Adsorption and co-adsorption of ethylene and carbon monoxide on silica-supported monodisperse Pt nanoparticles: volumetric adsorption and infrared spectroscopy studies.

The adsorption of carbon monoxide and ethylene, and their sequential adsorption, was studied over a series of Pt/SBA-15 catalysts with monodisperse particle sizes ranging from 1.7 to 7.1 nm by diffuse-reflectance infrared spectroscopy and chemisorption. Gas adsorption was dependent on the Pt particle size, temperature, and sequence of gas exposure. Adsorption of CO at room temperature on Pt/SBA-15 gives rise to a spectroscopic feature assigned to the C-O stretch: nu(CO) = 2075 cm-1 (1.9 nm); 2079 cm-1 (2.9 nm); 2082 cm-1 (3.6 nm); and 2090 cm-1 (7.1 nm). The intensity of the signal decreased in a sigmoidal fashion with increasing temperature, thereby providing semiquantitative surface coverage information. Adsorption of ethylene on Pt/SBA-15 gave rise to spectroscopic features at approximately 1340, approximately 1420, and approximately 1500 cm-1 assigned to ethylidyne, di-sigma-bonded ethylene, and pi-bonded ethylene, respectively. The ratio of these surface species is highly dependent on the Pt particle size. At room temperature, Pt particles stabilize ethylidyne as well as di-sigma- and pi-bonded ethylene; however, ethylidyne predominated on the surfaces of larger particles. Ethylidyne was the only identifiable species at 403 K, with its formation being more facile on larger particles. Co-adsorption experiments reveal that the composition of the surface layer is dependent on the order of exposure to gases. Exposure of a C2H4-covered Pt surface to CO resulted in an approximately 50% decrease in chemisorbed CO compared to a fresh Pt surface. The nu(CO) appeared at 2050 cm-1 on Pt/SBA-15 pretreated with C2H4 at room temperature. The di-sigma-bonded and pi-bonded species are the most susceptible to displacement from the surface by CO. The formation of ethylidyne appeared to be less sensitive to the presence of adsorbed carbon monoxide, especially on larger particles. Upon exposure of C2H4 to a CO-covered Pt surface, little irreversible uptake occurred due to nearly 100% site blocking. These results demonstrate that carbon monoxide competes directly with ethylene for surface sites, which will have direct implications on the poisoning of the heterogeneously catalyzed conversion of hydrocarbons.

Radial anisotropic growth of rhodium nanoparticles.

In this contribution, we report the synthesis of rhodium multipods that result from a homogeneous seeded growth mechanism. Small Rh nanocrystal seeds were synthesized by the reduction of RhCl3 in ethylene glycol in the presence of PVP. These seed particles could be subsequently used, without isolation, to form larger rhodium nanoparticles. A reaction temperature of 190 degrees C led to isotropic cubic Rh particles. Lowering the reaction temperature resulted in more anisotropic growth, which gave Rh cubes with horns at 140 degrees C, and Rh multipods at 90 degrees C. The anisotropic growth occurred in the (111) direction, as determined by high-resolution TEM (HRTEM). Anisotropic growth proceeds via a seeded growth mechanism, and not by oriented attachment.