Charge separation in CO oxidation involving supported gold clusters

The character of the catalytic oxidation of CO by supported gold cluster catalysts is analyzed with emphasis on the unique characteristics of this process. The scheme of this process used here has the reagent CO molecule captured in the interface between the cluster and support, with oxygen molecules or atoms located on the support surface to react with the CO. (Other models have also been presented.) The experimental data indicate that, together with configurational transitions that lead to the CO molecule joining an oxygen atom to form the CO₂ molecule, the charge separation due to capture of the CO molecule by the supported gold cluster is important. The process of release of the CO₂ molecule results in charge exchange; the time for this process is relatively long because of the large distance separating positive and negative charges, a distance exceeding the cluster radius. This provides a high efficiency of the oxidation of CO with this catalyst despite the relatively high activation energy for the configurational transition.     

Low temperature and low pressure CO oxidation on gold clusters supported on MgO(100)

CO oxidation has been investigated on Au/MgO(100) model catalysts at RT and low pressure. The gold particles prepared by UHV evaporation on clean MgO surfaces are characterized by HRTEM. The gold particles are FCC single crystals or multiple twins with five-fold symmetry. Infrared spectroscopy indicates that two types of adsorption sites are present which correspond to loosely and strongly bound CO. The equilibrium CO coverage for the strongly bound CO is smaller than 0.1 ML. CO titration experiments show that oxygen does not dissociate on the gold nanoparticles. The CO oxidation reaction is studied at RT by molecular beam methods. A steady state CO reaction probability up to 0.50 is measured, for the first time at low pressure, for gold particles with a mean size of 1.5 nm. A reaction mechanism is proposed in which CO adsorbed on low coordinated gold atoms reacts with oxygen adsorbed molecularly, possibly at the Au/MgO interface.     

Catalytically active gold clusters and nanoparticles for CO oxidation

Electronic states of gold nanoparticles in mordenite and their transformations under redox treatments have been studied by the methods of FTIR spectroscopy of adsorbed CO and diffuse reflectance UV-visible spectroscopy. Different states of ionic and metallic gold were detected in the zeolite channels and on the external surface of the zeolite - Au⁺ and Au³⁺ ions, charged clusters , and neutral nanoparticles Au_m. Catalytic tests of the samples revealed the existence of two types of active sites of gold in CO oxidation - gold clusters <2 nm (low-temperature activity) and gold nanoparticles (high temperature activity).     

High-pressure study on the adsorption and oxidation of CO on gold/titania model catalysts

The results of an IR study on the interaction of CO/O₂ gas mixtures with planar Au/TiO₂ model catalysts at elevated pressures and at room temperature are presented. The model catalysts were prepared by deposition of a flat titania film on a Ru(0 0 0 1) substrate and subsequent evaporation of gold on the titania film. In the presence of the gas mixtures, an IR band in the CO stretching region was formed, pointing to linearly adsorbed CO. The position of this band is nearly independent of the Au coverage employed. Compared to pure CO, the IR band is shifted to higher wave numbers when CO/O₂ gas mixtures are used. Although the production of CO₂ was detected in the CO oxidation reaction on the model catalysts, the formation of other IR bands, revealing the build-up of carbonates or other side-products which is usually observed for Au/TiO₂ real powder catalysts, was very weak.     

Promoting effect of tin oxides on alumina-supported gold catalysts used in CO oxidation

In this study the influence of SnO_x nanoparticles on the catalytic performance of alumina-supported gold catalysts was investigated in CO oxidation. The tin modified supports were prepared by grafting of tetraethyltin onto the surface of alumina via its hydroxyl groups. The decomposition of organometallic surface species in oxygen yielded highly dispersed tin oxide on the surface of alumina. Gold was introduced onto the tin modified alumina support by both deposition-precipitation with urea and direct anionic exchange techniques using HAuCl₄ solution. Based on catalytic and different spectroscopic measurements it is suggested that the presence of “Snⁿ⁺-Au ensemble sites” is responsible for the increased activity of these catalysts.     

