An atomic level understanding of the structure and stability of model catalysts is essential for surface science studies in heterogeneous catalysis. Scanning tunneling microscopy (STM) can operate both in UHV and under realistic pressure conditions with a wide temperature span while providing atomic resolution images. Taking advantage of the ability of STM, our research focuses on 1) investigating the structure and stability of supported Au catalysts, especially under CO oxidation conditions, and 2) synthesizing and characterizing a series of alloy model catalysts for future model catalytic studies. In our study, Au clusters supported on TiO2(110) have been used to model supported Au catalysts. Our STM studies in UHV reveal surface structures of TiO2(110) and show undercoordinated Ti cations play a critical role in the nucleation and stabilization of Au clusters on TiO2(110). Exposing the TiO2(110) surface to water vapor causes the formation of surface hydroxyl groups and subsequently alters the growth kinetics of Au clusters on TiO2(110). STM studies on Au/TiO2(110) during CO oxidation demonstrate the real surface of a working catalyst. Au clusters supported on TiO2(110) sinter rapidly during CO oxidation, but are mostly stable in the single component reactant gas, either CO or O2. The sintering kinetics of supported Au clusters has been measured during CO oxidation and gives an activation energy, which supports the mechanism of CO oxidation induced sintering. CO oxidation was also found to accelerate the surface diffusion of Rh(110). Our results show a direct correlation between the reaction rate of CO oxidation and the diffusion rate of surface metal atoms. Synthesis of alloy model catalysts have also been attempted in our study with their structures successfully characterized. Planar Au-Pd alloy films has been prepared on a Rh(100) surface with surface Au and Pd atoms distinguished by STM. The growth of Au-Ag alloy clusters have been studied by in-situ STM on a cluster-to-cluster basis. Moreover, the atomic structure of a solution-prepared Ru3Sn3 cluster has been resolved on an ultra-thin silica film surface. The atomic structure and adsorption sites of the ultrathin silica film have also been well characterized in our study.

Oxide thin films and bimetallic model catalysts have been studied using metastable impact electron spectroscopy (MIES), ultraviolet photoelectron spectroscopy (UPS), low energy ion scattering spectroscopy (LEISS), X – ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED), infrared reflection absorption spectroscopy (IRAS) and temperature programmed desorption (TPD) under ultra high vacuum (UHV) conditions. Of particular interest in this investigation was the characterization of the surface morphology and electronic/geometric structure of the following catalysts: SiO2/Mo(112), Ag/SiO2/Mo(112), Au–Pd/Mo(110), Au–Pd/SiO2/Mo(110), and Pd– Sn/Rh(100). Specifically, different types of oxide surface defects were directly identified by MIES. The interaction of metal clusters (Ag) with defects was examined by work function measurements. On various Pd related bimetallic alloy surfaces, CO chemisorption behavior was addressed by IRAS and TPD. Observed changes in the surface chemical properties during the CO adsorption-desorption processes were explained in terms of ensemble and ligand effects. The prospects of translating this molecular-level information into fundamental understanding of ‘real world’ catalysts are discussed.

The physical and catalytic properties of silica supported platinum or rhodium model catalysts are studied under both ultra high vacuum (UHV) and elevated pressure reaction conditions (>1torr). Platinum or rhodium nanoparticles are vapor deposited onto a SiO2/Mo(112) surface and characterized using various surface analytical methods. CO chemisorption is utilized as a surface probe to estimate the concentration of various sites on the nanoparticles through thermal desorption spectroscopy (TDS) and infrared reflection absorption spectroscopy (IRAS) along with microscopy techniques to estimate particle size. The results are compared with hard sphere models of face centered cubic metals described as truncated cubo-octahedron. Results demonstrate the excellent agreement between chemisorption and hard sphere models in estimating the concentration of undercoordinated atoms on the nanoparticle surface. Surfaces are then subjected to high pressure reaction conditions to test the efficacy of utilizing the rate of a chemical reaction to obtain structural information about the surface. The surfaces are translated in-situ to a high pressure reaction cell where both structure insensitive and sensitive reactions are performed. Structure insensitive reactions (e.g. CO oxidation) allow a method to calculate the total active area on a per atom basis for silica supported platinum and rhodium model catalysts under reaction conditions. While structure sensitive reactions allow an estimate of the types of reaction sites, such as step sites (≤C7) under reaction conditions (e.g. n-heptane dehydrocyclization). High pressure structure sensitive reactions (e.g. ethylene hydroformylation) are also shown to drastically alter the morphology of the surface by dispersing nanoparticles leading to inhibition of catalytic pathways. Moreover, the relationships between high index single crystals, oxide supported nanoparticles, and high surface area technical catalysts are established. Overall, the results demonstrate the utility of model catalysts in understanding the structure-activity relationships in heterogeneous catalytic reactions and the usefulness of high pressure reactions as an analytical probe of surface morphology.

