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The journal of physical chemistry / C 126(7), 3411 - 3418 (2022). doi:10.1021/acs.jpcc.1c10284, We have used grazing incidence X-ray absorption fine structure spectroscopy at the cobalt K-edge to characterize monolayer CoO films on Pt(111) under ambient pressure exposure to CO and O$_2$, with the aim of identifying the Co phases present and their transformations under oxidizing and reducing conditions. X-ray absorption near edge structure (XANES) spectra show clear changes in the chemical state of Co, with the 2+ state predominant under CO exposure and the 3+ state predominant under O$_2$-rich conditions. Extended X-ray absorption fine structure spectroscopy (EXAFS) analysis shows that the CoO bilayer characterized in ultrahigh vacuum is not formed under the conditions used in this study. Instead, the spectra acquired at low temperatures suggest formation of cobalt hydroxide and oxyhydroxide. At higher temperatures, the spectra indicate dewetting of the film and suggest formation of bulklike Co$_3$O$_4$ under oxidizing conditions. The experiments demonstrate the power of hard X-ray spectroscopy to probe the structures of well-defined oxide monolayers on metal single crystals under realistic catalytic conditions., Published by Soc., Washington, DC

Spark ablation is an advantageous method for the generation of metallic nanoparticles with defined particle sizes and compositions. The reaction of the metal particles with the carrier gas during the synthesis and, therefore, the incorporation of those light elements into structural voids or even compound formation was confirmed for hydrides and oxides but has only been suspected to occur for nitrides. In this study, dispersed nanoparticles of Mo3Ni2N and Mo with Janus morphology, and defined particle sizes were obtained by spark discharge generation as a result of carrier gas ionization and characterized using transmission electron microscopy and powder X-ray diffraction. Metal nitrides possess beneficial catalytic and thermoelectric properties, as well as high hardness and wear resistance. Therefore, this method offers the possibility of controlled synthesis of materials which are interesting for numerous applications.

Active sites in Mo-based hydrotreating catalysts are produced by sulfidation. To achieve insights that may enable optimization of the catalysts, this process should be studied in situ. Herein we present a comparative XAFS study where the in situ sulfidation of Mo/δ-Al2O3and Ni/δ-Al2O3is compared to that of δ-Al2O3supported NiMo catalysts with different NiMo ratios. The study also covers the comparison of sulfidation of Ni and Mo using different oxide supports as well as the sulfidation conditions applied in the reactor. The XAFS spectra confirms the oxide phase for all catalysts at the beginning of the sulfidation reaction and their conversion to a sulfidized phase is followed with in situ measurements. Furthermore, it is found that the monometallic catalysts are less readily sulfidized than bimetallic ones, indicating the importance of Ni-Mo interactions for catalyst activation. Mo K-edge XAFS spectra did not show any difference related to the support of the catalyst or the pressure applied during the reaction. Ni K-edge XAFS spectra, however, show a more complete sulfidation of the Ni species in the catalyst when SiO2is used as a support as compared to the Al2O3. Nevertheless, it is believed that stronger interactions with Al2O3support prevent sintering of the catalyst which leads to its stabilization. The results contribute to a better understanding of how different parameters affect the formation of the active phase of the NiMo catalysts used in the production of biofuel.

A fundamental understanding of the process parameters affecting the catalytic hydrodeoxygenation (HDO) of bio-oils is of significance for enabling further progression and improvement of industrial biofuel upgrading methods. Herein, a novel demonstration and evaluation of the effect of temperature, pressure, and weight hourly space velocity in the continuous HDO of vanillin to cresol over a Ni-Mo/δ-Al2O3 catalyst are presented. Response surface methodology was used as a statistical experimental design method, and the application of central composite design enabled the generation of a statistically significant simulation model and a true optimization parametric study. The distribution of Ni and Mo on δ-Al2O3 was confirmed using scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDX). No gradients with EDX mapping could be identified, and the elemental analysis showed well-dispersion of the metals. The mesoporous character of the catalyst-support system was unraveled using N2 physisorption. Experiments were conducted within the parametric range of 250–350 °C, 3–9 bar, and 15–35 h−1. Both temperature and pressure were found to have statistically significant linear and quadratic effects on the selectivity for cresol. The parametric interaction of temperature with pressure and space velocity also had a significant effect on the resulting response. The optimal temperature range becomes more critical at lower space velocities. Optimal selectivity for cresol was established at 314 °C, 5 bar, and 35 h−1. The fitting quality of the generated regression model was statistically confirmed and experimentally validated to describe the specified HDO process within the 95% two-sided confidence interval.