The surface diffusion in CO oxidation on small supported Pd particles: Experimental evidence

Thermo-programmed heterogeneous catalytic oxidation of CO on Pd small particle/mica catalysts has been used to study the influence of the Pd particle number density on the catalytic turnover rate. Rapid increase is observed in the maximum CO₂ turnover rate with decreasing particle density. This effect can be explained by the surface migration of gas molecules on the mica substrate. In previous papers devoted to CO oxidation on Pd particles we pointed out that both the initial sticking coefficient s₀ of CO on Pd and the turnover rate r_CO2 (for CO₂ formation) increase when the particles size decreased. Measurements of the CO consumation rate N_c during an oxidation reaction have also demonstrated a similar particle size dependence for Nc. If the quantities s₀ and r_CO2 are calculated relative to the impinging flux of CO molecules J_i (J_i given by the kinetic theory of gases), the obtained values are always higher than unity for particle diameter smaller than 8 nm. In the light of these results it seems that the real CO flux should be higher than J_i. Ladas, Poppa and Boudart have suggested that the edge of the particles can receive more collisions than the face atoms, which could explain an increase of the mean CO flux with decreasing particle size.     

Structural evolution and properties of small-size thiol-protected gold nanoclusters

Ligand-protected gold clusters are widely used in biosensors and catalysis. Understanding the structural evolution of these kinds of nanoclusters is important for experimental synthesis. Herein, based on the particle swarm optimisation algorithm and density functional theory method, we use [Au₁(SH)₂]_n, [Au₂(SH)₃]_n, [Au₃(SH)₄]_n (n?=?1–3) as basic units to research the structural evolution relationships from building blocks to the final whole structures. Results show that there is a ‘line-ring-core’ structural evolution pattern in the growth process of the nanoclusters. The core structures of the ligand-protected gold clusters consist of Au₃, Au₄, Au₆ and Au₇ atoms. The electronics and optics analysis reflects that stability and optical properties gradually enhance with increase in size. These results can be used to understand the initial growth stage and design new ligand-protected nanoclusters.     

Dissociation of CO on supported Rh

The adsorption and dissociation of CO have been investigated on alumina supported Rh at atmospheric pressure. The dissociation of CO was detected above 473 K. The carbon formed reacted with H₂ even at 300–473 K yielding CH₄. A significant aging of surface carbon occurred above 573 K.     

Observation of fractal nanoclusters on the pulsed laser deposition of gold

The results of studying the fractal structure of Au clusters arising in pulsed laser deposition under conditions of strong deviations from thermodynamic equilibrium are presented. A mechanism is suggested in which the formation of fractal nanoclusters is considered as a result of the decay of a strongly correlated initial state in a non-equilibrium system of adatoms. The geometrical shape of the fractal structures observed experimentally can be described within the given mechanism, and their dimensionality can be estimated.     

Formation of the structure of gold nanoclusters during crystallization

The structure formation in gold nanoparticles 1.6–5.0 nm in diameter is studied by molecular dynamics simulation using a tight-binding potential. The simulation shows that the initial fcc phase in small Au clusters transforms into other structural modifications as temperature changes. As the cluster size increases, the transition temperature shifts toward the melting temperature of the cluster. The effect of various crystallization conditions on the formation of the internal structure of gold nanoclusters is studied in terms of microcanonical and canonical ensembles. The stability boundaries of various crystalline isomers are analyzed. The obtained dependences are compared with the corresponding data obtained for copper and nickel nanoparticles. The structure formation during crystallization is found to be characterized by a clear effect of the particle size on the stability of a certain isomer modification. Nickel and copper clusters are shown to exhibit common features in the formation of their structural properties, whereas gold clusters demonstrate much more complex behavior.     