Heterogene Katalyse ist eine Schlüsseltechnologie der chemischen Industrie. Ceroxid wird für eine Reihe von katalytischen Reaktionen verwendet. Wegen seiner hervorragenden Eignung als Sauerstoffspeicher sind dies vor allem Oxidationsreaktionen. Studien zeigen, dass Ceroxid unter anderem als Substrat für Vanadiumoxid und Goldnanopartikel im Vergleich zu anderen Substraten zu einer erhöhten Aktivität führt. Diese Systeme wurden zur Untersuchung mittels oberflächenphysikalischer Messmethoden (LEED, STM, PES, IRAS) erfolgreich als Modellkatalysator nachgebildet. Dafür wurde ein zuverlässiges Rezept zur Präparation von CeO2(111)-Filmen auf Ru(0001) und CeOx-Nanopartikel auf einlagigen kristallinen Siliziumoxidfilmen auf Mo(112) entwickelt. Durch PES-, STM- und IRAS-Messungen wurden diese strukturell und elektronisch charakterisiert. In einer vergleichenden Untersuchung konnte festgestellt werden, dass Gold auf den Ceroxidnanopartikeln eine viel stärkere Wechselwirkung mit dem Ceroxidsubstrat zeigt als auf dem Ceroxidfilm. Gold bedeckt die Ceroxidnanopartikel; die teilweise geladene Au delta+-Spezies stabilisieren. Durch kombinierte STM, PES und IRAS–Messungen, zusammen mit DFT-Rechnungen der Arbeitsgruppe von J. Sauer an der Humboldt-Universität zu Berlin, konnte die Struktur sogenannter Vanadiumoxid – „monolayer“ – Katalysatoren entschlüsselt und die Nuklearität der Vanadiumoxidspezies an der Oberfläche den Streckschwingfrequenzen der Vanadylgruppen zugeordnet werden. Es wurde gezeigt, dass die bei geringer Bedeckung beobachteten Vanadiummonomere aus vanadylterminierten VO4-Tetraedern bestehen, die sich je nach Bedeckung und Temperatur vor allem zu Trimeren und Heptameren zusammenschließen. Die Vanadiumatome dieser Vanadiumspezies werden dabei durch den CeO2(111)-Film im Oxidationszustand 5+ bei gleichzeitiger Reduktion von Ce-Ionen der CeO2(111)-Oberfläche von 4+ auf 3+ in O2-Umgebung und unter UHV-Bedingungen stabilisiert. / Heterogenous catalysis is a key technology in chemical industry. Cerium oxide is used for a number of catalytic reactions. Due to its good oxygen-storage capabilities, it is mostly used in oxidation reactions. In comparison to other materials cerium oxide, as a support for gold and vanadium oxide, shows the highest activity. These systems were successfully prepared as model catalysts for investigation with surface science techniques (LEED, STM, PES, IRAS). Therefore a reliable recipe was developed for the preparation of CeO2(111) thin films on Ru(0001) and CeOx nanoparticles on monolayer crystalline silicon oxide films on Mo(112). These substrates were characterized using PES, STM, and IRAS measurements. In a comparative study, gold deposited on cerium oxide nanoparticles was shown to exhibit a much stronger interaction than on cerium oxide thin films. On cerium oxide nanoparticles, the gold preferentially binds to the nanoparticle surfaces and stabilizes partially-charged Au delta+-species. By means of combined STM, PES und IRAS measurements, together with DFT calculations by the research group of J. Sauer from the Humboldt-Universität zu Berlin, the atomic structure of the so-called vanadium oxide – “monolayer“ – catalyst has been resolved. A direct relationship between the nuclearity of vanadium oxide species on the surface and the vanadyl frequency was then established. It was shown, that the vanadium oxide monomers (observed at low coverages) consist of vanadyl-terminated VO4 tetrahedra. The monomers were observed to aglomerate mostly to trimers and heptamers by coverage or temperature increase. The vanadium atoms in these species are stabilized in the oxidation state 5+ by the simultaneous reduction of cerium ions in the cerium oxide substrate from the oxidation state +4 to +3, both in oxygen atmosphere and under UHV conditions.

