Jahn-Teller Distortions Induced by in situ Li Migration in λ-MnO2 for Boosting Electrocatalytic Nitrogen Fixation.
Angew Chem Int Ed Engl
; 63(8): e202318967, 2024 Feb 19.
Article
em En
| MEDLINE
| ID: mdl-38153676
ABSTRACT
Lithium-mediated electrochemical nitrogen reduction reaction (Li-NRR) completely eschews the competitive hydrogen evolution reaction (HER) occurred in aqueous system, whereas the continuous deposition of lithium readily blocks the active sites and further reduces the reaction kinetics. Herein, we propose an innovative in situ Li migration strategy to realize that Li substitutes Mn sites in λ-MnO2 instead of evolving into the dead Li. Comprehensive characterizations corroborate that the intercalation of Li+ at high voltage breaks the structural integrity of MnO6 octahedron and further triggers unique Jahn-Teller distortions, which promotes the spin state regulation of Mn sites to generate the ameliorative eg orbital configuration and accelerates N≡N bond cleavage via eg -σ and eg -π* interaction. To this end, the resulted cationic disordered LiMnO4 delivers the recorded highest NH3 yield rate of 220â
µg h-1 cm-2 and a Faradaic efficiency (FE) 83.80 % in organic electrolyte.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
/
Angew. Chem. (Int. ed., Internet)
/
Angewandte Chemie (International ed. Internet)
Ano de publicação:
2024
Tipo de documento:
Article
País de publicação:
Alemanha