Intrinsic spin shielding effect in platinum-rare-earth alloy boosts oxygen reduction activity

Abstract

Oxygen reduction reactions (ORRs) involve a multistep proton-coupled electron process accompanied by the conversion of the apodictic spin configuration. Understanding the role of spin configurations of metals in the adsorption and desorption of oxygen intermediates during ORRs is critical for the design of efficient ORR catalysts. Herein, a platinum-rare-earth-metal-based alloy catalyst, Pt2Gd, is introduced to reveal the role of spin configurations in the catalytic activity of materials. The catalyst exhibits a unique intrinsic spin reconfiguration because of interactions between the Gd-4f and Pt-5d orbitals. The adsorption and desorption of the oxygen species are optimized by modifying the spin symmetry and electronic structures of the material for increased ORR efficiency. The Pt2Gd alloy exhibits a half-wave potential of 0.95 V and a superior mass activity of 1.5 A center dot mgPt-1 in a 0.1 M HClO4 electrolyte, as well as higher durability than conventional Pt/C catalysts. Theoretical calculations have proven that the spin shielding effect of Gd pairs increases the spin symmetry of Pt-5d orbitals and adsorption preferences toward spin-polarized intermediates to facilitate ORR. This work clarifies the impact of modulating the intrinsic spin state of Pt through the interaction with the local high spin 4f orbital electrons in rare-earth metals, with the aim of boosting the spin-related oxygen reduction reaction, thus fundamentally contributing to the understanding of new descriptors that control ORR activity. Deliberately constructing the model for manipulating ORR performance of spin polarized catalysts and accurately decoupling the relationship between the spin state in spin reconfigured alloy and the adsorption strength of the oxide intermediate species.