Face-centered tetragonal (FCT) Fe and Co alloys of Pt as catalysts for the oxygen reduction reaction (ORR): A DFT study

Journal Article · 07 November 2018 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.5049674 · OSTI ID:1483302

Sharma, Shubham ^[1]; Zeng, Cheng ^[2]; Peterson, Andrew A.  ^[2]

---

1. Brown Univ., Providence, RI (United States). School of Engineering; Brown University
2. Brown Univ., Providence, RI (United States). School of Engineering

Proton exchange membrane fuel cells (PEMFCs) are promising candidates for alternate energy conversion devices owing to their various advantages including high efficiency, reliability, and environmental friendliness. The performance of PEMFCs is fundamentally limited by the sluggish kinetics of the oxygen reduction reaction (ORR) at the cathode. Various studies have addressed myriads of Pt-based alloys as potential catalysts for ORR. However, most of these studies only focus on the cubic-structured Pt-based alloys which require further improvements especially in terms of stability and required loading. We perform first-principle density functional theory calculations to explore Fe and Co alloys of Pt in a different face centered tetragonal (L1₀) geometry as potential catalysts for ORR. The work focuses on understanding the reaction mechanism of ORR by both dissociative and associative mechanisms on L1₀–FePt/Pt(111) and L1₀–CoPt/Pt(111) surfaces. The binding pattern of each reaction intermediate is studied along with the complete reaction free energy landscape as a function of Pt overlayers. The L1₀–FePt/Pt(111) and L1₀–CoPt/Pt(111) surfaces show higher calculated surface activity for ORR as compared to the native fcc Pt(111) surface. The decrease in the required overpotential (η) for the alloys with respect to the unstrained Pt(111) surface is found to be in the range (0.04 V–0.25 V) assuming the dissociative mechanism and (0.02 V–0.10 V) assuming the associative mechanism, where the variation depends on the thickness of Pt overlayers. We further correlate the binding behavior of the reaction intermediates to the applied biaxial strain on the Pt(111) surface with the help of a mechanical eigenforce model. The eigenforce model gives a (semi-) quantitative prediction of the binding energies of the ORR intermediates under applied biaxial strain. The numerical values of the limiting potential (U_L) obtained from the eigenforce model are found to be very close to ones obtained from electronic structure calculations (less than 0.1 V difference). Finally, the eigenforce model is further used to predict the ideal equi-biaxial strain range required on Pt(111) surfaces for optimum ORR activity.

• Research Organization: Brown Univ., Providence, RI (United States)
• Sponsoring Organization: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F)
• Grant/Contract Number: 89233218CNA000001
• OSTI ID: 1483302
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 4 Vol. 150; ISSN 0021-9606
• Publisher: American Institute of Physics (AIP)Copyright Statement
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
adsorption
alloys
catalyst
density functional theory
energy conversion
free energy landscapes
fuel cells
reaction mechanisms