Kinetic parameters from temperature programmed desorption spectra combined with energy relations: top and bridge CO on Rh(100).

A Monte Carlo model of CO on Rh(100) is presented that can correctly describe CO adsorption and desorption over the entire coverage region: from 0 ML to saturation coverage (0.83 ML). Experimental temperature-programmed desorption traces are fitted with simulated traces by differential evolution to obtain numerical values of kinetic parameters. Energy relations are used to limit the amount of fitted parameter sets to only include sets which can reproduce the experimentally observed adlayer structures. The fit that best approaches the actual kinetic parameters uses additional relations to improve the position of the desorption features. In both cases, an exact fit between the experimental and simulated desorption traces is not obtained. Because of this, the magnitude of the obtained kinetic parameters is determined only qualitatively.

Interaction and reaction of coadsorbed NO and CO on a Rh(100) single crystal surface.

In order to assess the possibility to follow surface reactions in a quantitative way by vibrational spectroscopy, a combination of temperature programmed reaction spectroscopy (TPRS) and reflection absorption infrared spectroscopy (RAIRS) has been used to study the decomposition of NO and the reaction between NO and CO on Rh(100). NO adsorbs in two configurations: in an almost parallel position at coverages below 0.18 ML and, in addition, in an upright position, probably on a bridge site, at all coverages. Coadsorbing NO and CO has only a minor influence on NO binding, whereas CO shifts gradually from top toward the bridge site under the influence of NO. Combining TP-RAIRS with TPRS during the reaction between CO and NO enabled us to simultaneously study site occupation and obtain qualitative surface coverages and desorption rates. At low surface coverages, NO dissociation is observed at lower temperatures than CO(2) formation. Near saturation, NO dissociation becomes blocked and shifts up in temperature. NO dissociation occurs simultaneously with CO(2) formation. To decompose NO, free surface sites have to be generated through surface diffusion or desorption of some CO. During NO decomposition, the formed oxygen atoms react with CO to form CO(2), creating more empty sites. This may lead to an explosive surface reaction.

Interactions between co-adsorbed CO and H on a Rh(100) single crystal surface.

Co-adsorption of CO and H(2) on a Rh(100) single crystal surface has been studied by a combination of temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), low energy electron diffraction (LEED), and density functional theory (DFT) calculations. Exposure of CO to a hydrogen precovered surfaces at 150 K results in some displacement of adsorbed hydrogen and a layer with 0.67 ML H and 0.67 ML CO is obtained. A c(3 square root(2) x square root(2))R45 degree structure is formed with CO occupying bridge sites and hydrogen occupying partly bridge sites on the surface and partly octahedral subsurface sites, causing hydrogen to desorb at temperatures around 230 K.

Chemistry of ethylene glycol on a Rh(100) single-crystal surface.

The adsorption and decomposition of ethylene glycol on Rh(100) have been studied with temperature-programmed reaction spectroscopy and reflection absorption infrared spectroscopy. Ethylene glycol adsorbs onto the surface via the hydroxyl groups. At 150 K, both hydroxyl bonds are broken, forming an ethylenedioxy intermediate. At high coverage, a portion of the ethylene glycol molecules dehydrogenate only one hydroxyl bond, forming a monodentate species. These intermediates decompose further, with complete dehydrogenation and simultaneous C--C bond breaking occurring at around 290 K. Hydrogen and carbon monoxide are formed, which desorb at 290 and 500 K, respectively.

Acetylene decomposition on Rh(100): theory and experiment.

The decomposition of acetylene on a Rh(100) single crystal was studied by a combination of experimental techniques [static secondary ion mass spectrometry (SSIMS), temperature-programmed desorption (TPD), and low-energy electron diffraction (LEED)] to gain insight into the reaction pathway and the nature of the reaction intermediates. The experimental techniques were combined with a computational approach using density functional theory (DFT). Acetylene adsorbs irreversibly on the Rh(100) surface and eventually decomposes to atomic carbon and gas-phase hydrogen. The combination of experimental and computational results enabled us to determine the most likely reaction pathway for the decomposition process.