Spin-Enhanced O-H Cleavage in Electrochemical Water Oxidation.
Angew Chem Int Ed Engl
; 62(20): e202300469, 2023 May 08.
Article
en En
| MEDLINE
| ID: mdl-36932854
ABSTRACT
Herein we report the vital role of spin polarization in proton-transfer-mediated water oxidation over a magnetized catalyst. During the electrochemical oxygen evolution reaction (OER) over ferrimagnetic Fe3 O4 , the external magnetic field induced a remarkable increase in the OER current, however, this increment achieved in weakly alkaline pH (pHâ
9) was almost 20 times that under strongly alkaline conditions (pHâ
14). The results of the surface modification experiment and H/D kinetic isotope effect investigation confirm that, at weakly alkaline pH, during the nucleophilic attack of FeIV =O by molecular water, the magnetized Fe3 O4 catalyst polarizes the spin states of the nucleophilic attacking intermediates. The spin-enhanced singlet O-H cleavage and triplet O-O bonding occur synergistically, which promotes the O2 generation more significantly than the strongly alkaline case involving only spin-enhanced O-O bonding.
Texto completo:
1
Colección:
01-internacional
Banco de datos:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Año:
2023
Tipo del documento:
Article