Sulfur-Coordinated Iron Overcomes Stability Limitations in Atomically Dispersed Metal-Nitrogen-Carbon Catalysts for CO ₂ Electrolysis
7 affiliations
- 1Department of Chemical Engineering
- 2McMaster University
- 3Department of Mechanical and Industrial Engineering
- 4University of Toronto
- 5Canadian Light Source Inc.
- 6University of Saskatchewan
- 7Department of Chemistry
Abstract
Metal-nitrogen-carbon (M-N x -C) catalysts are a versatile platform for electrochemical CO 2 reduction catalysis, yet the limited durability of Fe-containing active sites at industrially relevant current densities remains an obstacle. Here we report a synthesis strategy that selectively incorporates sulfur into the coordination environment of atomically dispersed iron centers within a dual-metal Fe-S y /Ni-N x -C catalyst, yielding sulfur rich coordinated Fe active sites, represented by a Fe-S 5 model, alongside predominantly Ni-N x coordinated active sites. Beyond modifying the coordination structure, sulfur incorporation is correlated with higher nitrogen retention and suppressed formation of metal-containing clusters during catalyst synthesis, increasing the abundance of atomically dispersed metal active centers. Operando and ex situ spectroscopic analyses reveal that sulfur coordination stabilizes iron active sites during CO 2 electrolysis in a membrane electrode assembly, mitigating degradation processes that have historically limited durability. The catalyst delivers near-unity CO selectivity and an energy efficiency of 44% at a current density of 500 mA cm -2 , surpassing the performance of state-of-the-art CO 2 to CO catalysts. These findings demonstrate how sulfur coordination can stabilize atomically dispersed iron active sites and establishes a more broadly applicable strategy for designing durable catalysts.
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BibTeX
@misc{jalab2026sulfurcoordinated,
title = {{Sulfur-Coordinated Iron Overcomes Stability Limitations in Atomically Dispersed Metal-Nitrogen-Carbon Catalysts for CO ₂ Electrolysis}},
author = {Rem Jalab and Reza Eslami and Siddhant Singh and Navid Noor and Zahra Teimouri and Robert Ngunjiri and Shayan Angizi and Shunquan Tan and Mahtab Masouminia and Kholoud Abousalem and Chenyu Li and Ashkan Irannezhad and Graham King and Adam Hitchcook and Drew Higgins},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010911/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010911/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Sulfur-Coordinated Iron Overcomes Stability Limitations in Atomically Dispersed Metal-Nitrogen-Carbon Catalysts for CO ₂ Electrolysis
AU - Rem Jalab
AU - Reza Eslami
AU - Siddhant Singh
AU - Navid Noor
AU - Zahra Teimouri
AU - Robert Ngunjiri
AU - Shayan Angizi
AU - Shunquan Tan
AU - Mahtab Masouminia
AU - Kholoud Abousalem
AU - Chenyu Li
AU - Ashkan Irannezhad
AU - Graham King
AU - Adam Hitchcook
AU - Drew Higgins
PY - 2026
DA - 2026/10/22
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010911/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010911/v1
AB - Metal-nitrogen-carbon (M-N x -C) catalysts are a versatile platform for electrochemical CO 2 reduction catalysis, yet the limited durability of Fe-containing active sites at industrially relevant current densities remains an obstacle. Here we report a synthesis strategy that selectively incorporates sulfur into the coordination environment of atomically dispersed iron centers within a dual-metal Fe-S y /Ni-N x -C catalyst, yielding sulfur rich coordinated Fe active sites, represented by a Fe-S 5 model, alongside predominantly Ni-N x coordinated active sites. Beyond modifying the coordination structure, sulfur incorporation is correlated with higher nitrogen retention and suppressed formation of metal-containing clusters during catalyst synthesis, increasing the abundance of atomically dispersed metal active centers. Operando and ex situ spectroscopic analyses reveal that sulfur coordination stabilizes iron active sites during CO 2 electrolysis in a membrane electrode assembly, mitigating degradation processes that have historically limited durability. The catalyst delivers near-unity CO selectivity and an energy efficiency of 44% at a current density of 500 mA cm -2 , surpassing the performance of state-of-the-art CO 2 to CO catalysts. These findings demonstrate how sulfur coordination can stabilize atomically dispersed iron active sites and establishes a more broadly applicable strategy for designing durable catalysts.
ER -