Niklas Nilius

Nanoparticles for Heterogeneous Catalysis: New Mechanistic Insights

Metallic nanoparticles finely dispersed over oxide supports have found use as heterogeneous catalysts in many industries including chemical manufacturing, energy-related applications and environmental remediation. The compositional and structural complexity of such nanosized systems offers many degrees of freedom for tuning their catalytic properties. However, fully rational design of heterogeneous catalysts based on an atomic-level understanding of surface processes remains an unattained goal in catalysis research. Researchers have used surface science methods and metal single crystals to explore elementary processes in heterogeneous catalysis. In this Account, we use more realistic materials that capture part of the complexity inherent to industrial catalysts. We assess the impacts on the overall catalytic performance of characteristics such as finite particle size, particle structure, particle chemical composition, flexibility of atoms in clusters, and metal-support interactions. To prepare these materials, we grew thin oxide films on metal single crystals under ultrahigh vacuum conditions and used these films as supports for metallic nanoparticles. We present four case studies on specifically designed materials with properties that expand our atomic-level understanding of surface chemistry. Specifically, we address (1) the effect of dopants in the oxide support on the growth of metal nanoclusters; (2) the effects of size and structural flexibility of metal clusters on the binding energy of gas-phase adsorbates and their catalytic activity; (3) the role of surface modifiers, such as carbon, on catalytic activity and selectivity; and (4) the structural and compositional changes of the active surface as a result of strong metal-support interaction. Using these examples, we demonstrate how studies of complex nanostructured materials can help revealing atomic processes at the solid-gas interface of heterogeneous catalysts. Among our findings is that doping of oxide materials opens promising routes to alter the morphology and electronic properties of supported metal particles and to induce the direct dissociation and reaction of molecules bound to the oxide surface. Also, the small size and atomic flexibility of metal clusters can have an important influence on gas adsorption and catalytic performance.

Gold supported on thin oxide films: From single atoms to nanoparticles

[Figure: see text]. Historically, people have prized gold for its beauty and the durability that resulted from its chemical inertness. However, even the ancient Romans had noted that finely dispersed gold can give rise to particular optical phenomena. A decade ago, researchers found that highly dispersed gold supported on oxides exhibits high chemical activity in a number of reactions. These chemical and optical properties have recently prompted considerable interest in applications of nanodispersed gold. Despite their broad use, a microscopic understanding of these gold-metal oxide systems lags behind their application. Numerous studies are currently underway to understand why supported nanometer-sized gold particles show catalytic activity and to explore possible applications of their optical properties in photonics and biology. This Account focuses on a microscopic understanding of the gold-substrate interaction and its impact on the properties of the adsorbed gold. Our strategy uses model systems in which gold atoms and clusters are supported on well-ordered thin oxide films grown on metal single crystals. As a result, we can investigate the systems with the rigor of modern surface science techniques while incorporating some of the complexity found in technological applications. We use a variety of different experimental methods, namely, scanning probe techniques (scanning tunneling microscopy and spectroscopy, STM and STS), as well as infrared (IR), temperature-programmed desorption (TPD), and electron paramagnetic resonance (EPR) spectroscopy, to evaluate these interactions and combine these results with theoretical calculations. We examined the properties of supported gold with increasing complexity starting from single gold atoms to one- and two-dimensional clusters and three-dimensional particles. These investigations show that the binding of gold on oxide surfaces depends on the properties of the oxide, which leads to different electronic properties of the Au deposits. Changes in the electronic structure, namely, the charge state of Au atoms and clusters, can be induced by surface defects such as color centers. Interestingly, the film thickness can also serve as a parameter to alter the properties of Au. Thin MgO films (two to three monolayer thickness) stabilize negatively charged Au atoms and two-dimensional Au particles. In three dimensions, the properties of Au particles bigger than 2-3 nm in diameter are largely independent of the support. Smaller three-dimensional particles, however, showed differences based on the supporting oxide. Presumably, the oxide support stabilizes particular atomic configurations, charge states, or electronic properties of the ultrasmall Au aggregates, which are in turn responsible for this distinct chemical behavior.

Quantum well states in two-dimensional gold clusters on MgO thin films

The electronic structure of ultrasmall Au clusters on thin MgO/Ag(001) films has been analyzed by scanning tunneling spectroscopy and density functional theory. The clusters exhibit two-dimensional quantum well states, whose shapes resemble the eigenstates of a 2D electron gas confined in a parabolic potential. From the symmetry of the highest occupied (HOMO) and lowest unoccupied molecular orbital (LUMO) of a particular cluster, its electron filling and charge state is determined. In accordance with a Bader charge analysis, aggregates containing up to 20 atoms accumulate one to four extra electrons due to a charge transfer from the MgO/Ag interface. The HOMO-LUMO gap is found to close for clusters containing between 70 and 100 atoms.

