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Title: A closer look at heterogeneous catalysis: reaction intermediates at the single-molecule level
Authors: Peronio, Angelo
Supervisore/Tutore: Dri, Carlo
Comelli, Giovanni
Issue Date: 9-Apr-2013
Publisher: Università degli studi di Trieste
The present work pertains to the surface science approach to heterogeneous catalysis. In particular model systems for CO2 hydrogenation to methanol, and NO selective catalytic reduction, are investigated by means of a combined approach, where the molecular-level insight provided by a low-temperature scanning tunneling microscope is complemented by density functional theory (DFT) calculations of their electronic structure. To this end, the Inelastic Electron Tunneling Spectroscopy (STM-IETS) technique was introduced for the first time in our laboratory, a recent development which allows to measure the vibrational spectrum of individual molecules adsorbed on a surface.

Regarding CO2, we provide single molecule imaging and characterization of CO2/Ni(110), chemisorbed with high charge transfer from the substrate, in an activated state that plays a crucial role in the hydrogenation process. We obtain a detailed characterization of the adsorption geometries and an estimate of the energies corresponding to the different adsorbed states. A consistent picture of CO2 chemisorption on Ni(110) is provided on the basis of the newly available information, yielding a deeper insight into the previously existing spectroscopic and theoretical data.

In the Selective Catalytic Reduction (SCR) process, nitrogen oxide is selectively transformed to N2 by reductants such as ammonia. The specificity of this reaction was tentatively attributed to the formation of NH3-NO coadsorption complexes, as indicated by several surface science techniques. Here we characterize the NH3-NO complex at the atomic scale on the (111) surface of platinum, investigating the intermolecular interactions that tune the selectivity. The structures that arise upon coadsorption of NH3 and NO are analyzed in terms of adsorption sites, geometry, energetics and charge rearrangement. An ordered 2 × 2 adlayer forms, where the two molecules are arranged in a configuration that maximizes mutual interactions. In this structure, NH3 adsorbs on top and NO on fcc-hollow sites, leading to a cohesional stabilization of the extended layer by 0.29 eV/unit cell. The calculated vibrational energies of the individually-adsorbed species and of the coadsorption structure fit the experimental values found in literature within less than 6%.

The characterizations and optimizations that had to be tackled in order to successfully perform STM-IETS measurement are eventually presented, focusing in particular on an original method which allows to increase the achieved resolution. Namely, the modulation broadening associated to phase-sensitive detection is reduced by employing a tailored modulation function, different from the commonly-used sinusoid. This method is not limited to STM-IETS, but can be easily applied whenever a lock-in amplifier is used to measure a second derivative.
Ciclo di dottorato: XXV Ciclo
metadata.dc.subject.classification: SCUOLA DI DOTTORATO DI RICERCA IN NANOTECNOLOGIE
Keywords: Scanning Tunnelling Microscopy
Inelastic Electron Tunnelling Spectroscopy
Density Functional Theory
heterogeneous catalysis
surface science
model system
reaction intermediates
single molecules
nitric monoxide
platinum (111)
surface-mediated interaction
carbon dioxide
nickel (110)
lock-in amplifier
instrumental function
noise characterization
Language: en
Type: Doctoral Thesis
Settore scientifico-disciplinare: FIS/03 FISICA DELLA MATERIA
NBN: urn:nbn:it:units-9982
Appears in Collections:Scienze fisiche

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