Self-limiting size distribution of supported cobalt nanoclusters at room temperature

Formation of monodispersed Co nanoclusters on a single-crystal Si3N4 dielectric film at room temperature is reported. A remarkably narrow size distribution with the average size of approximately 30 Co atoms has been obtained. We have confirmed that the average size of Co nanoclusters is independent of the Co coverage and the cluster areal density linearly proportions to the Co deposition amount even at high coverages. Also, we have found that Co nanoclusters deposited on Si3N4 are thermally stable with respect to cluster aggregation/coalescence. We propose that this novel phenomenon is a quantum size effect, manifested by local energy minima in the electronic shell structure of Co quantum dots.     

Bonding trends and dimensionality crossover of gold nanoclusters on metal-supported MgO thin films

Bonding of gold clusters, , 16, and 20, on MgO(100) and on thin MgO films supported on Mo(100) is investigated using first-principles density-functional theory. Enhanced adhesive bonding is found for clusters deposited on metal-supported MgO films of thickness up to about 1 nm, or 4 to 5 MgO layers, originating from electrostatic interaction between the underlying metal and metal-induced excess electronic charge accumulated at the cluster interface with the oxide film. The increased wetting propensity is accompanied by a dimensionality crossover from three-dimensional optimal cluster geometries on MgO(100) to energetically favored two-dimensional structures on the metal-supported films.     

Observation of electron localization in rough gold nanoclusters on the graphite surface

The results of scanning tunneling spectroscopy of the electronic states of Au nanoclusters on the graphite surface are presented. The tunneling current is found to be different at different points of a rough-surface nanocluster. The measured differential current-voltage curve of the clusters is nonmonotonic near the Fermi energy, and the tunneling conductance decreases by almost a factor of two as the cluster volume changes from 1 to 0.1 nm³. This decrease can be associated with the change in the density of the electronic states near the Fermi energy. The observed features are qualitatively described within the framework of the mechanism of electron localization in disordered systems.     

Synthesis and characterization of superparamagnetic nanoparticles coated with fluorescent gold nanoclusters

Multifunctional nanoparticles (NPs) combining the superparamagnetism of Mn−Zn ferrite and the fluorescence property of gold nanoclusters (NCs) have been prepared by wet chemistry. Magnetic NPs synthesized by co-precipitation method were coated several times with oppositely charged polyelectrolytes (PEs) using the layer-by-layer technique. Common techniques (Fourier transform infrared spectroscopy, electron microscopy, zeta potential, etc.) indicated the monodispersity and the stability of the coated NPs providing a positive charged surface. Fluorescent gold NCs bound to a standard protein bovine serum albumin were adsorbed on the surface of the magnetic NPs. Structural investigations proved the presence of small gold clusters (~2 nm) in a shell surrounding the magnetic nanomaterial. The stable nanocomposite kept the original fluorescence property of the metal clusters with 211-fold increase of the red emission (λ = 690 nm) compared to the uncoated NPs. These NPs can be moved with a permanent magnet despite a 72-wt% increase of the non-magnetic fraction due to the PE coating and the protein adsorption.     

Correlations between microstructure of plasma-modified gold nanoclusters and their optical properties

Gold nanoclusters with diameters up to 50 nm were grown in sandwich structures consisting in 15 nm of plasma deposited silicon nitride, 1 nm of gold grown by sputtering and 15 nm of plasma deposited silicon nitride (SiN/Au/SiN). Previous to the last step, ammonia plasma treatments of the gold surface were carried out with time as the main variable. The resulting structures were analyzed by high resolution transmission electron microscopy and spectroscopic ellipsometry. As a result of plasma treatments, island-like structures of as-grown gold clusters evolve to near spherical-shape features with decreasing diameter as the plasma treatment time rises. Ellipsometric spectra were modeled based on the Bruggeman effective medium approximation and the influence of size and shape of nanoparticles on the optical properties were calculated.