close to an operating model catalyst by planar laser induced fluorescence

In recent years, efforts have been made in catalysis related surface science studies to explore the possibilities to perform experiments at conditions closer to those of a technical catalyst, in particular at increased pressures. Techniques such as high pressure scanning tunneling/atomic force microscopy (HPSTM/AFM), near ambient pressure x-ray photoemission spectroscopy (NAPXPS), surface x-ray diffraction (SXRD) and polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS) at semi-realistic conditions have been used to study the surface structure of model catalysts under reaction conditions, combined with simultaneous mass spectrometry (MS). These studies have provided an increased understanding of the surface dynamics and the structure of the active phase of surfaces and nano particles as a reaction occurs, providing novel information on the structure/activity relationship. However, the surface structure detected during the reaction is sensitive to the composition of the gas phase close to the catalyst surface. Therefore, the catalytic activity of the sample itself will act as a gas-source or gas-sink, and will affect the surface structure, which in turn may complicate the assignment of the active phase. For this reason, we have applied planar laser induced fluorescence (PLIF) to the gas phase in the vicinity of an active model catalysts. Our measurements demonstrate that the gas composition differs significantly close to the catalyst and at the position of the MS, which indeed should have a profound effect on the surface structure. However, PLIF applied to catalytic reactions presents several beneficial properties in addition to investigate the effect of the catalyst on the effective gas composition close to the model catalyst. The high spatial and temporal resolution of PLIF provides a unique tool to visualize the on-set of catalytic reactions and to compare different model catalysts in the same reactive environment. The technique can be applied to a large number of molecules thanks to the technical development of lasers and detectors over the last decades, and is a complementary and visual alternative to traditional MS to be used in environments difficult to asses with MS. In this article we will review general considerations when performing PLIF experiments, our experimental set-up for PLIF and discuss relevant examples of PLIF applied to catalysis.

Comparison of AP-XPS and PLIF Measurements during CO Oxidation over Pd Single Crystals

The interaction between the gas-phase molecules and a catalyst surface is crucial for the surface structure and are therefore important to consider when the active phase of a catalyst is studied. In this study we have used two different techniques to study the gas phase during CO oxidation over Pd single crystals. Gas-phase imaging by planar laser-induced fluorescence (PLIF) shows that a spherical boundary layer with a decreasing gradient of CO2 concentration out from the surface, is present close to the surface when the Pd crystal is highly active. Within this boundary layer the gas composition is completely different than that detected at the outlet of the chamber. The PLIF images of the gas-phase distribution are used to achieve a better understanding of the gas composition between the surface and the detector of a set-up for ambient pressure X-ray photoelectron spectroscopy (AP-XPS), a common technique for surface structure determination of model catalysts. The results show that also the gas-phase peaks present in the AP-XPS spectra truly represent the gas closest to the surface, which facilitates the interpretation of the AP-XPS spectra and thereby also the understanding of the mechanism behind the reaction process.

Novel in Situ Techniques for Studies of Model Catalysts

Motivated mainly by catalysis, gas-surface interaction between single crystal surfaces and molecules has been studied for decades. Most of these studies have been performed in well-controlled environments and have been instrumental for the present day understanding of catalysis, providing information on surface structures, adsorption sites, and adsorption and desorption energies relevant for catalysis. However, the approach has been criticized for being too far from a catalyst operating under industrial conditions at high temperatures and pressures. To this end, a significant amount of effort over the years has been used to develop methods to investigate catalysts at more realistic conditions under operating conditions. One result from this effort is a vivid and sometimes heated discussion concerning the active phase for the seemingly simple CO oxidation reaction over the Pt-group metals in the literature. In recent years, we have explored the possibilities to perform experiments at conditions closer to those of a technical catalyst, in particular at increased pressures and temperatures. In this contribution, results from catalytic CO oxidation over a Pd(100) single crystal surface using Near Ambient Pressure X-ray Photo emission Spectroscopy (NAPXPS), Planar Laser-Induced Fluorescence (PLIF), and High Energy Surface X-ray Diffraction (HESXRD) are presented, and the strengths and weaknesses of the experimental techniques are discussed. Armed with structural knowledge from ultrahigh vacuum experiments, the presence of adsorbed molecules and gas-phase induced surface structures can be identified and related to changes in the reactivity or to reaction induced gas-flow limitations. In particular, the application of PLIF to catalysis allows one to visualize how the catalyst itself changes the gas composition close to the model catalyst surface upon ignition, and relate this to the observed surface structures. The effect obscures a straightforward relation between the active phase and the activity, since in the case of CO oxidation, the gas-phase close to the model catalyst surface is shown to be significantly more oxidizing than far away from the catalyst. We show that surface structural knowledge from UHV experiments and the composition of the gas phase close to the catalyst surface are crucial to understand structure-function relationships at semirealistic conditions. In the particular case of Pd, we argue that the surface structure of the PdO(101) has a significant influence on the activity, due to the presence of Coordinatively Unsaturated Sites (CUS) Pd atoms, similar to undercoordinated Ru and Ir atoms found for RuO2(110) and IrO2(110), respectively.

Planar laser induced fluorescence applied to catalysis

In this chapter we describe Planar Laser Induced Fluorescence (PLIF) to investigate the reactants or products in the vicinity of a catalyst at semi-realistic conditions. PLIF provides a 2D view of the gas-phase distribution of a pre-chosen gas. Here we present PLIF results from CO\(_2\) and CO from the oxidation of CO into CO\(_2\) by Pd single crystals and by various powder catalysts as well as from NH\(_3\) from the oxidation of NH\(_3\) above a Ag/Al\(_2\)O\(_3\) powder catalyst. We describe our experimental set-up in detail, and the laser instrumentation needed to enable detectable gas fluorescence from CO\(_2\), CO, and NH\(_3\), respectively. Further, intensity corrections of the PLIF signal due to scattering and temperature effects are described. In the case of the CO oxidation, the results directly show the creation of a CO\(_2\) boundary layer and thus a drastic change of the gas-phase composition close to the catalyst surface, illustrating the effect of gas diffusion and reaction speed, which in turn should affect the surface structure of the active catalyst. The 2D character of the PLIF images is used to investigate differences in catalyst activity by studying adjacent catalysts in the reaction cell during the reaction, and a solution to avoid spill-over effects between catalysts in the same reactor is presented. The results from PLIF images of CO of the same reaction show the corresponding depletion of the PLIF intensity above the catalyst, in accordance with observations from other techniques confirming the drastic difference between the gas composition close to the catalyst and at the inlet or outlet of the reactor. Finally we present NH\(_3\) PLIF results from above a Ag/Al\(_2\)O\(_3\) powder catalyst while the NH\(_3\) is being oxidized in an oxidizing environment with the assistance of H\(_2\).