Temperature‐Dependent Morphology, Magnetic and Optical Properties of Li‐Doped MgO

Li‐doped MgO is a potential catalyst for the oxidative coupling of methane, whereby surface Li+ O− centers are suggested to be the chemically active species. To elucidate the role of Li in the MgO matrix, two model systems are prepared and their morphological, optical and magnetic properties as a function of Li doping are investigated. The first is an MgO film deposited on Mo(001) and doped with various amounts of Li, whereas the second is a powder sample fabricated by calcination of Li and Mg precursors in an oxygen atmosphere. Scanning tunneling and transmission electron microscopy are performed to characterize the morphology of both samples. At temperatures above 700 K, Li starts segregating towards the surface and forms irregular Li‐rich oxide patches. Above 1050 K, Li desorbs from the MgO surface, leaving behind a characteristic defect pattern. Traces of Li also dissolve into the MgO, as concluded from a distinct optical signature that is absent in the pristine oxide. No electron paramagnetic resonance signal that would be compatible with Li+O− centers is detected in the two Li/MgO samples. Density‐functional theory calculations are used to determine the thermodynamic stability of various Li‐induced defects in the MgO. The calculations clarify the driving forces for Li segregation towards the MgO surface, but also rationalize the absence of Li+O− centers. From the combination of experimental and theoretical results, a detailed picture arises on the role of Li for the MgO properties, which can be used as a starting point to analyze the chemical behavior of the doped oxide in future.

Charge-mediated adsorption behavior of CO on MgO-supported Au clusters.

The CO binding behavior to gold particles supported on MgO thin films has been analyzed with scanning tunneling microscopy (STM) and infrared spectroscopy (IRAS). The ad-particles accommodate excess electrons that originate either from a charge transfer through the thin oxide film or from a local interaction with electron-rich oxide defects that act as Au nucleation centers. The enhanced electron density in the Au aggregates affects both the spatial distribution and the vibrational properties of adsorbed CO species. Whereas preferential CO attachment to the chemically unsaturated and electron-rich boundary sites of the Au islands is deduced from the STM data, a continuous downshift of the CO stretching frequency with decreasing particle size is observed in IRAS. Both results are interpreted in the light of CO adsorption to negatively charged metal aggregates and used to draw general conclusions on the interplay between charge and adsorption properties of confined metal systems.

Tailoring the Shape of Metal Ad-Particles by Doping the Oxide Support†

Doping is a versatile yet little examined approach to tailor the physical and chemical properties of oxide thin films. By means of scanning tunneling microscopy (STM), we demonstrate how tiny amounts of Mo embedded in a CaO matrix change the growth behavior of gold. Whereas 3D deposits are formed on the pristine oxide surface, strictly 2D growth prevails on the doped material. The crossover in particle shape is driven by charge-transfer processes from the Mo dopants into the Au islands, as elucidated with density-functional theory (DFT) calculations.

Oxidation of Au by Surface OH: Nucleation and Electronic Structure of Gold on Hydroxylated MgO(001)

The nucleation and electronic structure of vapor-deposited Au on hydroxylated MgO(001) surfaces has been investigated under ultrahigh vacuum conditions. Hydroxylated MgO(001) surfaces with two different hydroxyl coverages, 0.4 and 1 monolayer, respectively, were prepared by exposure to water (D(2)O) at room temperature. Scanning tunneling microscopy experiments show significantly higher gold particle densities and smaller particle sizes on the hydroxylated MgO surface as compared to gold deposited on clean MgO(001). Infrared spectroscopy and X-ray photoelectron spectroscopy experiments were performed to reveal details about the initial nucleation of gold. Gold atoms are found to chemically interact with a specific type of hydroxyl groups on the MgO surface, leading to the formation of oxidized gold particles. The enhanced adhesion of Au particles, which is due to the formation of strong Au-O interfacial bonds, is responsible for the observed higher stability of small Au clusters toward thermal sintering on hydroxylated MgO surfaces. The results are compared to similar studies on Au/TiO(2)(110) model systems and powder samples prepared by the deposition-precipitation route.

Au dimers on thin MgO(001) films: flat and charged or upright and neutral?

A combination of low temperature scanning tunneling microscopy (STM) and theoretical calculations is used to investigate Au dimers, supported on thin MgO(001) films, whose thickness was chosen such that charge transfer from the Ag substrate to the deposited Au is possible. Au dimers exist not only in an upright geometry--as theoretically predicted to be the most stable configuration--but also as flat lying dimers which populate a manifold of different azimuthal orientations. Apart from the difference in adsorption configurations, these two isomers exhibit rather different electronic structures: while upright dimers are neutral, flat ones are charged.

Adsorption, Activation, and Dissociation of Oxygen on Doped Oxides†

Charge transfer in the presence of dopants is relevant for the adorption and activation of small molecules, such as O2 . Scanning tunneling microscopy and DFT calculations provide evidence for the formation of strongly bound superoxo species on chemically inert, Mo-doped CaO films. This oxygen surface species shows a high propensity to dissociate. Dopants could also be important for the activation of hydrocarbons on inert oxides.

Formation of one-dimensional electronic states along the step edges of CeO2(111)

Scanning tunneling microscopy (STM) combined with density functional theory (DFT) are used to analyze the structural and electronic properties of step edges on the surface of CeO(2)(111) films grown on Ru(0001). Depending on the preparation conditions, 211 or 110-oriented steps develop on the surface, which results in the formation of ceria ad-islands with hexagonal or triangular shapes. STM conductance spectroscopy reveals pronounced differences in the electronic properties of the step edges, as reflected in different onset positions of the ceria conduction band. The band shifts are related to the development of distinct edge electronic states that split-off from the ceria conduction band, as shown with DFT calculations. The separation of the edge states from the main band is governed by the atom-coordination and local charge-distribution along the edge, the latter giving rise to the development of electrostatic dipoles. We expect that the observed edge morphologies determine not only the electronic properties but also the adsorption behavior of step edges on the CeO(2)(111) surface.