1. Metal-support spin orders: Crucial effect on electrocatalytic oxygen reduction.
- Author
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Chen, Yi-jie, Wen, Jun, Luo, Zhi-rui, Sun, Fu-Li, Chen, Wen-xian, and Zhuang, Gui-lin
- Subjects
PHASE transitions ,METALLIC bonds ,HETEROGENEOUS catalysts ,CATALYST supports ,MAGNETIC anisotropy ,OXYGEN reduction - Abstract
Magnetic property (e.g. spin order) of support is of great importance in the rational design of heterogeneous catalysts. Herein, we have taken the Ni-supported ferromagnetic (FM) CrBr
3 support (Nix /CrBr3 ) to thoroughly investigate the effect of spin-order on electrocatalytic oxygen reduction reaction (ORR) via spin-polarized density functional theory calculations. Specifically, Ni loading induces anti-FM coupling in Ni–Cr, leading to a transition from FM-to-ferrimagnetic (FIM) properties, while Ni–Ni metallic bonds create a robust FM direct exchange, benefiting the improvement of the phase transition temperature. Interestingly, with the increase in Ni loading, the easy magnetic axis changes from out-of-plane (2D-Heisenberg) to in-plane (2D-XY). The adsorption properties of Nix /CrBr3 , involving O2 adsorption energy and configuration, are not governed by the d-band center but strongly correlate with magnetic anisotropy. It is noteworthy that the applied potential and electrolyte acidity triggers spin-order transition phenomena during the ORR and induces the catalytic pathway change from 4e− ORR to 2e− ORR with the excellent onset potential of 0.93 V/reversible hydrogen electrode, comparable to the existing most excellent noble-metal catalysts. Generally, these findings offer new avenues to understand and design heterogeneous catalysts with magnetic support. [ABSTRACT FROM AUTHOR]- Published
- 2024
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