Performing fundamental operando catalysis studies under realistic conditions is a key to further develop and increase the efficiency of industrial catalysts. Operando X-ray photoelectron spectroscopy (XPS) experiments have been limited to pressures, and the relevance for industrial applications has been questioned. Herein, we report on the CO oxidation experiment on Pd(100) performed at a total pressure of 1 bar using XPS. We investigate the light-off regime and the surface chemical composition at the atomistic level in the highly active phase. Furthermore, the observed gas-phase photoemission peaks of CO$_2$, CO, and O$_2$ indicate that the kinetics of the reaction during the light-off regime can be followed operando, and by studying the reaction rate of the reaction, the activation energy is calculated. The reaction was preceded by an in situ oxidation study in 7% O$_2$ in He and a total pressure of 70 mbar to confirm the surface sensitivity and assignment of the oxygen-induced photoemission peaks. However, oxygen-induced photoemission peaks were not observed during the reaction studies, but instead, a metallic Pd phase is present in the highly active regime under the conditions applied. The novel XPS setup utilizes hard X-rays to enable high-pressure studies, combined with a grazing incident angle to increase the surface sensitivity of the measurement. Our findings demonstrate the possibilities of achieving chemical information of the catalyst, operando, on an atomistic level, under industrially relevant conditions.

The reaction of ammonia oxidation over PtRh binary alloy has been studied with a surface science approach by operando techniques such as Near Ambient Pressure X-Ray Photoemission Spectroscopy (NAP-...

We have used grazing incidence X-ray absorption fine structure spectroscopy at the cobalt K-edge to characterize monolayer CoO films on Pt(111) under ambient pressure exposure to CO and O

Curved crystal surfaces enable the systematic and accurate comparison of physical and chemical processes for a full set of vicinal crystal planes, which are probed in the very same environment. Here, we examine the early stages of the CO chemisorption on vicinal Rh(111) surfaces using a curved Rh crystal that exposes a smoothly variable density of {100} (A-type) and {111} (B-type) steps. We readily identify and quantify step and terrace species by resolving their respective core-level lines using X-ray photoelectron spectroscopy at different locations on the curved surface. Uptake experiments show similar sticking probabilities at all surface planes, subtle asymmetries between A- and B-type steps, and significantly lower saturation coverage at densely stepped surfaces as compared to the (111) plane. The analysis of the C 1s intensity variation across the curved sample allows us to discuss the adsorption geometry around the step edge., We acknowledge financial support from the Spanish Ministry of Economy (Grants MAT-2016-78293-C6, MAT-2017- 88374-P), Basque Government (Grant IT-1255-19), the VR funded Röntgen−Angström collaboration “Catalysis on the atomic scale” project number 349-2011-6491, and the Knut and Alice Wallenberg (KAW) funded project “Atomistic design of new catalysts” project number KAW 2015.0058.

