First principles study of O₂ dissociation on Pt(111) surface: Stepwise mechanism

Abstract

We have performed first‐principle density functional theory calculations to investigate O2 dissociation on Pt(111) surface. A stepwise mechanism has been proposed. First, the adsorbed O2 dissociate into two oxygen atoms to get adsorbed on the nearby adsorption sites. Then, oxygen atoms further migrate to other more stable adsorption sites. The influence of solvent water on oxygen dissociation was also examined. The results show that the co‐adsorption of water has little impact on O2 dissociation. However, when water participates in the reaction, the energy barriers were reduced greatly. These results have very important significance to understand the mechanism of oxygen reduction. © 2016 Wiley Periodicals, Inc.

Adsorption Energetics of Atoms and Diatomic Gases with Electrocatalysis Approach towards Hydrogen and Oxygen Evolution Reaction on Pt Surfaces

“…These are the key reactions for improving air quality, especially in the automotive industries, where platinum is used as the active metal in three‐way catalyst . Over the past few decades, the interaction of atoms or molecules with the platinum surfaces are intensively studied in surface science and achieved a great deal of attention both experimentally as well as computationally majorly due to its scientific and industrial importance in chemical and petroleum applications.…”

“…Furthermore, the chemisorption of atoms (H, C, N, O, and S) takes an important role in the reactions of the chemical industries mainly contained in the reactions of hydrocarbon production, ammonia synthesis, oxidation, corrosion, and petroleum re‐forming . The intrinsically fundamental interest of the interaction of atoms with metal surfaces is relevant to catalytic chemistry.…”

“…Nevertheless, platinum is one of the most expensive metal and consequently, our main interest is to modify its properties to achieve higher activity or selectivity in a catalytic reaction so that less metal would be required. In this regard, computational simulations can deliver useful and rational perspectives into chemical reactions by predicting a system's geometric and/or electronic structure at the atomic scale …”

“…Atomic and molecular interactions of hydrogen,,− and oxygen,−, are most intensively and extensively studied on platinum surfaces which play an important role in numerous processes central to clean energy sources. Simultaneously, it will provide a platform to study the hydrogen/oxygen bonding between intermediates for the many chemical reactions which are performed on the transition metal surfaces.…”

“…Simultaneously, it will provide a platform to study the hydrogen/oxygen bonding between intermediates for the many chemical reactions which are performed on the transition metal surfaces. In the past few decades, countless experimental and DFT studies have been carried out for atomic hydrogen,,− and oxygen,−, adsorption on platinum surfaces and found that the fcc hollow is the most stable adsorption site on Pt(111) surface whereas hcp and top are less stable for the adsorption of H and O. However, for the Pt(100) surface bridge site is the most promising site.…”