<p>The strong metal support interaction (SMSI) is among the best-known classes of metal-oxide interfacial interactions in heterogeneous catalysis, which is defined by the coverage of surface oxide on metal nanoparticles, forming a metal-oxide interface. However, there is limited insight in the atomic scale understanding of the structure of the SMSI oxide. In this work, surface science techniques including scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HREELS) and low energy electron diffraction (LEED) were employed to investigate interfacial interactions in multiple catalytic systems, including ZnO-Pd, ZnO-Pt, and MoOx-Pt. To utilize the capabilities of the surface science techniques and to mimic a catalytic metal nanoparticle in SMSI state, ultrathin oxide films were prepared on metal single crystals as inverse model catalysts.</p> <p>The structural and chemical transformations of ultrathin zinc (hydroxy)oxide films on Pd(111) were studied under varying gas phase conditions (UHV, 5×10−7 mbar of O2 and D2/O2 mixture). Under oxidative conditions, zinc oxide forms partially hydroxylated bilayer islands on Pd(111). Sequential treatments of the submonolayer ZnOxHy films in D2/O2 mixture (1:4) at 550 K evoked structural transformations from bilayer to monolayer and to a PdZn near-surface alloy, in accompany with the reduction of Zn, demonstrating that zinc oxide as a non-reducible oxide, can spread on metal surface and show an SMSI-like behavior in the presence of hydrogen. A mixed canonical – grand canonical phase diagram revealed that the monolayer intermediate structure is a metastable structure formed during the kinetic transformation, and the near-surface alloys are stable under the D2/O2 conditions. Grand canonical phase diagram predicted that under real SMSI conditions zinc oxide films on Pd nanoparticles would be stabilized by hydroxylation with stoichiometries such as ZnOH and Zn2O3H3. Based on the experimental and theoretical observations, we propose that the mechanism of metal nanoparticle encapsulation involves both surface (hydroxy)oxide formation as well as alloy formation, depending on the environmental conditions.</p> <p>Hydroxylation plays a more important role in the ZnO/Pt(111) system. Different from Pd(111), zinc oxide tends to form monolayer graphite-like ZnO films on Pt(111) under oxidative conditions at submonolayer coverages. This structure is extremely susceptible to hydroxylation at room temperature, leading to spontaneous formation of honeycomb-like Zn6O5H5 films in hydrogen. The interaction of the two distinct structures with Pt were investigated by XPS, STM, and HREELS with CO, C2H4, and NO as probe molecules. Zn exhibits a partially reduced oxidation state in Zn6O5H5 and donates negative charge to surface Pt in the confined rings, leading to a switch from linear CO adsorption to bridged CO adsorption in accompany with a 50 cm-1 shift of ν(CO) towards lower frequencies. C2H4 readily forms ethylidyne (*CCH3) species at room temperature once adsorbed on Pt(111), while the formation of ethylidyne is weakened on the Zn6O5H5/Pt(111) surface. In summary, this study demonstrated a unique metal-hydroxide interaction, which serves as a novel approach for the modification of metal catalysts.</p> <p>The partial coverage of metal surfaces by oxides could be utilized to passivate specific sites of catalysts, improving the activity and stability. Herein, we studied the structure of surface Mo oxides on Pt(111) and Pt(544) using STM, XPS, and HREELS. At 0.08 ML coverage, Mo oxide tends to form 1~2 nm clusters and the majority of Mo is in +5 oxidation state. The Mo oxide clusters tend to aggregate near the monoatomic Pt steps, showing a higher local density compared to the wide terraces. Therefore, our results provide experimental evidence for the site-selective growth of Mo oxides at step sites, which could prevent the leaching of active component in catalysts under real reaction conditions.</p> <p>Overall, through atomic-level characterization of inverse model catalysts, we provided insights into the nature of metal-oxide interactions in multiple systems. The surface oxide films influence the property of metal surfaces in various ways, including migration, alloy formation, electronic perturbation, geometric confinement, and site-selective blocking. These findings emphasize the necessity of understanding the real structure of catalytic surfaces under different reaction conditions and shed light on rational design of oxide supported metal nanoparticle catalysts.</p>