The catalytic oxidation of CO on transition metals, such as Pt, is commonly viewed as a sharp transition from the CO-inhibited surface to the active metal, covered with O. However, we find that minor amounts of O are present in the CO-poisoned layer that explain why, surprisingly, CO desorbs at stepped and flat Pt crystal planes at once, regardless of the reaction conditions. Using near-ambient pressure X-ray photoemission and a curved Pt(111) crystal we probe the chemical composition at surfaces with variable step density during the CO oxidation reaction. Analysis of C and O core levels across the curved crystal reveals that, right before light-off, subsurface O builds up within (111) terraces. This is key to trigger the simultaneous ignition of the catalytic reaction at different Pt surfaces: a CO-Pt-O complex is formed that equals the CO chemisorption energy at terraces and steps, leading to the abrupt desorption of poisoning CO from all crystal facets at the same temperature., We acknowledge financial support from the Spanish Ministry of Science and Innovation (Grants MAT-2017-88374-P, PID2019-107338RB-C63, PID2019-107338RB-C66), the Basque Government (Grants IT-1255-19, IT-1246-19), the Knut and Alice Wallenberg foundation (DNR KAW 2015.0058 „Atomistic Design of new Catalysts“) and the Swedish Research Council (DNR 349-2011-6491 „Catalysis on the atomic scale“).

Industrial catalysts are often comprised of nanoparticles supported on high-surface-area oxides, in order to maximise the catalytically active surface area and thereby utilise the active material better. These nanoparticles expose steps and corners that, due to low coordination to neighboring atoms, are more reactive and, as a consequence, are often assumed to have higher catalytic activity. We have investigated the reaction between CO and preadsorbed O on a stepped Rh(553) surface, and show that CO oxidation indeed occurs faster than on the flat Rh(111) surface at the same temperature. However, we do find that this is not a result of reactions at the step sites but rather at the terrace sites close to the steps, due to in-plane relaxation enabled by the step. This insight can provide ways to optimize the shape of the nanoparticles to further improve the activity of certain reactions.

A direct correlation between the reaction activity and the surface structure of a catalyst is generally needed to better understand the mechanisms behind the heterogeneous catalysis process. In this work, we employed planar laser-induced fluorescence (PLIF) to spatially resolve the CO2 distribution just above a Pd(100) surface, and simultaneously monitored the optical reflectance of the surface, during CO oxidation. We show that when the reaction is in the mass transfer limited regime, the inhomogeneity of the gas composition over the sample can lead to an inhomogeneity of the surface reflectance change arising from oxide formation and surface roughening. The combination of PLIF and surface reflectance also makes it possible to spatially resolve and simultaneously follow the dynamics of the gas phase and the surface on a subsecond time scale during self-sustained reaction oscillations of a Pd(100) surface, providing insights into the gas–surface interaction.

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 RuO

Journal of physics / D 53(22), 224001 (2020). doi:10.1088/1361-6463/ab77df, High energy surface x-ray diffraction (HESXRD), x-ray reflectivity (XRR), mass spectrometry (MS) and surface optical reflectance (SOR) have been combined to simultaneously obtain sub-second information on the surface structure and morphology from a Pd(100) model catalyst during in situ oxidation at elevated temperatures and pressures resulting in Pd bulk oxide formation. The results show a strong correlation between the HESXRD and SOR signal intensities during the experiment, enabling phase determination and a time-resolved thickness estimation of the oxide by HESXRD, complemented by XRR measurements. The experiments show a remarkable sensitivity of the SOR to changes in the surface phase and morphology, in particular to the initial stages of oxidation/reduction. The data imply that SOR can detect the formation of an ultrathin PdO surface oxide layer of only 2–3 Å thickness., Published by IOP Publ., Bristol

A stagnation flow reactor has been designed and characterized for both experimental and modeling studies of single-crystal model catalysts in heterogeneous catalysis. Using CO oxidation over a Pd(100) single crystal as a showcase, we have employed planar laser-induced fluorescence (PLIF) to visualize the CO2 distribution over the catalyst under reaction conditions and subsequently used the 2D spatially resolved gas phase data to characterize the stagnation flow reactor. From a comparison of the experimental data and the stagnation flow model, it was found that characteristic stagnation flow can be achieved with the reactor. Furthermore, the combined stagnation flow/PLIF/modeling approach makes it possible to estimate the turnover frequency (TOF) of the catalytic surface from the measured CO2 concentration profiles above the surface and to predict the CO2, CO and O2 concentrations at the surface under reaction conditions.

