Abstract
The effects of strain σ on the binding position preference of oxygen atoms and hydroxyl groups adsorbed on Pt(111) have been investigated using density functional theory. A transition between the bridge and FCC binding occurs under compressive strain of the O/Pt(111) surface. A significant reconstruction occurs under compressive strain of the OH/Pt(111) surface, and the surface OH groups preferentially occupy on‐top (bridge) positions at highly compressive (less compressive/tensile) strains. Changes to magnetisation of the O‐ and OH‐populated surfaces are discussed and for O/Pt(111) oxygenation reduces the surface magnetism via a delocalised mechanism. The origins of the surface magnetisation for both O‐ and OH‐bearing systems are discussed in terms of the state‐resolved electronic populations and of the surface charge density.
Highlights
Pt-based materials are effective catalysts for the oxygen reduction reaction (ORR).[1,2] Early experimental reports demonstrated the highly active character of Pt3Ni(111)[3] and across a sequence of related Pt3M (M = Ni, Co, Fe, Ti, and V) surfaces.[4]
O/Pt(111) Figure 2 shows the behaviour of the oxygen binding energy EB as a function of strain s for oxygen atoms bound in the HCP, FCC, bridge and on-top positions
The curves show that, as the strain becomes increasingly compressive (s < 0), the preferred binding position changes from the FCC to the bridge position and that this transition occurs at s = À0.03
Summary
Pt-based materials are effective catalysts for the oxygen reduction reaction (ORR).[1,2] Early experimental reports demonstrated the highly active character of Pt3Ni(111)[3] and across a sequence of related Pt3M (M = Ni, Co, Fe, Ti, and V) surfaces.[4] The ORR mechanism concerns the hydrogenation of O2 and mainly occurs along either a four-electron reduction pathway producing H2O or along a two-electron pathway producing H2O2. The mechanisms of these pathways, are not understood and this lack of understanding is, in part, due to the number of concurrent processes that occur during the reaction. These phenomena include, at larger length scales, OH and H2O island formation and, at shorter length scales, the effects of attractive adsorbate-adsorbate interactions caused by hydrogen bonds between adsorbed molecules
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
