Enhanced Nitric Oxide Electroreduction to Ammonia via Modulating Spin-Polarization of Fe Single-Atom Catalysts

Jialing Song; Ziqi Wei; Lupeng Han; Zhenlin Wang; Chenghao  Fan; Donglin Han; Chunwei Dong; Haiyan Duan; Xiyang Wang; Sam  Fong Yau Li; Eslam Hamed; Ming Xie; Emiliano Cortes

doi:10.1002/adfm.202523040

Enhanced Nitric Oxide Electroreduction to Ammonia via Modulating Spin-Polarization of Fe Single-Atom Catalysts

Jialing Song, Ziqi Wei, Lupeng Han, Zhenlin Wang, Chenghao Fan, Donglin Han, Chunwei Dong, Haiyan Duan, Xiyang Wang, Sam Fong Yau Li, Eslam Hamed, Ming Xie, Emiliano Cortes

Research output: Contribution to journal › Article › peer-review

Abstract

Electrochemical nitric oxide reduction (NORR) offers a sustainable pathway to ammonia (NH3) while removing toxic NO from industrial emissions. However, high efficiency is hindered by the difficulty of synchronizing multi-proton/electron transfers to accelerate NO hydrogenation and suppress competing hydrogen evolution. Here, an Fe single-atom catalyst (FeSAC) is reported that achieves record NORR activity through spin-state engineering. Using a top-down electrospinning approach, self-supported S,N-doped carbon fiber films hosting Fe-N3S1 sites are fabricated. This catalyst delivers an NH3 yield rate of 140.58 µmol h−1 cm−2 with a Faradaic efficiency of 96.28%, outperforming nearly all reported SACs. Mechanistic analysis reveals that sulfur doping induces a high-spin Fe3+ → low-spin Fe2+ transition, suppressing spin polarization, strengthening NO adsorption, and facilitating proton supply to accelerate hydrogenation. These results establish spin-state modulation as a powerful paradigm for designing next-generation single-atom catalysts for complex multi-proton/electron electrocatalytic transformations, such as the electrosynthesis of ammonia.

Original language	English
Article number	e23040
Journal	Advanced Functional Materials
Early online date	5 Nov 2025
DOIs	https://doi.org/10.1002/adfm.202523040
Publication status	E-pub ahead of print - 5 Nov 2025

Data Availability Statement

The data that support the findings of this study are available from the corresponding author upon reasonable request.

Supporting Information

Funding

This work was financially supported by the National Natural Science Foundation of China (22125604, 22436003, 22406122), the Science & Technology Commission of Shanghai Municipality (23230713700, 24230711600), Shanghai Pujiang Programme (23PJD035), China Postdoctoral Science Foundation (2023M742200), and the Postdoctoral Fellowship Program of CPSF (GZB20240417). The authors acknowledge funding and support from the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany´s Excellence Strategy – EXC 2089/1–390776260, the Bavarian program Solar Technologies Go Hybrid (SolTech), and the Center for NanoScience (CeNS). The authors appreciate Phadcalc (www.phadcalc.com) for the DFT calculations. The authors thank Pengfei Hu from Instrumental Analysis and Research Center of Shanghai University for conducting the AC-HAADF-STEM characterization. The XAFS measurements were performed at BL14W1 of the Shanghai Synchrotron Radiation Facility (SSRF). Open access funding enabled and organized by Projekt DEAL.

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title = "Enhanced Nitric Oxide Electroreduction to Ammonia via Modulating Spin-Polarization of Fe Single-Atom Catalysts",