Review of scientific instruments 90(3), 033703 (2019). doi:10.1063/1.5086925, We have combined three techniques, High Energy Surface X-Ray Diffraction (HESXRD), Surface Optical Reflectance, and Planar Laser Induced Fluorescence in an operando study of CO oxidation over a Pd(100) catalyst. We show that these techniques provide useful new insights such as the ability to verify that the finite region being probed by techniques such as HESXRD is representative of the sample surface as a whole. The combination is also suitable to determine when changes in gas composition or surface structure and/or morphology occur and to subsequently correlate them with high temporal resolution. In the study, we confirm previous results which show that the Pd(100) surface reaches high activity before an oxide can be detected. Furthermore, we show that the single crystal catalyst surface does not behave homogeneously, which we attribute to the surface being exposed to inhomogeneous gas conditions in mass transfer limited scenarios, Published by American Institute of Physics, [S.l.]

Understanding how specific atom sites on metal surfaces lower the energy barrier for chemical reactions is vital in catalysis. Studies on simplified model systems have shown that atoms arranged as steps on the surface play an important role in catalytic reactions, but a direct comparison of how the light-off temperature is affected by the atom orientation on the step has not yet been possible due to methodological constraints. Here we report in situ spatially resolved measurements of the CO production over a cylindrical-shaped Pd catalyst and show that the light-off temperature at different parts of the crystal depends on the step orientation of the two types of steps (named A and B). Our finding is supported by density functional theory calculations, revealing that the steps, in contrast to what has been previously reported in the literature, are not directly involved in the reaction onset but have the role of releasing stress., The authors thank the Knut and Alice Wallenberg Foundation, the Swedish Research Council, the Swedish Foundation for Strategic Research, and the Crafoord Foundation. Support by the MAX IV staff is gratefully acknowledged. The calculations were performed at C3SE through a SNIC grant. J.E.O. acknowledges support from the Spanish Ministry of Economy (MAT2013-46593-C6-4-P) and the Basque Government (IT621-13).

We use multiscale modeling to analyze laser-induced fluorescence (LIF) measurements of the CO oxidation reaction over Pd(100) at near-ambient reaction conditions. Integrating density functional theory-based kinetic Monte Carlo simulations of the active catalyst into fluid-dynamical simulations of the mass transport inside the reactor chamber, we calculate the reaction product concentration directly above the catalyst surface. Comparing corresponding data calculated for different surface models against the measured LIF signals, we can discriminate the one that predominantly actuates the experimentally measured catalytic activity. For the probed CO oxidation reaction conditions, the experimental activity is due to pristine Pd(100) possibly coexisting with other (oxidic) domains on the surface.

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.

Journal of synchrotron radiation 25(5), 1389 - 1394 (2018). doi:10.1107/S1600577518010597, High-energy surface X-ray diffraction (HESXRD) provides surface structural information with high temporal resolution, facilitating the understanding of the surface dynamics and structure of the active phase of catalytic surfaces. The surface structure detected during the reaction is sensitive to the composition of the gas phase close to the catalyst surface, and the catalytic activity of the sample itself may affect the surface structure, which in turn may complicate the assignment of the active phase. For this reason, planar laser-induced fluorescence (PLIF) and HESXRD have been combined during the oxidation of CO over a Pd(100) crystal. PLIF complements the structural studies with an instantaneous two-dimensional image of the CO$_2$ gas phase in the vicinity of the active model catalyst. Here the combined HESXRD and PLIF operando measurements of CO oxidation over Pd(100) are presented, allowing for an improved assignment of the correlation between sample structure and the CO$_2$ distribution above the sample surface with sub-second time resolution., Published by Wiley-Blackwell, [S.l.]