Die Umsetzung von alpha,beta-ungesättigten Aldehyden und Ketonen mit Wasserstoff über Pd-Modellkatalysatoren wurde anhand von Molekularstrahlmethoden, kombiniert mit Infrarot-Reflexions-Absorptions-Spektroskopie (IRAS), Quadrupol-Massenspektrometrie (QMS) und Röntgen-Nahkanten-Absorptions-Spektroskopie (NEXAFS), unter wohldefinierten Ultrahochvakuumbedingungen untersucht. Das Ziel dieser Arbeit war es, ein atomistisches Verständnis der strukturellen Faktoren zu gewinnen, die die Aktivität und Selektivität eines Pd(111)-Einkristalls und Eisenoxid-geträgerter Pd-Nanopartikel für die Hydrierung der C=C- und C=O-Bindungen bestimmen. Exemplarisch für diese Art von Kohlenwasserstoffen wurden das Aldehyd Acrolein und das Keton Isophoron gewählt. Die NEXAFS- und IRAS-Studien zeigten, dass Isophoron bei niedrigen Bedeckungen auf Pd(111) in einer flachliegenden Geometrie adsorbiert wird. Die Neigungswinkel der C=C- und C=O-Bindungen in Bezug auf die Pd(111)-Ebene nehmen mit zunehmender Oberflächenbedeckung zu. Auf reinem Pd(111) ist die Neigung der C=C-Bindung stärker ausgeprägt, was auf eine Verzerrung des konjugierten pi-Systems hindeutet. Bei Anwesenheit von Wasserstoff wird eine schwächere Bindung von Isophoron an Pd beobachtet. Die selektive partielle Hydrierung über einer Pd(111)-Oberfläche und geträgerten Pd-Nanopartikeln unterschiedlicher Größen wurde unter Verwendung von Acrolein untersucht. Molekularstrahlmethoden wurden mit IRAS- und QMS-Messungen kombiniert, um gleichzeitig die Bildung von Adsorbaten auf der Oberfläche und die der Produkte in der Gasphase verfolgen zu können. Über einem Pd(111)-Kristall wird Propenol mit nahezu 100% Selektivität durch Hydrierung der C=O-Gruppe gebildet, während über Pd-Partikeln Propanal durch selektive Hydrierung der C=C-Gruppe erzeugt wird. IRAS-Untersuchungen zeigten, dass die Propenol-Bildung eine Modifikation der Pd(111)-Oberfläche mit einer dichten Oxopropyl-Monolage voraussetzt. / The conversion of alpha,beta-unsaturated aldehydes and ketones with hydrogen over model Pd catalysts was investigated using molecular beam techniques combined with infrared reflection-absorption spectroscopy (IRAS), quadrupole mass spectrometry (QMS), and near-edge X-ray absorption fine structure (NEXAFS) studies under well-defined ultra-high vacuum conditions. The aim of this work was to gain atomistic-level understanding of structural factors governing the selectivity and activity of a Pd(111) single crystal and iron-oxide-supported Pd nanoparticles for C=C and C=O bond hydrogenation. The ketone isophorone and the aldehyde acrolein were chosen as prototypical alpha,beta-unsaturated carbonyl compounds. NEXAFS and IRAS studies showed that isophorone is adsorbed on Pd(111) in a flat-lying geometry at low coverages. With increasing coverage, both C=C and C=O bonds tilt with respect to the surface plane. The tilting is more pronounced for the C=C bond on pristine Pd(111), indicating a strong distortion of the conjugated pi system upon interaction with Pd. Co-adsorbed hydrogen leads to a conservation of the in-plane geometry of the conjugated pi system, pointing to a much weaker interaction of isophorone with Pd in the presence of hydrogen. The selective partial hydrogenation over a Pd(111) surface and supported Pd nanoparticles with different particle sizes was investigated using acrolein. Molecular beam techniques were combined with IRAS and QMS measurements in order to simultaneously monitor the evolution of surface species and the formation of the final gas-phase products. Over a Pd(111) single crystal, acrolein is hydrogenated at the C=O bond to form propenol with nearly 100% selectivity, while over supported Pd particles, selective conversion of the C=C bond to propanal occurs. IRAS investigations showed that a distinct modification of the Pd(111) surface with a dense overlayer of an oxopropyl species is required for propenol formation.