abstract = "Electrochemical nitric oxide reduction (NORR) offers a sustainable pathway to ammonia (NH3) while removing toxic NO from industrial emissions. However, high efficiency is hindered by the difficulty of synchronizing multi-proton/electron transfers to accelerate NO hydrogenation and suppress competing hydrogen evolution. Here, an Fe single-atom catalyst (FeSAC) is reported that achieves record NORR activity through spin-state engineering. Using a top-down electrospinning approach, self-supported S,N-doped carbon fiber films hosting Fe-N3S1 sites are fabricated. This catalyst delivers an NH3 yield rate of 140.58 µmol h−1 cm−2 with a Faradaic efficiency of 96.28\%, outperforming nearly all reported SACs. Mechanistic analysis reveals that sulfur doping induces a high-spin Fe3+ → low-spin Fe2+ transition, suppressing spin polarization, strengthening NO adsorption, and facilitating proton supply to accelerate hydrogenation. These results establish spin-state modulation as a powerful paradigm for designing next-generation single-atom catalysts for complex multi-proton/electron electrocatalytic transformations, such as the electrosynthesis of ammonia.",

author = "Jialing Song and Ziqi Wei and Lupeng Han and Zhenlin Wang and Chenghao Fan and Donglin Han and Chunwei Dong and Haiyan Duan and Xiyang Wang and \{Fong Yau Li\}, Sam and Eslam Hamed and Ming Xie and Emiliano Cortes",

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AU - Song, Jialing

AU - Wei, Ziqi

AU - Han, Lupeng

AU - Wang, Zhenlin

AU - Fan, Chenghao

AU - Han, Donglin

AU - Dong, Chunwei

AU - Duan, Haiyan

AU - Wang, Xiyang

AU - Fong Yau Li, Sam

AU - Hamed, Eslam

AU - Xie, Ming

AU - Cortes, Emiliano

PY - 2025/11/5

Y1 - 2025/11/5

N2 - Electrochemical nitric oxide reduction (NORR) offers a sustainable pathway to ammonia (NH3) while removing toxic NO from industrial emissions. However, high efficiency is hindered by the difficulty of synchronizing multi-proton/electron transfers to accelerate NO hydrogenation and suppress competing hydrogen evolution. Here, an Fe single-atom catalyst (FeSAC) is reported that achieves record NORR activity through spin-state engineering. Using a top-down electrospinning approach, self-supported S,N-doped carbon fiber films hosting Fe-N3S1 sites are fabricated. This catalyst delivers an NH3 yield rate of 140.58 µmol h−1 cm−2 with a Faradaic efficiency of 96.28%, outperforming nearly all reported SACs. Mechanistic analysis reveals that sulfur doping induces a high-spin Fe3+ → low-spin Fe2+ transition, suppressing spin polarization, strengthening NO adsorption, and facilitating proton supply to accelerate hydrogenation. These results establish spin-state modulation as a powerful paradigm for designing next-generation single-atom catalysts for complex multi-proton/electron electrocatalytic transformations, such as the electrosynthesis of ammonia.

AB - Electrochemical nitric oxide reduction (NORR) offers a sustainable pathway to ammonia (NH3) while removing toxic NO from industrial emissions. However, high efficiency is hindered by the difficulty of synchronizing multi-proton/electron transfers to accelerate NO hydrogenation and suppress competing hydrogen evolution. Here, an Fe single-atom catalyst (FeSAC) is reported that achieves record NORR activity through spin-state engineering. Using a top-down electrospinning approach, self-supported S,N-doped carbon fiber films hosting Fe-N3S1 sites are fabricated. This catalyst delivers an NH3 yield rate of 140.58 µmol h−1 cm−2 with a Faradaic efficiency of 96.28%, outperforming nearly all reported SACs. Mechanistic analysis reveals that sulfur doping induces a high-spin Fe3+ → low-spin Fe2+ transition, suppressing spin polarization, strengthening NO adsorption, and facilitating proton supply to accelerate hydrogenation. These results establish spin-state modulation as a powerful paradigm for designing next-generation single-atom catalysts for complex multi-proton/electron electrocatalytic transformations, such as the electrosynthesis of ammonia.

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DO - 10.1002/adfm.202523040

M3 - Article

SN - 1616-301X

JO - Advanced Functional Materials

JF - Advanced Functional Materials

M1 - e23040

ER -

Enhanced Nitric Oxide Electroreduction to Ammonia via Modulating Spin-Polarization of Fe Single-Atom Catalysts

Abstract

Data Availability Statement

Funding

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