Understanding nanoparticle catalysis requires novel approaches in which adjoining crystal orientations can be studied under the same reactive conditions. Here we use a curved palladium crystal and near-ambient pressure X-ray photoemission spectroscopy to characterize chemical species during the catalytic oxidation of CO in a whole set of surfaces vicinal to the (111) direction simultaneously. By stabilizing the reaction at fixed temperatures around the ignition point, we observe a strong variation of the catalytic activity across the curved surface. Such spatial modulation of the reaction stage is straightforwardly mapped through the photoemission signal from active oxygen species and poisoning CO, which are shown to coexist in a transient regime that depends on the vicinal angle. Line-shape analysis and direct comparison with ultrahigh vacuum experiments help identifying and quantifying all such surface species, allowing us to reveal the presence of surface oxides during reaction ignition and cooling-off., We acknowledge financial support from the Spanish Ministry of Economy (Grants MAT-2012-38567-C02-02, MAT-2016-78293-C6, MAT-2017-88374-P) and Basque Government (Grant IT-1255-19).

We have studied the oxidation and reduction of Rh(100) and SiO2 supported Rh particles using high pressure X-ray photoelectron spectroscopy. We show that the formation and reduction of Rh bulk oxide can be followed in situ in O-2 and CO pressures in the range of 0.1 Torr. In general, the oxidation/reduction processes are similar on Rh(100) and the nanoparticles, but there are significant differences in temperature dependence. Already at a sample temperature of 140 degrees C, the particles show clear signs of a thin bulk oxide, while an ultra-thin so-called surface oxide covers the single crystal at the same temperature. Both of these oxide films, however, hinder further oxidation, and a thick oxide is only found at a temperature of at least 300 degrees C, for both samples. The reduction, in contrast, starts at a higher temperature on the particles as compared to the single crystal, but once started the particles are completely reduced at lower temperatures. (C) 2014 Elsevier B.V. All rights reserved. (Less)

Reduction of the (root 5 x root 5)R27 degrees surface oxide on Pd(1 0 0) and Pd75Ag25(1 0 0) surfaces by H-2 has been studied using high-resolution photoelectron spectroscopy in situ at H-2 pressures 5 x 10(-9) mbar and 5 x 10(-8) mbar and selected temperatures in the range 30 degrees C to 170 degrees C. The reduction is slower on Pd75Ag25(1 0 0) compared to Pd(1 0 0) for all temperatures and pressures investigated. For Pd(1 0 0), the surface oxide reduction rate is rather independent of temperature, while for Pd75Ag25(1 0 0) a nonmonotonic variation is observed. As indicated by kinetic analysis, the complex reduction behavior is not well described by Avrami kinetics. Oxygen spillover effects contribute to this picture for Pd(1 0 0), while surface compositional effects appear to dominate the performance for Pd75Ag25(1 0 0). These findings may have implications for understanding the oxidation, reduction and hydrogen transport properties of Pd-Ag membranes. (C) 2014 Elsevier B.V. All rights reserved. (Less)

High-pressure X-ray photoelectron spectroscopy, mass spectrometry, and density functional theory calculations have been combined to study methane oxidation over Pd(100). The measurements reveal a high activity when a two-layer PdO(101) oriented film is formed. Although a one-layer PdO(101) film exhibits a similar surface structure, no or very little activity is observed. The calculations show that the presence of an oxygen atom directly below the coordinatively unsaturated Pd atom in the two-layer PdO(101) film is crucial for efficient methane dissociation, demonstrating a ligand effect that may be broadly important in determining the catalytic properties of oxide thin films.

Surface structures formed by exposing Ag(111) to atomic oxygen have been studied by X-ray photoelectron spectroscopy, scanning tunneling microscopy, and density functional theory calculations. From the combination of the experimental and theoretical results, a model is proposed for the 0.5 ML oxygen coverage with a c(4 x 8) periodicity. Moreover, we find that a bulk-like Ag2O phase starts to form at coverages above 0.5 ML.

