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High performance layer-by-layer Pt₃Ni(Pt-skin)-modified Pd/C for the oxygen reduction reaction.

ABSTRACT: Bimetallic Pt-Ni with Pt on the outermost layer and an innermost layer enriched in Ni, referred to as Pt₃Ni(Pt-skin), is a promising configuration of an electrocatalyst for the oxygen reduction reaction (ORR) in fuel cells. We prepare a core (Pd)/shell (Pt₃Ni(Pt-skin)) catalyst (Pt₃Ni(Pt-skin)/Pd/C) from Zn underpotential deposition (UPD) on a Ni UPD modified Pd/C catalyst, facilitating Pt atomic layer-by-layer growth on the Ni surface through the galvanic replacement process. Pt₃Ni(Pt-skin)/Pd/C shows the best ORR performance, with a Pt specific activity of 16.7 mA cm^-2 and Pt mass activity of 14.2 A mg_Pt^-1, which are 90- and 156- fold improvements over commercial Pt/C catalysts. The Pt₃Ni(Pt-skin) structure effectively inhibits Ni leaching to improve the durability in two accelerated durability test modes mimicking the catalyst lifetime and start-up/shut-down cycles.

SUBMITTER: Huang JF

PROVIDER: S-EPMC6053971 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature

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High performance layer-by-layer Pt3Ni(Pt-skin)-modified Pd/C for the oxygen reduction reaction.

Huang Jing-Fang JF Tseng Po-Kai PK

Chemical science 20180626 28

Bimetallic Pt-Ni with Pt on the outermost layer and an innermost layer enriched in Ni, referred to as Pt3Ni(Pt-skin), is a promising configuration of an electrocatalyst for the oxygen reduction reaction (ORR) in fuel cells. We prepare a core (Pd)/shell (Pt3Ni(Pt-skin)) catalyst (Pt3Ni(Pt-skin)/Pd/C) from Zn underpotential deposition (UPD) on a Ni UPD modified Pd/C catalyst, facilitating Pt atomic layer-by-layer growth on the Ni surface through the galvanic replac ...[more]

PMID: 30090301

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Project description:Recently Debe et al. reported that Pt3Ni7 leads to extraordinary Oxygen Reduction Reaction (ORR) activity. However, several reports show that hardly any Ni remains in the layers of the catalysts close to the surface ("Pt-skin effect"). This paradox that Ni is essential to the high catalytic activity with the peak ORR activity at Pt3Ni7 while little or no Ni remains close to the surface is explained here using large-scale first-principles-based simulations. We make the radical assumption that processing Pt-Ni catalysts under ORR conditions would leach out all Ni accessible to the solvent. To simulate this process we use the ReaxFF reactive force field, starting with random alloy particles ranging from 50% Ni to 90% Ni and containing up to ∼300 000 atoms, deleting the Ni atoms, and equilibrating the resulting structures. We find that the Pt3Ni7 case and a final particle radius around 7.5 nm lead to internal voids in communication with the exterior, doubling the external surface footprint, in fair agreement with experiment. Then we examine the surface character of these nanoporous systems and find that a prominent feature in the surface of the de-alloyed particles is a rhombic structure involving 4 surface atoms which is crystalline-like but under-coordinated. Using density-functional theory, we calculate the energy barriers of ORR steps on Pt nanoporous catalysts, focusing on the Oad-hydration reaction (Oad + H2Oad → OHad + OHad) but including the barriers of O2 dissociation (O2ad → Oad + Oad) and water formation (OHad + Had → H2Oad). We find that the reaction barrier for the Oad-hydration rate-determining-step is reduced significantly on the de-alloyed surface sites compared to Pt(111). Moreover we find that these active sites are prevalent on the surface of particles de-alloyed from a Pt-Ni 30 : 70 initial composition. These simulations explain the peak in surface reactivity at Pt3Ni7, and provide a rational guide to use for further optimization of improved catalytic and nanoporous materials.

Dataset Information

High performance layer-by-layer Pt₃Ni(Pt-skin)-modified Pd/C for the oxygen reduction reaction.

Publications

High performance layer-by-layer Pt<sub>3</sub>Ni(Pt-skin)-modified Pd/C for the oxygen reduction reaction.

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