Methane catalytic combustion on Pd9/gamma-Al2O3 with different degrees of Pd oxidation.

This research is focused on the analysis of adsorbed CH4 intermediates at oxidized Pd9 nanoparticles supported on gamma-alumina. From first-principle density functional theory (DFT) calculations, several configurations, charge transfer and electronic density of states have been analyzed in order to determine feasible paths for the oxidation process. Furthermore methane oxidation cycles have been investigated on Pd nanoparticles with different degrees of oxidation. In case of low oxidized Pd nanoparticles, activation of methane is observed, whereby hydrogen from methane is adsorbed at one oxygen atom. This reaction is exothermic. In a subsequent step, two water molecules desorb. Additionally, a very interesting structural effect becomes evident; Pd-carbide formation, which is also an exothermic reaction. Furthermore, oxidation of such carbidized Pd-nanoparticles leads to CO2 formation, which is an endothermic reaction. One important result is that the support is involved in the CO2 formation. A different mechanism of methane oxidation was discovered for highly oxidized Pd nanoparticles. When the Pd nanoparticle is more strongly exposed to oxidative conditions, adsorption of methane is also possible, but it leads to carbonic acid production at the interface between the Pd nanoparticles and support. This process is endothermic.

CH4 combustion cycles at Pd/Al2O3--important role of support and oxygen access.

This research is focused on the analysis of adsorbed CH4 intermediates at oxidized Pd9 nanoparticles supported on γ-alumina. From first-principle density functional theory calculations, several configurations, charge transfer and electronic density of states have been analyzed in order to determine feasible paths for the oxidation process. Methane oxidation cycles have been considered as a further step at differently oxidized Pd nanoparticles. For low oxidized Pd nanoparticles, activation of methane is observed, whereby hydrogen from methane is adsorbed at one oxygen atom. This reaction is exothermic with adsorption energy equal to -0.38 eV. In a subsequent step, desorption of two water molecules is observed. Additionally, a very interesting structural effect is evident, mainly Pd-carbide formation, which is also an exothermic reaction with an energy of -0.65 eV. Furthermore, oxidation of such carbidized Pd nanoparticles leads to CO2 formation, which is an endothermic reaction. Important result is that the support is involved in CO2 formation. A different mechanism of methane oxidation has been found for highly oxidized Pd nanoparticles. When the Pd nanoparticle is more strongly exposed to oxidative conditions, adsorption of methane is also possible, but it will proceed with carbonic acid production at the interface between Pd nanoparticles and support. However, this step is endothermic.

DFT studies of oxidation routes for Pd9 clusters supported on γ-alumina.

This research is focused on the analysis of adsorbed bare and oxidized Pd(9) nanoparticles supported on γ-alumina. From first-principle density functional theory calculations, several configurations, charge transfer and electronic density of states have been analyzed in order to determine feasible paths for the oxidation process. Studies of Pd/PdO nanoparticles prove that they are stable at γ-alumina supports. It is shown that the Pd(9) nanoparticle favors dissociative adsorption of oxygen molecules. The most energetically preferable sites for adsorption are close to the contact between the cluster and the support, where one oxygen atom interacts with a 5-coordinated aluminium atom, and the remaining oxygen is in contact with the closest palladium atom. After first dissociation, one oxygen atom creates a bridge between the palladium atom and the 5-coordinated aluminium atom and the second oxygen atom moves to the top of the Pd(9) cluster, making a bridge between two palladium atoms. Subsequent dissociations arise analogously, with the difference that oxygen atoms in the second layer of the palladium cluster occupy hollow sides of the cluster. Investigation of the charge distribution in each oxidation step reveals that charge transfer increases towards the Pd/PdO nanoclusters. The electronic density of states indicates that gradual oxygen molecule adsorption and dissociation shift the highest states of the Pd/PdO nanoparticles in different ways. The overall investigation is found to be beneficial for studying methane oxidation.

Quantum size effects in ambient CO oxidation catalysed by ligand-protected gold clusters.

Finely dispersed nanometre-scale gold particles are known to catalyse several oxidation reactions in aerobic, ambient conditions. The catalytic activity has been explained by various complementary mechanisms, including support effects, particle-size-dependent metal-insulator transition, charging effects, frontier orbital interactions and geometric fluxionality. We show, by considering a series of robust and structurally well-characterized ligand-protected gold clusters with diameters between 1.2 and 2.4 nm, that electronic quantum size effects, particularly the magnitude of the so-called HOMO-LUMO energy gap, has a decisive role in binding oxygen to the nano-catalyst in an activated form. This can lead to the oxidation reaction 2CO + O(2) â†’ 2CO(2) with low activation barriers. Binding of dioxygen is significant only for the smallest particles with a metal core diameter clearly below 2 nm. Our results suggest a potentially viable route to practical applications using ligand-protected gold clusters for green chemistry.

First-principles simulations of hydrogen peroxide formation catalyzed by small neutral gold clusters.

Energetics and dynamical pathways for hydrogen peroxide formation from H(2) and O(2) bound to neutral gold dimers and tetramers have been investigated by applying several strategies: T = 0 K geometry optimizations, constrained Car-Parrinello molecular dynamics simulations at T = 300 K and metadynamics at T = 300 K. The competing reaction channels for water and hydrogen peroxide formation have been found and characterized. In each case, the reaction barriers for Au cluster catalyzed proton transfer are less than 1 eV. Water formation is a competitive reaction channel, and the relative weight of H(2)O and H(2)O(2) products may depend on the chosen Au cluster size. Dynamic simulations demonstrate the significance of the geometric fluxionality of small catalytic Au clusters. These results indicate that neutral Au clusters could work as catalysts in aerobic H(2)O(2) formation in ambient conditions.

A density functional investigation of thiolate-protected bimetal PdAu(24)(SR)(18)(z) clusters: doping the superatom complex.

Structure, electronic properties, optical absorption and charging properties of methylthiolate-protected bimetal PdAu(24)(SR)(18)(z) (R = Me) clusters with various charge states (-3