The reduction of the (A root 5x root 5)R27 degrees surface oxide on Pd(100) and Pd75Ag25(100) surfaces by CO has been investigated by high-resolution X-ray photoelectron spectroscopy in combination with kinetic analysis using the Avrami-Erofeev theory. For both surfaces we observed faster reduction with increasing temperature. Kinetic analysis indicates that the reduction process is phase boundary controlled for Pd(100) in the temperature range investigated, from 30 degrees C to 120 degrees C On Pd75Ag25(100) the surface oxide reduction is significantly slower compared to Pd(100). Also in this case, a phase boundary controlled reduction of the surface oxide is observed at temperatures of 120 C and above, while at T

An in-depth understanding of the reaction mechanism is required for the further development of Mo-based catalysts for biobased feedstocks. However, fundamental studies of industrial catalysts are challenging, and simplified systems are often used without direct comparison to their industrial counterparts. Here, we report on size-selected bimetallic NiMo nanoparticles as a candidate for a model catalyst that is directly compared to the industrial system to evaluate their industrial relevance. Both the nanoparticles and industrial supported NiMo catalysts were characterized using surface- and bulk-sensitive techniques. We found that the active Ni and Mo metals in the industrial catalyst are well dispersed and well mixed on the support, and that the interaction between Ni and Mo promotes the reduction of the Mo oxide. We successfully produced 25 nm NiMo alloyed nanoparticles with a narrow size distribution. Characterization of the nanoparticles showed that they have a metallic core with a native oxide shell with a high potential for use as a model system for fundamental studies of hydrotreating catalysts for biobased feedstocks.

X-ray photoelectron spectroscopy and density functional theory calculations are used to investigate NO adsorption at low (100 K) and room temperature (RT) over preoxidized Ag(111). At 100 K, the data indicates presence of NO and N2O2, with little or no nitrite/nitrate formation. This is consistent with the calculated surface core level shifts and the pronounced barrier for nitrite formation. At RT, the recorded spectra indicate a complex interconversion between adsorbed species with an initial formation of a p(4 x 4) nitrate overlayer. With increasing NO pressure, the experimental results are best rationalized by partial nitrate decomposition into nitrites and subsequent NO physisorption, which leads to the formation of N2O3-like species. (C) 2013 Elsevier B.V. All rights reserved.

PdAg nanoparticles with a diameter of 10 nm have been generated by an aerosol particle method, and supported on a silica substrate. By using a combination of X-ray Energy Dispersive Spectroscopy and X-ray Photoelectron Spectroscopy it is shown that the size distribution of the particles is narrow and that the two metals form an alloy with a mixture of 75% Pd and 25% Ag. Under oxidizing conditions, Pd is found to segregate to the surface and a thin PdO like oxide is formed similar to the surface oxide previously reported on extended PdAg and pure Pd surfaces.

High-resolution core-level spectroscopy (HRCLS) and density functional theory (DFT) calculations have been used to investigate the adsorption and dissociation of hydrogen on a PdO(101) film grown on Pd(111). Energy-dependent measurements of the O 1s and Pd 3d(5/2) binding energies enable identification of surface components that correspond to undercoordinated Pd and O atoms. HRCLS data obtained at 110 K, after hydrogen exposure at the same temperature, reveal hydrogen adsorption and formation of Pd-H and O-H groups. Adsorption at room temperature results instead in complete reduction of the oxide. The experimental results are supported by the DFT calculations of core-level shifts and barriers for water formation.

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\(_2\).

High resolution photoelectron spectroscopy and density functional theory calculations have been used to study the composition of clean and oxidized Pd75Ag25( 100). The results for the clean surface confirm earlier reports of surface segregation by Wouda et al. (1998), where the top most layers are rich in Ag. The Pd 3d core level component from the surface region is observed at higher binding energies than the contribution from the bulk which is found to be a signature of Pd embedded in Ag. Low energy electron diffraction and scanning tunneling microscopy measurements reveal that oxidation of the Pd75Ag25(100) surface results in a (root 5 x root 5)R27 degrees-O structure similar to the one reported for Pd(100). The calculations suggest that the stable structure is a PdO(101) monolayer supported on a (100) surface rich in Ag at the interface to the stoichiometric alloy. The calculated core level shifts for the oxidized surface are in good agreement with the experimental observations.

