Metal-support spin orders: Crucial effect on electrocatalytic oxygen reduction.

J Chem Phys

H-PSI Computational Chemistry Lab, Institute of Industrial Catalysis, State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, People's Republic of China.

Published: June 2024

AI Article Synopsis

  • The study examines how the magnetic properties of a ferromagnetic CrBr3 support combined with nickel (Ni) influence the electrocatalytic oxygen reduction reaction (ORR) using advanced theoretical methods.
  • Increased Ni loading alters the magnetic behavior, shifting from ferromagnetic to ferrimagnetic characteristics while enhancing the material's stability and performance in catalytic applications.
  • The relationship between oxygen adsorption properties and magnetic properties is emphasized, revealing that changes in spin-order can affect the catalytic pathways during ORR under varying conditions, showing potential improvements over traditional noble-metal catalysts.

Article 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) CrBr3 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.

Download full-text PDF

Source
http://dx.doi.org/10.1063/5.0207891DOI Listing

Publication Analysis

Top Keywords

electrocatalytic oxygen
8
oxygen reduction
8
design heterogeneous
8
heterogeneous catalysts
8
metal-support spin
4
spin orders
4
orders crucial
4
crucial electrocatalytic
4
magnetic
4
reduction magnetic
4

Similar Publications

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!