Oxidation state and symmetry of magnesia-supported Pd13O(x) nanocatalysts influence activation barriers of CO oxidation.

Combining temperature-programmed reaction measurements, isotopic labeling experiments, and first-principles spin density functional theory, the dependence of the reaction temperature of catalyzed carbon monoxide oxidation on the oxidation state of Pd(13) clusters deposited on MgO surfaces grown on Mo(100) is explored. It is shown that molecular oxygen dissociates easily on the supported Pd(13) cluster, leading to facile partial oxidation to form Pd(13)O(4) clusters with C(4v) symmetry. Increasing the oxidation temperature to 370 K results in nonsymmetric Pd(13)O(6) clusters. The higher symmetry, partially oxidized cluster is characterized by a relatively high activation energy for catalyzed combustion of the first CO molecule via a reaction of an adsorbed CO molecule with one of the oxygen atoms of the Pd(13)O(4) cluster. Subsequent reactions on the resulting lower-symmetry Pd(13)O(x) (x < 4) clusters entail lower activation energies. The nonsymmetric Pd(13)O(6) clusters show lower temperature-catalyzed CO combustion, already starting at cryogenic temperature.

Control and manipulation of gold nanocatalysis: effects of metal oxide support thickness and composition.

Control and tunability of the catalytic oxidation of CO by gold clusters deposited on MgO surfaces grown on molybdenum, Mo(100), to various thicknesses are explored through temperature-programmed reaction measurements on mass-selected 20-atom gold clusters and via first-principles density functional theory calculations. Au(20) was chosen because in the gas phase it is characterized as an extraordinarily stable tetrahedral-pyramidal structure. Dependencies of the catalytic activities and microscopic reaction mechanisms on the thickness and stoichiometry of the MgO films and on the dimensionalities and structures of the adsorbed gold clusters are demonstrated and elucidated. Langmuir-Hinshelwood mechanisms and reaction barriers corresponding to observed low- and high-temperature CO oxidation reactions are calculated and analyzed. These reactions involve adsorbed O(2) molecules that are activated to a superoxo- or peroxo-like state through partial occupation of the antibonding orbitals. In some cases, we find activated, dissociative adsorption of O(2) molecules, adsorbing at the cluster peripheral interface with the MgO surface. The reactant CO molecules either adsorb on the MgO surface in the cluster proximity or bind directly to the gold cluster. Along with the oxidation reactions on stoichiometric ultrathin MgO films, we also study reactions catalyzed by Au(20) nanoclusters adsorbed on relatively thick defect-poor MgO films supported on Mo and on defect-rich thick MgO surfaces containing oxygen vacancy defects.

Micromechanical sensor for studying heats of surface reactions, adsorption, and cluster deposition processes.

We present a newly designed highly sensitive micromechanical sensor devoted to thermodynamic studies involving supported clusters. The thermally sensitive element of the sensor consists of a micromachined silicon cantilever array, onto which a thin metal film is evaporated. Due to the difference between the thermal expansion coefficients of silicon and the metal employed, thermal bending is observed when heat is exchanged with the cantilever. The sensitivity and the response time of the cantilever are studied as a function of the film material (gold or aluminum) and the thickness of the metal film. With our routinely prepared cantilevers, a minimum power of 120 nW is measurable with a submillisecond response time, corresponding to a limit of detection in the femtojoule range. The high sensitivity of the sensor is demonstrated by measuring the heat exchange which occurs during the deposition of clusters on the cantilever. Experimentally, we illustrate the 1,3-butadiene hydrogenation reaction using a cluster model catalysts created by soft-landing palladium clusters onto the cantilever surface.

Microkinetic simulations of the oxidation of CO on Pd based nanocatalysis: a model including co-dependent support interactions.

The catalysed oxidation of CO using mass-selected Pd(13) clusters supported on thin MgO films was modelled using a microkinetic simulation of the reaction. The model of the system includes reverse spill-over calculations which were intrinsically incorporated into the formulation of the kinetics. The spill-over model is based on a capture-zone approach including a co-dependence on the variables of the kinetic equations. The experimental values were determined using dual pulsed-molecular beam measurements and recorded at a range of temperatures. The experiment allowed the turn-over frequency and reaction probability to be determined as a function of mole fraction. Comparison of the kinetic model with the experimental data gives excellent agreement and strongly highlights the importance of substrate effects. In particular, the origin of the low temperature catalysis of the Pd clusters is elucidated. The model allows the mole fraction and temperature dependent values such as the sticking coefficients for these clusters to be predicted.