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Layered Antiferromagnetic Ordering in the Most Active Perovskite Catalysts for the Oxygen Evolution Reaction
Author(s) -
Lim Tingbin,
Niemantsverdriet J. W. Hans,
Gracia Jose
Publication year - 2016
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201600611
Subject(s) - antiferromagnetism , oxygen evolution , perovskite (structure) , magnetism , magnetic moment , chemistry , oxygen , electronic structure , spin states , ab initio quantum chemistry methods , ground state , spin (aerodynamics) , chemical physics , condensed matter physics , inorganic chemistry , atomic physics , molecule , computational chemistry , crystallography , physics , electrochemistry , organic chemistry , electrode , thermodynamics
We have performed an in‐depth ab initio study of the magnetic structure within the most active perovskites for the oxygen evolution reaction. In all cases, the ground state exhibits an extended antiferromagnetic coupling in the unit cell. Layered antiparallel alignment of the magnetic moments appears to be related to their electrocatalytic activity. All the perovskites calculated within this paper show space‐separated charge‐transport channels depending on the spin orientation. Comparing the electronic structures with the reported activities, we find a direct correlation between the magnetic accumulation on the spin channels in the bulk material and the catalytic activity. We discuss the possible implications of such observations in terms of magnetic interactions. During oxygen evolution in water electrolysis, reactants and products do not preserve spin. For triplet state oxygen to evolve, the catalyst at the anode can speed up the reaction if it is able to balance the magnetism of the oxygen molecule by extracting electrons with an opposite magnetic moment, conserving the overall spin.