SFG experiment and ab initio study of the chemisorption of CN- on low-index platinum surfaces
| Autor: | A. Le Rille, M. Tadjeddine, J.-P. Flament, Abderrahmane Tadjeddine |
|---|---|
| Přispěvatelé: | Laboratoire des mécanismes réactionnels (DCMR), École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie Physique D'Orsay (LCPO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2006 |
| Předmět: |
Analytical chemistry
Ab initio chemistry.chemical_element Resonance Surfaces and Interfaces 010402 general chemistry Condensed Matter Physics 01 natural sciences 0104 chemical sciences Surfaces Coatings and Films Adsorption chemistry Chemisorption Ab initio quantum chemistry methods 0103 physical sciences Materials Chemistry Density functional theory [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] 010306 general physics Spectroscopy Platinum |
| Zdroj: | Surface Science Surface Science, Elsevier, 2006, 600 (10), pp.2138-2153 |
| ISSN: | 0039-6028 |
| Popis: | A dual analysis is proposed in order to have a better understanding of the adsorption of the cyanide ions on a platinum electrode. The SFG (Sum Frequency Generation) spectroscopy allows the in situ vibrational study and the SFG spectra of the CN − species adsorbed on single crystal Pt electrode allow a systematic study of the low-index platinum surfaces. This experimental work is supported by ab initio calculations using density functional theory and cluster models. For each surface orientation and each geometry, a cluster model of 20–30 Pt atoms has been built in order to interpret the chemisorption of the CN − ions through four kinds of adsorption geometry: on-top or bridge site, bonding via C or N atoms. Geometries have been optimized and adsorption energies, electronic properties and vibrational frequencies have been computed. From the electronic properties, we can propose an analysis of the bonding mechanism for each studied kind of adsorption. The SFG spectra of the CN − /Pt(1 1 1) system present an unique resonance owing to the top C adsorption. It is mainly the same for the CN − /Pt(1 0 0) system. It is also the case for the SFG spectra of the CN − /Pt(1 1 0) system recorded at negative electrochemical voltage; at more positive voltage, a second resonance appears at a lower frequency, owing to the top N adsorption. Experimental and theoretical values of the C–N stretching frequencies are in excellent agreement. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
Full Text from ScienceDirect