We have studied the (0001) surface termination of Rh2O3 on a Rh(111) single crystal using a combination of high resolution core level spectroscopy, low energy electron diffraction, scanning tunneling microscopy and density functional theory. By exposing the Rh(111) to atomic oxygen we are able to grow Rh2O3 layers exposing the (0001) surface. The experiments support the theoretical predictions stating that the surface is terminated with an O-Rh-O trilayer yielding a RhO2 termination instead of a bulk Rh2O3 termination. The structural details as found by the DFT calculations are presented and reasons for the previously observed strong differences in catalytic activity between the structurally similar RhO2 surface oxide, and the Rh2O3(0001) surface are discussed. (C) 2012 Elsevier B.V. All rights reserved. (Less)

We present a method to deposit Pd nanoparticles with a very small size distribution by an aerosol process onto oxide substrates for the creation of model systems in catalytic research. The Pd nanoparticles are characterized by transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. We confirm the small size dispersion from the desired particle size, and we show that the particle surface coverage can be highly controlled. Further, our measurements indicate that an amorphous shell surrounding a crystalline core of the Pd particles may form during the particle synthesis and that the shell contains carbon.

In heterogeneous catalysis the reactions occur on the surface of a catalyst. To understand the reaction pathways, a detailed understanding on an atomic level is critical. However, the gas atmosphere surrounding the surface dictates the interaction between the surface and the gas. At low pressures this is often neglected, but as the community turns to higher pressures it becomes important to consider gas related effects. We have used laser diagnostics to characterize the gas distributions during catalysis and thereby been able to deduce information that would otherwise lay hidden. Several of our recent results are summarized and highlighted and simultaneous measurements of the surface structure using synchrotron based methods and the gas phase using laser diagnostics is discussed.

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., Visualization of the gas distribution around working catalyst is crucial for understanding structure–activity relationships. Here, the authors show that gas distribution can be imaged in situ with high spatial and temporal resolution using infrared planar laser-induced fluorescence.

We have studied the oxidation of CO over Rh(100) using high pressure x-ray photoelectron spectroscopy under CO and O2 pressures ranging from 0.01 to 1 mbar. The results show a very low or no conversion for the CO covered surface found at low temperatures, while the activity rises slightly when the temperature is high enough for some CO to desorb, exposing surface sites for dissociative O2 adsorption. As the temperature is increased further, more CO desorbs and oxygen replaces CO as the dominating species at the surface. At the same time we find a sudden increase in the reactivity, such that all CO that reaches the surface is instantly transformed into CO2. We find that the O coverage in the active state is highly dependent on the total pressure and, although we do not detect any presence of a surface oxide as in previous surface x-ray diffraction studies, the highest O coverage indicates that the surface is close to being oxidized.

In situ knowledge of the gas phase around a catalyst is essential to make an accurate correlation between the catalytic activity and surface structure in operando studies. Although ambient pressure X-ray photoelectron spectroscopy (AP-XPS) can provide information on the gas phase as well as the surface structure of a working catalyst, the gas phase detected has not been spatially resolved to date, thus possibly making it ambiguous to interpret the AP-XPS spectra. In this work, planar laser-induced fluorescence (PLIF) is used to visualize the CO2 distribution in a model AP-XPS reactor, during CO oxidation over a Pd(100) catalyst. The results show that the gas composition in the vicinity of the sample measured by PLIF is significantly different from that measured by a conventional mass spectrometer connected to a nozzle positioned just above the sample. In addition, the gas distribution above the catalytic sample has a strong dependence on the gas flow and total chamber pressure. The technique presented has the potential to increase our knowledge of the gas phase in AP-XPS, as well as to optimize the design and operating conditions of in situ AP-XPS reactors for catalysis studies.

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 CO2 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.

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.

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.

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.

