Main-Group Metal-Nonmetal Dynamic Proton Bridges Enhance Ammonia Electrosynthesis.
Angew Chem Int Ed Engl
; : e202412426, 2024 Aug 13.
Article
en En
| MEDLINE
| ID: mdl-39136320
ABSTRACT
The electrochemical nitrogen reduction reaction is a crucial process for the sustainable production of ammonia for energy and agriculture applications. However, the reaction's efficiency is highly dependent on the activation of the inert N≡N bond, which is hindered by the electron back-donation to the π* orbitals of the N≡N bond, resulting in low eNRR capacity. Herein, we report a main-group metal-non-metal (O-In-S) eNRR catalyst featuring a dynamic proton bridge, with In-S serving as the polarization pair and O functioning as the dynamic electron pool. In-situ spectroscopic analysis and theoretical calculations reveal that the In-S polarization pair acts as asymmetric dual-sites, polarizing the N≡N bond by concurrently back-donating electrons to both the πx* and πy* orbitals of N2, thereby overcoming the significant band gap limitations, while inhibiting the competitive hydrogen evolution reaction. Meanwhile, the O dynamic electron pool acts as a "repository" for electron storage and donation to the In-S polarization pair. As a result, the O-In-S dynamic proton bridge exhibits exceptional NH3 yield rates and Faradaic efficiencies (FEs) across a wide potential window of 0.3 V, with an optimal NH3 yield of 80.07 ± 4.25 µg h-1 mg-1 and an FE of 38.01 ± 2.02%, outperforming most previously reported catalysts.
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Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Año:
2024
Tipo del documento:
Article
País de afiliación:
Singapur
Pais de publicación:
Alemania