Adsorption of CO on cluster models of platinum (111): A four-component relativistic density-functional approach

Abstract

We report on results of a theoretical study of the adsorption process of a single carbon oxide molecule on a platinum ͑111͒ surface. A four-component relativistic density-functional method was applied to account for a proper description of the strong relativistic effects. A limited number of atoms in the framework of a cluster approach is used to describe the surface. Different adsorption sites are investigated. We found that CO is preferably adsorbed at the top position.

CO oxidation on stepped-Pt(111) under electrochemical conditions: insights from theory and experiment

“…Indeed, CO adsorption on Pt surfaces is indeed a non-trivial system to be calculated with DFT in general as the approach usually tends to overestimate the 3-fold hollow sites over atop sites, which in low temperature experiments were found to be preferred. As our aim is to investigate the co-adsorption of CO and OH, here we point the reader to the extensive discussions about the so-called "CO/Pt(111) puzzle" [41][42][43][44][45][46][47][48][49][50][51][52][53].…”

Different support effect of M/ZrO2 and M/CeO2 (M=Pd and Pt) catalysts on CO adsorption: A periodic density functional study

“…CO adsorption on precious metal surfaces is one of the most prototypical catalytic reactions and hence, has been studied with various experimental [1][2][3][4][5][6][7] and theoretical [8][9][10][11][12][13][14][15][16][17] methods. On the other hand, precious metals such as Rh, Pd and Pt are the essential ingredients for the so-called three-way catalyst (TWC), which simultaneously decreases the amount of the exhaust pollutants, viz., CO, HCs (hydrocarbons) and NO x .…”

Influence of Carbon Support on Electronic Structure and Catalytic Activity of Pt Catalysts: Binding to the CO Molecule

“…The results are also compared to experimental and previous theoretical data on the CO molecule and the CO−Pt complexes to validate how well our calculations estimate the electronic and structural characteristics of these complexes, and also serves as a reference when we discuss the effect of the carbon support on the catalytic activity. Binding of a CO molecule to a metallic surface, in particular Pt, has been studied extensively by a variety of theoretical approaches [56][57][58][59][60] and it is usually discussed using the Dewar-Chatt-Duncanson model. [61][62][63][64] The main characteristics of this model are a charge transfer from the lone-pair (5σ ) orbital of the CO molecule to the 5d orbitals of the Pt atom (σ donation) and a back donation of electron density from the 5d orbitals of the Pt atom to the antibonding 2π * orbitals of the CO molecule, 65 which is in agreement with photoelectron spectroscopy experiments.…”