@article{Teng2026, 
author = {Wenkai Teng and Hang Xiao and Chaoqun Jia and Wei Liu and Changshuo Liang and Honghui Ou and Yang Li and Guidong Yang},
title = {Engineering asymmetric Co−O−Fe motifs with misaligned electronic environment toward near-unity nitrate-to-ammonia conversion},
year = {2026},
journal = {Nano Research},
keywords = {asymmetric electronic structure, bimetallic motifs, metal-organic framework, *NO regulation, electrocatalytic ammonia synthesis},
url = {https://www.sciopen.com/article/10.26599/NR.2026.94909049},
doi = {10.26599/NR.2026.94909049},
abstract = {Electrocatalytic nitrate reduction (eNO3−RR) is widely recognized as sustainable green ammonia production strategy. However, the complex adsorption–activation–hydrogenation behavior of multiple nitrogen-oxygen intermediates and the intrinsic mismatch in proton-coupled electron transfer kinetics severely hinder the NH3 yield. Herein, a structurally engineered FeCo-MOF electrocatalyst featuring an asymmetric Co−O−Fe center was constructed via competitive coordination. The unique electronic orbital distribution in the Co−O−Fe bimetallic center promotes O-mediated charge transfer from Co to Fe. This charge redistribution induces enhanced electronic localization and asymmetry within the Co−O−Fe unit, thereby facilitating the activation and reduction of nitrogen-oxygen intermediates. Notably, in this asymmetric electronic configuration, the Co site enables efficient electron provisioning and promotes water dissociation to generate active hydrogen (Hads) species, ensuring well-matched proton-coupled electron transfer kinetics and accelerating the rapid conversion of the key *NO intermediate on electron-enriched Fe sites. Theoretical calculations further demonstrate that the asymmetric Co−O−Fe motif significantly lowers the thermodynamic barrier of *NO → *NOH step. The catalyst delivers a NH3 production rate of 0.653 mmol cm−2 h−1 (1306 mmol gcat−1 h−1) with a near-unity Faradaic efficiency of 99.8%. This study provides comprehensive insights into optimizing proton-coupled electron transfer dynamics and elucidating structure-performance relationships for advanced green-ammonia electrocatalysis.}
}