Physical review / B 86, 035407 (2012). doi:10.1103/PhysRevB.86.035407, We investigated the interaction of oxygen with the Pd(112) surface from ultrahigh vacuum up to 5 mbars oxygen partial pressure in a temperature range from 523 to 673 K. We combined in situ surface x-ray diffraction with scanning tunneling microscopy, high-resolution core-level spectroscopy, and low-energy electron diffraction. A structural model of the clean Pd(112) is proposed based on the x-ray-diffraction data. The morphology of the Pd(112) surface is strongly influenced by the oxidation conditions: at 673 K, upon exposure to oxygen at pressures from 2×10−8 to 5×10−5 mbar, the (112) surface undergoes a massive rearrangement and (113)- and (335)-type facets are formed. Further increase of the O2 partial pressure leads to a new rearrangement into (111)- and (113)-type facets. This is in contrast to the previous observation that (112) facets are stabilized on MgO supported Pd nanoparticles under oxygen exposure [P. Nolte, A. Stierle, N. Kasper, N. Y. Jin-Phillipp, N. Jeutter, and H. Dosch, Nano Lett. 11, 4697 (2011)]. Based on the core-level spectroscopy and scanning tunneling microscopy measurements, the transition from chemisorbed oxygen to surface oxide formation was identified to take place at pressures of 10−3 mbar O2 and 623 K. Kinetic barriers for the formation of the PdO bulk oxide are observed to be reduced compared to low index Pd surfaces., Published by APS, College Park, Md.

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.

High-resolution core-level spectroscopy and density-functional theory calculations have been used to investigate CO adsorption on the p(4 x 4) structure of oxidized Ag(111). CO adsorption with subsequent carbonate formation was observed at 100 K. The experimental results are consistent with calculations that reveal low activation barriers to form CO(2) and CO(3)(2-) from adsorbed CO. On the basis of a good match between calculated and experimental shifts in the Ag 3d and O 1s core-level binding energies, a model for a monolayer of carbonates on p(4 x 4)-O/Ag(111) is proposed.

We have studied the ultrathin aluminum oxide film on NiAl(110) by a combination of high-resolution core-level spectroscopy and density functional theory calculations. Energy-dependent core-level data from the O 1s and Al 2p levels allows for a distinction between oxygen and aluminum atoms residing at the surface or inside the aluminum oxide film. A comparison to calculated core-level binding energies from the recent model by Kresse et al. [Science 308, 1440 (2005)] reveals good agreement with experiment, and the complex spectroscopic signature of the thin Al oxide on NiAl(110) can be explained. Our assignment of a shifted component in the O 1s spectra to oxygen atoms at the surface with a particular Al and oxygen coordination may have implications for the interpretation of photoelectron-diffraction experiments from similar ultrathin aluminum oxide films.

Using in situ high-pressure x-ray photoelectron spectroscopy, we have followed the oxidation and the reduction of Pd model catalysts in oxygen and CO pressures in the millibar range. The study includes a Pd(100) single crystal as well as SiOx-supported Pd nanoparticles of 15 or 35 nm diameter, respectively. We demonstrate that nanoparticles also form ultrathin surface oxides prior to the onset of the bulk PdO. The Pd nanoparticles are observed to bulk oxidize at sample temperatures 40 degrees lower than the single-crystal surface. In the Pd 3d(5/2) and the O 1s spectrum, we identify a component corresponding to undercoordinated atoms at the surface of the PdO oxide. The experimentally observed PdO core-level shift is supported by density functional theory calculations. In a CO atmosphere, the Pd 3d(5/2) component corresponding to undercoordinated PdO atoms is shifted by + 0.55 eV with respect to PdO bulk, demonstrating that CO molecules preferably adsorb at these sites. CO coordinated to Pd atoms in the metallic and the oxidized phases can also be distinguished in the C 1s spectrum. The initial reduction by CO is similar for the single-crystal and the nanoparticle samples, but after the complete removal of the oxide we detect a significant deviation between the two systems, namely that the nanoparticles incorporate carbon to form a Pd carbide. Our results indicate that CO can dissociate on the nanoparticle samples, whereas no such behavior is observed for the Pd(100) single crystal. These results demonstrate the similarities, as well as the important differences, between the single crystals used as model systems for catalysis and nm-sized particles on oxide supports.