Ostwald ripening | EPFL Graph Search

Ostwald ripening is a phenomenon observed in solid solutions or liquid sols that describes the change of an inhomogeneous structure over time, i.e., small crystals or sol particles dissolve, and redeposit onto larger crystals or sol particles. Dissolution of small crystals or sol particles and the redeposition of the dissolved species on the surfaces of larger crystals or sol particles was first described by Wilhelm Ostwald in 1896. For colloidal systems, Ostwald ripening is also found in water-in-oil emulsions, while flocculation is found in oil-in-water emulsions. Mechanism This thermodynamically-driven spontaneous process occurs because larger particles are more energetically favored than smaller particles. This stems from the fact that molecules on the surface of a particle are energetically less stable than the ones in the interior. Consider a cubic crystal of atoms: all the atoms inside are bonded to 6 neighbours and are quite stable, but atoms on the surface are

Etude des propriétés morphologiques et catalytiques d'agrégats d'or triés en taille et déposés sur le TiO2(110)

Raphaël Vallotton

This thesis aims to find, for the first time, a direct relation between the size and morphology of small metallic nanostructures (gold in this case) supported on a metal-oxide surface to their catalytic activity. In this perspective, three main topics have been treated during this thesis. The first part concerns the design and realization of a Scanning Tunneling Microscope (STM) supposed to work over a wide temperature range (4K < T ≤ 300K). This new device replaces an existing solution. The coarse approach of the scanning tip towards the sample is realized by an axial motor based on a sapphire prism gliding on shear piezos in the stick&slip mode. The new STM is very rigid moving the resonance frequencies to higher values with respect to the existing solution. Operation of the motor down to T = 8K has been proven, however topographic imaging has been performed only in the temperature range 77K < T ≤ 300K. The second part of this work focuses on a study of the evolution of the morphology of gold nanoparticles on a TiO2(110) surface. Size-selected clusters Aun+ (n = 5, 7) are deposited at a well defined kinetic energy on the surface held at room temperature. Subsequent annealing of the sample has been performed stepwise. After each temperature increase, the morphology has been determined by STM. The evolution as a function of surface temperature has been studied for two different surface reconstructions, TiO2(110)-(1×1) and TiO2(110)-(2×1). The deposition process leads only to small fragmentation and the morphology is stable up to T = 400K. Further increase of the surface temperature leads to sintering of the particles by Ostwald ripening as shown by an exponential decrease of the island density with temperature. The main topic of this thesis, the correlation between morphology and catalytic activity, is described in the last part of this manuscript. For the first time we are able to relate the onset of CO2 production from CO and O2 to a clear change in the morphology. The catalytic activity of the particles strongly depends on their size and dimensionality. The relative activity per particle has been determined and we find a clear maximum for clusters containing 60 atoms and are 3 to 4 monolayers high. These results are discussed in contrast of literature data on the same but also on different metal-oxide surfaces.

EPFL2009

Metal Clusters on Surfaces

Michael Hugentobler

The morphology, stability and reactivity of nanometre-sized particles (Au, Pt) is investigated on three different supports. Gold nanoparticles with a diameter comprised between 4 and 6nm are stabilized in nanosized pits of well defined depth in highly oriented pyrolytic graphite (HOPG). These pits are produced by creation of artificial defects, followed by etching under a controlled oxygen atmosphere. At low Au coverage, clusters are found on the edges of the hexagonal pits maximizing the contact to dangling bonds on graphite multisteps. Larger coverage results in Au beads of well defined shape and with a constant bead density per unit length. Most remarkable is the stability of these nanostructures under ambient conditions. Temperatures as high as 650 K do not alter the morphology of the gold clusters. Above 700 K, the gold clusters catalyze the etching of graphite layers when heated under atmospheric conditions. The depth of the etching channel is defined by the depth of the pit and the channel width can be controlled by the cluster size. Hydrogen, oxygen and water are dissociated on the Au clusters at low temperatures (> 400 K). CO and CO2 is produced above 700 K which confirms the etching of the multilayer graphene sheets. The so-called water-gas shift reaction has been observed where oxygen and water dissociate on the Au clusters at low temperatures. Thermal desorption spectroscopy (TDS) measurements on the Pt=YSZ system have been performed and the desorption peaks of CO and O2 have been evidenced. Carbon monoxide desorbs from the surface at a temperature of 535 K and oxygen at 705 K, in good agreement with values reported in literature. Catalytic measurements have confirmed the known strong catalytic activity of Pt. The CO oxidation takes place at temperatures between 450 K and 700 K. The adsorption and desorption temperature of the two educts have been confirmed during the catalysis measurements. Size-selected Aun clusters (n = 5, 7) are deposited from the gas phase at room temperature with well-controlled kinetic energy on rutile TiO2 . Two different surface reconstructions have been used as support: TiO2(110) – (1 × 1) and TiO2(110) – (1 × 2). Systematic studies of morphology, stability and adsorption sites have been performed using scanning tunnelling microscopy (STM). The mean size of the clusters is maintained during deposition at a kinetic energy of 7.1eV per atom, indicating that there is no fragmentation. Au clusters are not stable neither on the TiO2(110) – (1 × 1) nor on the TiO2(110) – (1 × 2) reconstruction during annealing of the substrate to 800 K. A progressive transition into a pronounced 3-d formation is observed. The size distribution of the particles is small and the growth mode (Ostwald ripening) independent of the surface reconstruction. The higher corrugation of the TiO2(110) – (1 × 2) reconstruction results in a pronounced stabilization of the clusters on terraces, in contrast to the TiO2(110) – (1 × 1) reconstruction where 90% of the clusters are found on step edges at elevated temperatures. The catalytic activity of the Au clusters sets in during the 2d - 3d transition. These measurements have to be confirmed and a full understanding of the process should be found.

EPFL2010

Thermal stability of size-selected copper nanoparticles: Effect of size, support and CO2 hydrogenation atmosphere

Alexandre Borsay, Mostapha Dakhchoune, Mo Li, Wen Luo, Kun Zhao, Andreas Züttel

Metal nanoparticles with a precisely controlled particle size distribution are ideal model catalysts for fundamental studies in catalysis. In this work, the thermal stability of size-selected Cu nanoparticles (Cu NPs) were deposited by magnetron sputtering, and their thermal stability was investigated using transmission electron microscopy and X-ray photoelectron spectroscopy. The influence of particle size, support, temperature, as well as CO2 hydrogenation atmosphere was systematically studied. We found that at 220 °C in ultra-high vacuum (UHV), carbon-supported 4 nm Cu NPs sintered through particle migration while the 8 nm Cu NPs were relatively stable. As the temperature increased to 320 and 460 °C, both samples sintered severely, and Ostwald ripening was suggested to be the dominant mechanism. In addition, we observed that SiO2 support can better stabilize Cu NPs upon heat treatment under both UHV and CO2 hydrogenation atmosphere (1 mbar of 1:1 CO2/H2 mixture), due to the stronger interaction between SiO2 and Cu compared to that between carbon and Cu. Furthermore, under a CO2 hydrogenation atmosphere, the stability of Cu NPs is suggested to be influenced by the interplay of redispersion, agglomeration, and volatilization. These findings from model systems can offer new insights for understanding the deactivation of Cu-based catalysts.